Bull Volcanol (2012) 74:559–577
DOI 10.1007/s00445-011-0543-3
RESEARCH ARTICLE
Spherulites and thundereggs from pitchstones of the Deccan
Traps: geology, petrochemistry, and emplacement
environments
Pooja V. Kshirsagar & Hetu C. Sheth &
Sheila J. Seaman & Badrealam Shaikh &
Poonam Mohite & Trupti Gurav & D. Chandrasekharam
Received: 4 January 2011 / Accepted: 22 August 2011 / Published online: 20 October 2011
# Springer-Verlag 2011
Abstract Spherulites and thundereggs are rounded, typically
spherical, polycrystalline objects found in glassy silicic rocks.
Spherulites are dominantly made up of radiating microscopic
fibers of alkali feldspar and a silica mineral (commonly
quartz). They form due to heterogeneous nucleation in highly
supercooled rhyolitic melts or by devitrification of glass.
Associated features are lithophysae (“stone bubbles”), which
have an exterior (sometimes concentric shells) of fine quartz
and feldspar, and internal cavities left by escaping gas; when
filled by secondary silica, these are termed thundereggs. Here,
we describe four distinct occurrences of spherulites and
thundereggs, in pitchstones (mostly rhyolitic, some trachytic)
of the Deccan Traps, India. The thundereggs at one locality
were previously misidentified as rhyolitic lava bombs and
products of pyroclastic extrusive activity. We have character-
ized the thundereggs petrographically and geochemically and
have determined low contents of magmatic water (0.21–
0.38 wt.%) in them using Fourier transform infrared spectros-
copy. We consider that the spherulite-bearing outcrops at one
of the localities are of lava flows, but the other three represent
subvolcanic intrusions. Based on the structural disposition of
the Deccan sheet intrusions studied here and considerations of
Editorial responsibility: D.B. Dingwell
P. V. Kshirsagar : H. C. Sheth (*) : B. Shaikh : P. Mohite :
T. Gurav : D. Chandrasekharam
Department of Earth Sciences,
Indian Institute of Technology Bombay (IITB),
Powai, Mumbai 400076, India
e-mail: hcsheth@iitb.ac.in
S. J. Seaman
Department of Geosciences, University of Massachusetts,
Amherst, MA 01003, USA
regional geology, we suggest that they are cone sheets
emplaced from a plutonic center now submerged beneath the
Arabian Sea.
Keywords Spherulites . Lithophysae . Thundereggs .
Rhyolite . Pitchstone . Deccan Traps . Volcanism
Introduction
Spherulites are polycrystalline growths, typically rounded
or spherical, found in rhyolitic glass (obsidians, pitchstones,
and vitrophyres). Rapid cooling of rhyolitic melt produces
volcanic glass, and further slow cooling may allow
nucleation and growth of crystals (devitrification) in the
hot glass, producing spherulites and related features like
lithophysae (Keith and Padden 1963; Lofgren 1971; Davis
and McPhie 1996). Spherulites are composed of anhydrous
minerals, usually needles or fibers of alkali feldspar a few
microns wide that radiate from the center, along with a
silica polymorph (often quartz). Spherulites probably begin
to form by heterogeneous nucleation on submicroscopic
seed crystals, bubbles, or fractures, in a highly supercooled
(>150–200°C) and highly viscous melt (Swanson et al.
1989; Granasy et al. 2005; Castro et al. 2008; Watkins et al.
2009). Spherulites can also form by devitrification of silicic
glass, as glass is unstable and over time devitrifies and
converts to an assemblage of quartz, feldspar, clays, zeolites,
sericite, and chlorite, as a result of metamorphism, hydro-
thermal activity, or hydration by meteoric waters (Marshall
1961; Lipman 1965; Lofgren 1970, 1971; Friedman and
Long 1984).
Lithophysae (“stone bubbles”), often spatially associated
with spherulites (e.g., Tuffen and Castro 2009), are
560
subspherical masses in rhyolitic lava flows and compacted
tuffs, generally a few centimeters in diameter and com-
posed of concentric onion-like shells of fine-grained quartz
and alkali feldspar separated by empty spaces (Tyrrell
1926). Their origin may involve rhythmic exsolution and
expansion of volatiles during crystallization, and vapor-phase
precipitates including quartz commonly occur in them (Best
2002). Lithophysae are often filled with secondary silica
(quartz or chalcedony), in which case they are known as
thundereggs, geodes, and agates (Shaub 1979). Thus,
thundereggs are rounded or spherical objects in glassy
silicic rocks that lack the radial structure of spherulites and
are solid rather than hollow, usually containing secondary
silica in their cores and fractures.
Spherulites, lithophysae, and thundereggs commonly
range in size from microscopic to a few centimeters, but
much larger examples (~1 m) are known (e.g., Smith et al.
2001). They occur in obsidian domes, large-volume
vitrophyric ash-flow tuffs, and in shallow volcanic con-
duits, as well as lava flows, and have been the subject of
considerable curiosity since their earliest reports (e.g.,
Cross 1891). Here, we present the first study of spherulites
and thundereggs from pitchstones of the Deccan Traps,
India. We present field observations, petrographic and
geochemical (major and trace element) data on the
spherulites, thundereggs, and their host rocks, and data on
their magmatic water concentrations. Based on these data-
sets, we discuss the emplacement paleoenvironments of
these rock suites.
By pitchstone, we mean silicic volcanic glass which
contains much more H2O (up to 6%) and crystalline material
than obsidian (<1% H2O) and which therefore has a waxy or
resinous luster unlike the vitreous luster (and characteristic
conchoidal fracture) of obsidian (Hatch et al. 1983).
Silicic magmatism in the Deccan Traps
Most continental flood basalt provinces contain at least
some silicic (rhyolite-dacite-trachyte) igneous rocks, and
these are variably interpreted as derived by crystal
fractionation of mafic magmas, partial melting of under-
plated mafic rocks or the deeper parts of the flood basalt
pile, combined assimilation and fractionation processes,
or anatexis of older basement crust (e.g., Lightfoot et al.
1987; Sheth and Melluso 2008; Sheth et al. 2011a). Silicic
rocks (rhyolite, granophyre, and trachyte) are abundant in
the western and northwestern parts of the Deccan province,
particularly the Saurashtra peninsula and the Mumbai area,
on the western Indian rifted margin (Fig. 1). Both these
regions possess special features that make them very
different from the main Deccan province in west-central
India, which is characterized over vast areas by flat-lying
Bull Volcanol (2012) 74:559–577
flood tholeiites. The special features of Saurashtra include
several volcanoplutonic complexes, and a great composi-
tional diversity overall, from rhyolites and granophyres to
picrites, gabbros, and lamprophyres (e.g., Melluso et al.
1995; Sheth et al. 2011a, b). Linear dike swarms of varied
composition cross Saurashtra and also form radial and
arcuate patterns around the central complexes such as the
silicic Barda and Alech complexes (Auden 1949; Misra
1999). Rhyolites outcrop in the entire coastal belt from
Rajula to Shihor and Chogat (Fig. 1; Chatterjee and
Bhattacharji 2001).
The Mumbai area is similarly notable for its voluminous
subaqueous volcanic deposits (pillow basalts and spilites,
hyaloclastites, tuffs, and inter-flow volcanosedimentary
beds), as well as its silicic (rhyolite and trachyte) lava
flows and subvolcanic intrusions (Lightfoot et al. 1987;
Zellmer et al. 2011).
Rhyolite and trachyte flows and plugs are also known in
the Deccan Traps from other areas than Saurashtra and
Mumbai, namely the Pavagadh, Rajpipla, and Chhota Udaipur
areas (Fig. 1) in the western and northwestern parts of the
province (e.g., Mahoney et al. 1985; Sheth and Melluso
2008). Neither spherulites nor thundereggs have been
reported from any of the Deccan silicic rock suites so far.
Field geology of the Deccan spherulites and thundereggs
Spherulites from Osham Hill, western Saurashtra
The Osham Hill (Fig. 1) in western Saurashtra, northwest of
Mount Girnar, shows a flow sequence of rhyolite, pitch-
stone, and basaltic andesite (Sheth et al. 2011b). The
summit rhyolite flow is very fine-grained and contains
patches of devitrified glass besides quartz and alkali
feldspars. Flows of massive (non-banded) and banded
pitchstone underlie the rhyolite. The pitchstones and
rhyolite contain many tiny scattered spherulites 0.5 mm to
a few mm in size, with a few reaching 1 cm, and the
spherulites are noticeable even in hand specimens of the
pitchstones due to their whitish color against a shiny black
background (Fig. 2a).
Spherulites from Kagvadar, southern Saurashtra
At Kagvadar village near Rajula (Fig. 1), a ridge of fresh
pitchstone has been reported by Misra (1999). The pitch-
stone is dark gray with a waxy to resinous luster. The
pitchstone ridge shows very numerous small (3–4 mm
diameter) spherulites in outcrop (Fig. 2b, c). The spherulites
occur along distinct quasi-horizontal layers in the host
pitchstone and are much more abundant than those in the
Osham pitchstone.
Bull Volcanol (2012) 74:559–577 561

Fig. 1 Geological maps of Sau-

rashtra and the Deccan Traps of
India (inset, shaded region), with Pavagadh
important central complexes, Saura- Chhota Udaipur
dike swarms (black lines, sche- shtra Rajpipla
matically shown), and localities
including those mentioned in the DECCAN
text marked (after Misra 1999; Mumbai TRAPS 23o
Sheth et al. 2011a, b) 200 km
Arabian
India
Sea

chh
fK ach Jamnagar Khambhat
Gulf o Dhandhuka
(Cambay)
Rajkot
S
A
U 22o
R
A

Gulf of Cambay
Barda Alech S Chogat-Chamardi Hills
Hills Hills H
T
Osham R
A
Hill Amreli Shihor
Porbandar
Palitana
Junagadh Mount Girnar Talaja
Arabian Sea
Bhaguda
Dedan Longdi
Tertiary & Mahuva Surat
Quaternary Barman Mota Rajula
21o
Deccan Traps Una Kagvadar postulated
submerged
Mesozoic Diu plutonic focus
50 km
70o 71o 72o

Thundereggs from Bhaguda-Longdi, southeastern
Saurashtra
The villages of Bhaguda and Longdi are spaced 5 km apart
and are located close to the southeastern Saurashtra coast
(Fig. 1). At Bhaguda-Longdi, rhyolite and pitchstone form
low hills and ridges (Fig. 2d) and contain abundant thunder-
eggs. Whereas many thundereggs are seen contained within
the pitchstone, others have been removed by weathering and
lie buried in the soil (Fig. 2e), either complete or broken
along fractures. We randomly collected 82 thundereggs from
the area between the two villages and measured their sizes,
which are from <1 to 10 cm. A representative subset is
shown in Fig. 2f. Besides the common single thundereggs,
there are twins, triplets, and even quadruplets (Fig. 2g). We
call them thundereggs because of the absence of a radial
structure in slices cut through their centers and the presence
of secondary silica in the cores and fractures of most of
them (Fig. 2h).
The size distribution of 37 intact (unbroken) single
thundereggs (Fig. 3a) shows a mode at 3–4 cm (average
diameter). The mode remains unchanged if we include the
broken thundereggs as well, i.e., all 82 single thundereggs
(Fig. 3b). Large (~10 cm) thundereggs are few. The
thundereggs irrespective of size are also nearly spherical
in shape, as shown by the plot of maximum diameter vs.
minimum diameter (measured perpendicular to the former)
for the unbroken thundereggs (37 individuals, Fig. 3c).
Misra (1999) reported sizes from well under 1 cm to as
much as 15 cm for the Bhaguda-Longdi thundereggs but
interpreted them as “rhyolitic lava bombs” produced by
pyroclastic volcanism. We discuss below why this inter-
pretation is untenable.
Thundereggs from Borivli, Mumbai
This occurrence is in a previously unreported pitchstone
from the Borivli area of Mumbai. The pitchstone
outcrops below the Gandhi Smriti Memorial within the
Sanjay Gandhi National Park. The pitchstone occupies an
area of a few hundred square meters and is cut
throughout by a three-dimensional network of fractures
(Fig. 4a). The fractures are filled up by fine-grained,
weathered-looking material which is more resistant to
erosion than the host pitchstone so that the fracture fills
stand a little higher than the polygonal areas they enclose.
We believe that these planar to subplanar fractures are
cooling joints.
The polygonal areas of the host pitchstone show other
linear parallel cracks and contain a few thundereggs
562 Bull Volcanol (2012) 74:559–577

Fig. 2 a Spherulites in the

Osham Hill pitchstone (sample
OSH2). Scale is in centimeters.
b, c Outcrop photographs of the
Kagvadar pitchstone ridge with
spherulites. d The Bhaguda
rhyolite-pitchstone hill. e Sever-
al of the smaller Bhaguda hill
thundereggs in outcrop. Coin for
scale is 2 cm in diameter. f A
subset of the Bhaguda-Longdi
thundereggs chosen to depict the
size range. Hammer for scale. g
Bhaguda-Longdi thundereggs
forming two twins, a triplet, and
a quadruplet. h Hand specimens
of Bhaguda-Longdi thundereggs
sliced through their centers and
polished to enhance the contrast
between the host glass and the
central voids (star-shaped and
filled by banded agate). The
triaxial star shape of the agate
filling in the larger thunderegg is
indicated by the black lines.
Scale in (g, h) is in centimeters

(Fig. 4a, b). The pitchstone under the surface weathering
rind is fresh and shiny black, with many small (millimeter
size) feldspar phenocrysts with locally developed trachytic
(flow) texture noticeable even in hand specimen. The
Borivli thundereggs are much more sparse and much less
fractured compared to the Bhaguda-Longdi ones, though
they show the same types of intergrown twins, triplets, and
quadruplets (Fig. 4c, d).
The maximum and minimum (perpendicular to the
former) dimensions of 75 Borivli thundereggs were
Bull Volcanol (2012) 74:559–577 563

Fig. 3 a, b Size distributions of

37 unbroken, and 82 broken and
unbroken, thundereggs from
Bhaguda-Longdi. c Plot of min-
imum vs. maximum diameter
for 37 unbroken thundereggs
from Bhaguda-Longdi. Also
shown is a reference line for
the ratio of both diameters
equal to 1

measured in outcrop. As for the Bhaguda-Longdi thunder- as shown by the plot of maximum diameter vs. minimum
eggs, the size distribution for the Borivli thundereggs diameter (measured perpendicular to the former) for the 75
shows a mode at 3–4 cm average diameter (Fig. 5a), and specimens (Fig. 5b). Thundereggs ~10 cm in diameter are
irrespective of size, they are also nearly spherical in shape, rare.
564
Fig. 4 a–d Field photos of
Borivli thundereggs (marked th)
and host pitchstone. Pen for scale
in (b) is 15 cm long, and coin in
(c, d) is 2 cm wide. Note the
coalesced thundereggs in (c, d)
Petrography
We carried out petrographic studies of the spherulites and
thundereggs collected in this study with the aim of identifying
the mineral phases present in them besides glass and
deciphering their textural features and microstructures, if any.
Spherulites in the banded pitchstone from Osham Hill
(sample OSH2) are shown in Fig. 6a. These have a distinct
radial structure and show the characteristic extinction cross
between crossed polars. The Osham pitchstones also contain
perlitic cracks which we ascribe to secondary hydration (e.g.,
Ross and Smith 1955). Additional photomicrographs and
field and geochemical data on the Osham Hill lava sequence
can be found in Sheth et al. (2011b). The Kagvadar
spherulites also display a distinct radial structure in thin
section (Fig. 6b) defined by K-feldspar and quartz crystals.
In thin section, the Bhaguda pitchstone (sample SS8)
shows phenocrysts of alkali feldspar, amphibole, quartz,
and Fe-rich olivine in a glassy groundmass which shows
millimeter-scale flow layering, but notably no perlitic
fractures (Fig. 6d, e). Many pitchstones with quartz and
fayalitic olivine are known (e.g., Tyrrell 1926; Harris and
Brindley 1954; Hatch et al. 1983). The rhyolite sampled at
the summit of the Bhaguda hill (SS6) shows quartz and
both alkali and plagioclase feldspars. The feldspars are
highly altered and show sieve and embayed morphology.
These minerals form phenocrysts embedded in a fine,
microlitic, hypocrystalline groundmass of fine quartz and
feldspar. No radial or any other arrangement of mineral
Bull Volcanol (2012) 74:559–577
grains is recognizable in the Bhaguda-Longdi thundereggs
with the naked eye or the microscope (Fig. 6d–f).
The Borivli pitchstone (sample GS1) shows phenocrysts
of quartz, fayalitic olivine, plagioclase, and alkali feldspar,
sometimes forming glomeroporphyritic clots against a
groundmass containing glass but also abundant feldspar
microlites that define a trachytic texture (Fig. 6g, h). The
thundereggs contained in this pitchstone contain the same
mineral assemblage and no internal structure.
Minerals present in samples SS9-48 (Bhaguda thunder-
egg) and GS2 (Borivli thunderegg) have been identified
using the X-ray diffraction technique (Rigaku D-max IC;
Cu target with scan speed of 1o/min) together with search–
match software at IIT Bombay. The XRD spectra are shown
in Fig. 7a, b. Quartz and sanidine are the two prominent
phases present in both of the samples whereas a small
amount of albite was detected in sample GS2. The results
are consistent with the petrographic identifications.
Geochemistry
We carried out geochemical analyses of the Bhaguda-
Longdi and Borivli thundereggs, their host pitchstones, and
associated rocks of southern Saurashtra, aiming to deter-
mine their bulk rock compositions and nomenclature. Major
and trace element concentrations and loss on ignition (LOI)
values were determined at the Department of Earth
Sciences, IIT Bombay. To obtain these, ultrasonically
Bull Volcanol (2012) 74:559–577
Fig. 5 a Size distributions of 75
measured thundereggs from
Borivli. b Plot of minimum vs.
maximum diameter for these 75
thundereggs. It should be noted
that unlike the size data on the
Bhaguda-Longdi thundereggs
(Fig. 3), the sizes of the Borivli
thundereggs shown in Fig. 5 are
apparent sizes only, because
most of these would be difficult
to separate from the host pitch-
stone without breaking them
cleaned chips of the samples, free of secondary minerals,
were first ground to powders of <75 μm grain size using a
Retsch PM-100 planetary ball mill and stainless steel
grinding balls. Then, 0.25 g of sample powders were mixed
with 0.75 g lithium metaborate (LiBO2) and 0.50 g of
lithium tetraborate (LiB4O7) in platinum crucibles and
fused in a muffle furnace at 1050°C for 10 min. After
cooling, the crucibles were carefully immersed in 80 ml of
1 N HCl in 150-ml glass beakers and then magnetically
stirred for 1 h until the fusion beads had dissolved
completely. Sample volume was made up to 100 ml in
volumetric flasks. For major elements, 10 ml of this mother
solution diluted ten times with distilled water, and for trace
elements, the mother solution itself, were analyzed by
inductively coupled plasma atomic emission spectrometry
(instrument: Jobin Yvon Ultima-2). Several USGS rock
standards including AGV-2 and GSP-2 were dissolved
along with the samples and used for calibrating the
instrument, and the standard QLO-1 was analyzed along
565
with the samples to estimate the analytical accuracy. LOI
values were determined by heating rock powders at 1000°
C, after overnight drying in an oven at 110°C to drive away
adsorbed moisture (H2O−). The Bhaguda-Longdi thunder-
eggs have LOI values from 1.50% to 4.53%, and the
associated rocks have LOI values in this range, whereas the
Borivli thunderegg sample GS2 has a value of 3.73%, its
host rock (GS1) containing as much as 6.29%. Table 1
presents the major and trace element data and LOI values
for the samples along with brief descriptions of the samples
and sample localities.
Table 1 also presents the CIPW norms for the samples
computed using the SINCLAS Program (Verma et al.
2002) which recalculates the major oxide data on a LOI-
free basis and divides total iron into Fe+2 and Fe+3
varieties (following, for example, Middlemost 1989),
computes parameters such as Mg Number, and also
provides a rock name consistent with the IUGS Sub-
commission on the Systematics of Igneous Rocks (Le Bas
566 Bull Volcanol (2012) 74:559–577

Fig. 6 a Photomicrograph of
Osham Hill banded pitchstone
(sample OSH3). Note spherulites
(sp), perlitic cracks (pc), and
flow layers. b, c Photomicro-
graphs of the Kagvadar spheru-
lites in pitchstone sample SS4. kf
potassium feldspar, qz quartz. c
Three spherulites or parts thereof.
d–f Photomicrographs of
Bhaguda-Longdi thundereggs
(samples SS8 and SS9-77),
showing phenocryst minerals (kf
potassium feldspar, amp amphi-
bole, ol olivine, qz quartz) as
well as glass containing many
microlites and flow layers. Note
the characteristic fractures and
alteration in the (presumably
fayalitic) olivine. g, h Photomi-
crographs of Borivli pitchstone
(sample GS1), showing pheno-
cryst minerals (kf potassium
feldspar, pl plagioclase, ol oliv-
ine, ox Fe–Ti oxide) and glass
(gl). Note microlite-rich glassy
groundmass with a trachytic tex-
ture in (g). Photomicrographs (d,
e, h) were taken over the polar-
izer, and the rest between crossed
polars

et al. 1986). As determined by the program, southern
Saurashtra samples SS1 (Barman Mota ridge) and SS2
(Khalsa Kanthariya ridge) are dacites, and all other
Saurashtra samples of this study, including all thundereggs
and host rocks, are rhyolites. The Borivli pitchstone
sample GS1 is a trachyte, and the thunderegg sample
GS2 a trachydacite.
As seen in the total alkali-silica diagram of Le Bas et al.
(1986) (Fig. 8), almost all samples of this study are
subalkalic in character. Also plotted for comparison are data
for rock suites from various areas of the Deccan (Saurashtra,
Mumbai, Rajpipla, Pavagadh, Chogat-Chamardi, and
Osham) that contain silicic rocks (rhyolites, microgranites,
granophyres, dacites, and trachytes). Figure 9 shows a
Bull Volcanol (2012) 74:559–577
Fig. 7 a, b X-ray diffraction
spectra for the Bhaguda-Longdi (a)
and Mumbai thundereggs,
showing the identified minerals
(b)
comparison of the rocks of this study to the other Deccan
silicic rocks in Zr content and the Ba/Y ratio. Whereas
several of the suites, such as the Mumbai trachytes, show
considerable variation in the Zr content and Ba/Y ratio, the
Mumbai rhyolite data form a very distinct cluster with very
high Zr contents of >1,500 ppm, and the Osham rhyolites
also do so, at lower Zr contents. Data for the southern
Saurashtra dacites and rhyolites of this study, as well as the
Borivli trachytes, plot in the same general region as do the
other Deccan silicic suites.
Differences in trace element contents between spherulites
and enclosing vitrophyres have been interpreted as variably
involving expulsion of water from the crystallizing quartz and
alkali feldspar, a late-stage hydrothermal fluid phase, as well
as groundwater interaction, such that the hygromagmatophile
incompatible elements like Rb, Ba, and Sr are depleted in the
spherulites and enriched in the host rock (Smith et al. 2001).
Studies of this kind on thundereggs do not exist, but we note
that there is no systematic pattern of variation of incompat-
ible elements between the Deccan thundereggs (analyzed
free of their silica fillings) and their host rocks (Fig. 10).
Determination of magmatic water contents
Water is an extremely important volatile constituent of
magmas, with major effects on melt structure, viscosity, and
liquidus temperature, as well as elemental diffusion.
Rhyolitic and dacitic magmas can contain 4–6% dissolved
567
H2O under pressure (e.g., Newman et al. 1986; Dunbar et
al. 1989; Hervig et al. 1989; Lowenstern and Mahood
1991). Such water-rich ascending rhyolite magmas would
begin to vesiculate at depths of 3 km (Seaman et al. 2009).
The spherulite- and thunderegg-bearing pitchstones of this
study are almost completely free of vesicles. Determination
of dissolved (magmatic) water in these pitchstones should
therefore help in understanding their emplacement depths
and environments, as well as degassing history.
Secondary hydration of the pitchstones by the percola-
tion and diffusion of meteoric water can significantly raise
their total water contents. Perlitic cracks in silicic glassy
rocks are generally ascribed to hydration (Ross and Smith
1955; Best 2002), though Marshall (1961) argued that
perlitic cracks reflect strain due to rapid cooling and
provide the pathways for the subsequent hydration of the
glass. According to Davis and McPhie (1996), the
formation of classical perlite depends on both rapid cooling
and exposure to external water. In particular, the textural
consequences of glass hydration depend in part on the rate
of cooling and the temperature at which hydration begins
(Keller and Pickett 1954; Drysdale 1979). Rapidly cooled
glass subject to hydration at low temperature undergoes
structural re-arrangement that results in contraction and
perlitic fracturing (Drysdale 1979; Davis and McPhie 1996;
Denton et al. 2009). On the other hand, hydration that
begins at relatively high temperature in relatively slowly
cooling glass, such as in intrusions, results in a structure
that can accommodate later low-temperature hydration
Table 1 Major and trace element data and CIPW norms (in italics) for the spherulite- and thunderegg-bearing pitchstones and rhyolites and other associated silicic rocks, southern Saurashtra and
568

Borivli (Mumbai) areas, Deccan Traps

Rock type Dacite Dacite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Rhyolite Trachyte Trachydacite Std. Ref. Std. Meas.
Sample SS-1 SS-2 SS-3 SS-4 SS-5 SS-6 SS-7 SS-8 SS-9-29 SS-9-48 SS-9-77 SS-10 SS-11 GS-1 GS-2 QLO-1 QLO-1

wt.%
SiO2 67.22 67.02 70.07 74.10 72.53 72.47 74.72 69.00 72.92 70.95 70.28 72.13 70.14 63.78 64.33 65.6 65.36
TiO2 0.75 0.78 0.29 0.26 0.19 0.51 0.42 0.51 0.43 0.49 0.50 0.48 0.65 0.57 0.59 0.62 0.61
Al2O3 13.80 13.75 11.76 11.19 13.62 12.05 10.24 12.27 11.04 12.18 11.95 11.43 13.36 13.21 13.54 16.2 16.31
Fe2O3T 7.28 7.13 3.77 2.76 2.52 3.51 3.34 4.68 5.12 3.54 4.02 4.59 5.03 5.23 5.38 4.35 4.32
MnO 0.10 0.10 0.07 0.01 0.01 0.04 0.01 0.06 0.03 0.01 0.02 0.02 0.06 0.14 0.09 – 0.09
MgO 0.95 0.75 0.10 0.26 0.17 0.21 0.46 0.32 0.10 0.19 0.16 0.13 0.84 0.40 0.34 1.00 1.00
CaO 2.74 2.69 1.21 0.16 0.53 0.89 0.73 1.54 1.07 0.66 0.66 0.25 1.96 1.72 1.36 3.17 3.24
Na2O 3.20 3.28 3.98 2.47 3.49 2.36 0.32 2.85 2.42 1.65 1.66 1.39 2.35 4.91 2.53 4.20 4.28
K2 O 4.17 4.31 3.86 5.31 5.16 5.44 6.15 4.41 4.86 5.40 5.28 7.48 4.93 3.63 7.20 3.60 3.70
P2O5 0.09 0.15 0.01 0.01 0.01 0.10 0.10 0.13 0.04 0.08 0.06 0.09 0.15 0.09 0.09 0.25 0.26
LOI 1.72 1.88 4.49 1.88 2.09 2.05 3.74 4.59 1.50 3.81 4.53 1.61 2.56 6.29 3.73
Total 102.02 101.84 99.61 98.41 100.32 99.63 100.23 100.36 99.53 98.96 99.12 99.60 102.03 99.97 99.18 98.99 99.17
Mg# 26.0 22.1 7.05 21.3 16.2 14.7 28.3 16.4 5.29 13.3 10.3 7.52 32.4 18.0 15.4
wt.%
Q 23.28 22.88 30.30 39.22 30.84 35.88 48.12 32.05 37.04 40.20 39.95 34.24 31.26 17.69 18.39
Or 24.70 25.61 24.05 32.57 31.10 33.03 37.76 27.30 29.41 33.63 33.08 45.26 29.39 22.99 44.75
Ab 27.14 27.91 35.50 21.70 30.11 20.51 2.81 25.27 20.97 14.71 14.89 12.04 20.06 44.52 22.52
An 11.00 10.12 2.97 0.76 2.61 3.86 3.08 7.11 5.02 2.90 3.05 0.67 8.82 3.52 4.55
C – – – 1.15 1.38 0.93 2.05 0.33 – 2.75 2.60 0.83 0.96 – –
Di 1.74 1.98 2.90 – – – – – 0.13 – – – – 4.32 1.67
Hy 7.70 6.89 1.88 2.77 2.40 2.93 3.55 4.40 4.15 2.96 3.35 3.71 5.62 3.06 4.17
Mt 2.80 2.75 1.79 1.29 1.16 1.62 1.56 2.20 2.36 1.68 1.92 2.11 2.28 2.52 2.55
Il 1.43 1.49 0.58 0.51 0.37 0.99 0.83 1.01 0.84 0.98 1.01 0.93 1.25 1.16 1.18
Ap 0.21 0.35 0.02 0.02 0.02 0.24 0.24 0.31 0.09 0.19 0.15 0.21 0.35 0.22 0.22
ppm
Ni 19.2 19.6 20. 6 22.4 21.1 21.9 22.3 21.0 21.9 21.9 21.5 21.9 20.3 19.4 19.7 – 19.0
Sr 115 123 125 81.2 38.5 55.5 41.0 67.7 56.5 71.7 60.2 57.8 75.2 116 112 340 342
Y 57.7 58.6 138 120 92.0 56.3 47.4 57.6 56.4 70.4 50.7 54.2 50.8 83.5 67.4 24 23.4
Zr 389 379 825 707 512 399 342 409 355 377 381 375 350 583 590 185 178
Nb 25.2 27.7 60.8 58.2 41.2 27.1 22.1 22.7 24.1 31.1 27.8 21.7 24.9 119 132 10 8.82
Ba 672 704 1327 1463 1066 711 288 643 609 627 850 752 685 1411 1626 1370 1444

Mg#=[atomic Mg/(Mg+Fe2+ )]×100, where Fe2+ and Fe3+ are computed using the Middlemost (1989) criteria, as well as CIPW norms and rock type names, using the SINCLAS program
SS1 brown porphyritic rhyolite ridge, Barman Mota, east of Raydi dam; SS2 brown porphyritic rhyolite north of Khalsa Kanthariya, near Barman Mota; SS3 and SS4 Pitchstone and spherulitic
pitchstone, Kagvadar; SS5 flow-banded rhyolite near Rajula-Mahuva Highway; SS6 red rhyolite, Bhaguda hill summit; SS7 green rhyolite, Bhaguda hill; SS8 pitchstone, Bhaguda; SS9-29,48,77
thundereggs, Bhaguda; SS10 dark red rhyolite dyke, Longdi; SS-11 porphyritic gray rhyolite, Rajula quarry; GS1 Pitchstone, Gandhi Smriti Udyan, Sanjay Gandhi National Park, Borivli; GS2
Bull Volcanol (2012) 74:559–577

thunderegg in Borivli pitchstone; Ref. recommended values (Smith 1998); Meas. measured values on USGS standard QLO-1 (Quartz Latite Oregon)
Bull Volcanol (2012) 74:559–577
Fig. 8 Data for the Deccan spherulites, host pitchstones, as well as
associated silicic rocks from the Bhaguda-Longdi, Kagvadar, and
Borivli areas plotted on the total alkali-silica (TAS) diagram (Le Bas
et al. 1986). Also shown for comparison are the known silicic-rock-
bearing suites from the Deccan Traps. CB01 Chatterjee and
Bhattacharji (2001), L87 Lightfoot et al. (1987), M85 Mahoney et
without contraction, preventing the formation of perlite
(Drysdale 1979; Davis and McPhie 1996). Therefore, the
absence of perlitic fractures is not evidence for the absence
of secondary hydration. The high LOI values measured on
several thundereggs and their host pitchstones in this study
(Table 1) are arguably due to secondary hydration:
examples are sample SS3, the Kagvadar rhyolitic pitchstone
without spherulites (LOI=4.49%), sample SS8, the Bha-
guda rhyolitic pitchstone (LOI=4.59%), and GS1, the
Borivli trachytic pitchstone (LOI=6.29%).
We therefore determined magmatic water contents in
several pitchstone samples of our study using Fourier
transform infrared (FTIR) spectroscopy.
Fig. 9 Binary plot of Ba/Y vs.
Zr for the Deccan thundereggs,
host pitchstones, and associated
silicic rocks, with published data
for various Deccan silicic rocks
(rhyolites, dacites, trachytes, and
granophyres). Data sources are
as in Fig. 8, with data for four
Mumbai trachytes added (Z11
Zellmer et al. 2011)
569
al. (1985), SM08 Sheth and Melluso (2008), S11a Sheth et al. (2011a),
S11b Sheth et al. (2011b), M96 Maithani et al. (1996), and M95
Melluso et al. (1995). Boundary lines between the subalkalic and
alkalic fields proposed by Macdonald and Katsura (1964, short heavy
line) and Irvine and Baragar (1971, curved dashed line) are also
shown
FTIR spectroscopic analyses of water concentrations
Instrumentation and sample preparation
Identification of water in glass was performed using FTIR
spectroscopy. Spectra were collected in the Department of
Geosciences at the University of Massachusetts using a
Bruker Vertex 70 spectrometer with a Hyperion 3000
microscope. The instrument has a KBr beamsplitter and a
MCT-B detector. It is equipped with a 64×64 focal plane
array detector that was used for rapidly imaging water
concentrations in the samples to evaluate the homogeneity
of distribution of water in the glasses. Each detector of the
570 Bull Volcanol (2012) 74:559–577

Fig. 10 a Nb vs. Ba and b Nb 140

vs. Zr plots comparing data for
the Bhaguda-Longdi thunder- Bhaguda-Longdi host rocks
120 GS2
eggs and host pitchstone and Bhaguda-Longdi thundereggs
rhyolites (SS samples), and the GS1
Borivli host pitchstone
Borivli thunderegg and host 100
Borivli thunderegg
pitchstone (GS samples)

Nb (ppm)
80

60
SS9-48
40 SS6
SS7 SS9-77
20
SS9-29 SS8 SS10

0
0 200 400 600 800 1000 1200 1400 1600 1800
Ba (ppm)
140
GS2
Bhaguda-Longdi host rocks
120 Bhaguda-Longdi thundereggs
Borivli host pitchstone GS1
100 Borivli thunderegg
Nb (ppm)

80

60
SS9-29 SS9-77
SS9-48 SS6
40 SS7
SS8
20
SS10
0
300 400 500 600
Zr (ppm)

focal plane array has a spatial resolution of 2.6 μm,
producing a 166×166 μm image. In addition, the user can
build images in a two-dimensional array of steps, resulting
in rapid collection of much larger images. Spectra were
collected on discrete points in the glassy portions of
spherical structures. Spot sizes were approximately 10×
10 μm. Spectra were typically collected using 128 scans,
and a polynomial flexicurve baseline correction was applied
prior to calculation of peak heights.
Five samples were analyzed for water concentration. In
all cases, thin section-sized billets were polished using
silicon carbide grit and diamond paste. The highly polished
surface was cemented to a glass slide with acetone-soluble
epoxy (Crystalbond). The bulk of the billet was sawed off
and the remaining rock slab was ground to approximately
100 μm, and then polished, as before, with silicon carbide
grit and diamond paste. Each slide was then placed in an
acetone bath to dissolve the Crystalbond, liberating the rock
slab from the glass. Each slab was rinsed several times in
acetone to remove any trace of Crystalbond, and was
thoroughly dried before analysis. A Starrett #733 digital
micrometer was used to determine the thickness of the
samples. For FTIR analysis, each slab was placed on a glass
slide into which a 1-cm diameter central hole had been drilled.
FTIR spectroscopy of glass
The following form of the Beer–Lambert Law was used
for calculating water concentration in glass (Stolper 1982):
C ¼ ð18:02  AbsorbanceÞ=ðt  D  "Þ ð1Þ
where C is the weight fraction of water, 18.02 is the
molecular weight of water, absorbance is the height of the
absorption peak, t is the thickness of the sample in
centimeters, D is density of the material being analyzed in
grams per liter, and ε is the linear absorption coefficient, in
liters per mole centimeter. The linear absorption coefficient
Bull Volcanol (2012) 74:559–577
for total water used in this study is 90±2 (Hauri et al. 2002)
and that for molecular water (~1,630 cm−1) is 55±2
(Newman et al. 1986).
The following form of the Beer–Lambert Law was used
to calculate water concentration in samples that consist of
finely crystalline material (Libowitzsky and Rossman
1997):
C ¼ A  1:8=ðt  D  lÞ ð2Þ
where C is concentration in weight percent H2O, A is area
under the absorption peak in cm−1, 1.8 is a factor used to
express hydrogen concentrations as their equivalent water
concentrations, t is thickness in centimeters, D is density
in grams per liter, and l is the integral absorption
coefficient in liters per mole H2O cm2. The absorption
coefficient used for calculating water concentration in the
crystals is the universal feldspar absorption coefficient,
107,000±5000 L mol−1 cm−2, derived by Johnson and
Rossman (2003) for calculating water concentration in
feldspar crystals.
A broad, asymmetric band that spans an interval from
3,800 to 3,000 cm−1 is commonly used to determine total
water concentration in glasses (e.g., Dixon et al. 1988;
Dixon and Clague 2001; Saito et al. 2001; King et al. 2002;
Wysoczanski and Tani 2006). The band results from
symmetric H–O–H stretching vibrations, H–O–H bending
vibrations, and symmetric Si–OH stretching vibrations
(Stolper 1982; Ihinger et al. 1994; King et al. 2004). In
this study, peaks in this band occur at various wavenumbers
(e.g., 3386, 3401, 3422, 3563, 3570). The wavenumber of
the peak(s) in the band are affected by the degree to which
hydrogen bonds with neighboring oxygen atoms or ions. With
increasing H-bonding, peak positions shift from higher to
lower wavenumber (King et al. 2004). In this study, we have
used the height of this band, which commonly extends from
approximately 3,700 to 2,900 cm−1, to calculate water
concentration in glass (Stolper 1982; Dixon et al. 1988;
Ohlhorst et al. 2001; Mandeville et al. 2002; King et al.
2002). For isotropic materials such as glasses (quenched
melts), OH− and H2O complexes should have no crystallo-
graphic preferred orientation; hence, any optical direction
should have the same value for A. Thus, the water
concentration of a glass can be measured with a single FTIR
spectrum.
Characteristics of FTIR Spectra of glasses in thundereggs
Water concentrations were measured in five thunderegg
samples, namely samples SS-9-5, SS-9-32, and SS-9-58
from Bhaguda-Longdi, and GS2a and GS2b from Borivli,
Mumbai. Samples SS-9-5 and SS-9-32 are almost entirely
glass, with very sparse microlites approximately 20 μm
571
long and oxide grains of similar diameter. Sample SS-9-58
is similar, with slightly more devitrified glass. Therefore,
Eq. 1 above was used to calculate water concentrations for
all of these samples. Samples GS2a and GS2b, however,
consist entirely of very fine crystalline material dominated
by feldspar and oxide microlites approximately 30 μm
long. Therefore, Eq. 2 above was used to calculate water
concentrations for samples GS2a and GS2b.
FTIR spectra of samples dominated by glass (SS-9-5,
SS-9-32, and SS-9-58) were collected on ~20×20 μm spots
free of microlites. The spectra have a broad, slightly
asymmetric band from approximately 3,700–2,900 cm−1
(Fig. 11) from which total water concentrations were
calculated, and these have low values (0.21–0.38 wt.%,
Table 2). Ideally, absorption bands at 4,520 and 5,320 cm−1
would be used to calculate OH− and molecular water
concentrations, respectively. However, for materials of low
water concentration, the 4,520 and 5,320 cm−1 band
intensities are weak, and the absorbance becomes so small
that peaks are difficult or impossible to resolve. Zhang
(1999) cited 0.2 wt.% as the value below which the near-IR
bands should not be used. At these low water concen-
trations, we have used the broad 3,700–2,900 cm−1 band to
measure total water concentration and the ~1,630 cm−1
band to measure molecular water concentration. However,
the 1,630 cm−1 band is difficult to isolate in many spectra
because it is obscured by several bands produced by Si–O
bonds. The band was not measured in spectra in which its
interpretation was uncertain.
FTIR spectra of thundereggs consisting of very finely
crystalline groundmass (GS2a and GS2b) were collected on
~100×100 μm spots free of oxides. Like the spectra
collected on glass, these spectra have a broad band from
approximately 3,700–2,900 cm−1 from which total water
concentrations were calculated (Table 3). For anisotropic
phases such as feldspar, determination of water concentration
ideally requires collection of FTIR spectra from measurement
in three mutually orthogonal orientations and summing of
concentrations measured in each orientation (Libowitzsky and
Rossman 1997; Johnson and Rossman 2003). The infrared
beam does not have sufficient resolution to allow for the
collection of spectra from individual microlites in even two
mutually perpendicular orientations. If spectra were being
collected on single crystals, collection of FTIR spectra in
only one, rather than three, orientations would mean that
water concentrations calculated would be systematically too
low by a factor of ~3, and one would multiply the values by
three to make an approximation of measuring water
concentration in three mutually perpendicular orientations.
In this study, total water concentrations in the samples GS2a
and GS2b are calculated as 0.19 to 0.39 wt.% (Table 3), but
this is based on analysis of the groundmass as feldspar
crystals (which it dominantly is). In these samples, 100×
572
Fig. 11 FTIR spectrum for a
20×20 μm area of glass in
sample SS-9-5. The height of
the molecular water bending
band at approximately
1,630 cm−1 is indicated
100 μm areas measured include microlites in various
orientations. The microlites are sufficiently plentiful (on the
order of thousands in the area illuminated by the infrared
beam) that it is likely that crystals in all three orientations are
present, so that the values above are taken to approximate the
true water concentration of the groundmass crystals.
Precision of analyses of total water in glass is approxi-
mately ±5%. Dixon et al. (1991) and Dixon and Clague
(2001) estimated the accuracy of total water analyses
at ±10% based on the accuracy of absorption coefficients.
Propagation of error estimates in determining the IR band
areas (±10%), in molar absorption coefficients (~±10%), and
in sample thickness (±1%) through Eqs. 1 and 2 yields total
precision estimates of ~±21% for total water concentrations.
Total water concentrations in all glass samples analyzed
are between 0.21 and 0.38 wt.% (Table 2). In all samples,
the concentration range is based on 10 spot analyses.
Homogeneity of water concentration varies from sample to
sample, as reflected in the standard deviations shown in
Table 2. Most glass analyses have both OH− and molecular
water, because water dissolves in silicate melts as both OH−
and as molecular water based on the equilibrium relation
(Stolper 1982; Dingwell and Webb 1990; Nowak and
Behrens 1995; Shen and Keppler 1995; Sowerby and
Keppler 1999; Mandeville et al. 2002):
H2 OðmeltÞ þ O2 ðmeltÞ ¼ 2OH ðmeltÞ ð3Þ
At low total water concentrations, OH− is the more
abundant water species in glass, and as total water
concentration increases, molecular water becomes dominant
(Zhang 1999). The equilibrium constant that describes Eq.
3 is, of course, temperature-dependent, so the water
concentration at which OH− and H2O attain equal concen-
trations in a glass depends on the temperature at which the
glass quenched. As shown by Zhang (1999, his figure 2), at
470°C, the two water species are equally abundant in the
glass at a total water concentration of approximately 2.5 wt.
%; at 840°C, the two species are equally abundant at a total
water concentration of approximately 9.5 wt.%. In glass
Bull Volcanol (2012) 74:559–577
samples in which molecular water could be measured
relatively unambiguously, in many cases (Table 2), it makes
up essentially all of the water in the glass. Wysoczanski and
Tani (2006) found similar dominance of molecular water in
glasses from the Izu-Bonin arc and suggested that the high
proportions of molecular water were consistent with slow
cooling, which drives Eq. 3 to the left (Zhang et al. 1997).
The same situation may have existed for some domains of
samples analyzed in this study. Overall, the low magmatic
water concentrations (0.21–0.74 wt.%) in the glasses are
consistent with the absence of vesiculation in these glasses.
Discussion
The fact that spherulites occur almost exclusively in glasses
suggests conditions of low nucleation rate but relatively
rapid crystal growth rate. Spherulites may owe their
spherical shape to the isotropic physical properties of the
host melt or glass, implying the absence of any preferred
direction of growth, or to non-crystallographic branching of
mineral fibers (Watkins et al. 2009).
After nucleation, crystal growth and its rate are con-
trolled by the magnitude of undercooling (ΔT, the
difference between the liquidus temperature and the actual
magma temperature). At large ΔT, elemental diffusivities
are very low in anhydrous, viscous silicic magma. The
glass transition temperature in magmas, marking a transi-
tion from viscous or liquid-like behavior to brittle or solid-
like behavior, has been suggested as a lower limit for
spherulite growth (Ryan and Sammis 1981; Manley 1992;
Davis and McPhie 1996). This temperature depends on
composition and cooling rate and is between 620°C and
750°C for anhydrous rhyolite (Gottsmann and Dingwell
2002). Outcrops in which spherulites deflect flow layers in
the host glass indicate that the spherulites formed above the
glass transition, but outcrops also exist where undeformed
spherulites cut across flow layers, suggesting that they grew
at least partly below the glass transition. Various spherulite
growth models (e.g., size-dependent growth and diffusion-
Bull Volcanol (2012) 74:559–577 573

Table 2 Total dissolved H2O, molecular water, and OH− concen- Table 3 Total dissolved H2O contents, measured in the microcrystal-
trations in glasses in the Bhaguda-Longdi thundereggs determined by line groundmass of the Borivli (Mumbai) thundereggs with FTIR
FTIR spectroscopy spectroscopy

Absorbancea Absorbancea Thickness H2O H2O Absorbancea (cm−1) Thickness (cm) H2O wt.%
(3,380– (1,630 cm−1) (cm) molecular total (3,700–2,900 cm−1)
3,550 cm−1) (wt.%) (wt.%)
Sample GS2a
Sample SS-9-5 1 482 0.0087 0.36
1 0.39 0.24 0.0184 0.26 0.27 2 600 0.0087 0.45
2 0.31 0.0184 0.21 3 621 0.0087 0.47
3 0.19 0.0184 0.13 4 437 0.0087 0.33
4 0.21 0.0184 0.14 5 522 0.0087 0.39
5 0.19 0.0184 0.13 6 446 0.0087 0.33
6 0.42 0.27 0.0184 0.30 0.29 7 587 0.0087 0.44
7 0.33 0.0184 0.23 8 468 0.0087 0.35
8 0.26 0.0184 0.17 9 499 0.0087 0.37
9 0.32 0.0184 0.21 10 530 0.0087 0.40
10 0.42 0.0184 0.28 Average 0.39
Average 0.21 Std.dev. 0.05
Std.dev. 0.06 Sample GS2b
Sample SS-9-32 1 346 0.0097 0.20
1 0.52 0.0204 0.25 2 297 0.0097 0.17
2 0.34 0.0204 0.16 3 217 0.0097 0.12
3 0.44 0.0204 0.20 4 344 0.0097 0.20
4 0.26 0.0204 0.12 5 387 0.0097 0.22
5 0.13 0.0204 0.06 6 367 0.0097 0.21
6 0.39 0.0204 0.18 7 221 0.0097 0.13
7 1.35 0.0204 0.63 8 468 0.0097 0.27
8 0.91 0.0204 0.43 9 337 0.0097 0.19
9 0.41 0.30 0.0204 0.19 0.19 10 405 0.0097 0.23
10 0.31 0.30 0.0204 0.14 Average 0.19
Average 0.24 Std.dev. 0.04
Std.dev. 0.17
a
Sample SS-9-58 Area of absorbance band was used to calculate water concentration
in finely crystalline samples
1 0.75 0.29 0.0215 0.25 0.40
2 0.88 0.0215 0.47
3 0.43 0.0215 0.23 lites grow to large sizes on the order of days at eruptive
4 0.82 0.48 0.0215 0.42 0.44 temperatures, continue growing across the glass transition,
5 0.70 0.0215 0.37 and growth rates become extremely slow or zero below
6 0.70 0.0215 0.37 about 400°C.
7 0.82 0.0215 0.44
8 0.81 0.0215 0.43 A comparison of the Deccan and some North American
9 0.72 0.0215 0.39 spherulites
10 0.52 0.0215 0.28
Average 0.38 Many spherulites in North American rhyolites and vitro-
Std.dev. 0.07 phyres have been well studied. Mathews and Watson
a
(1953) described spherulitic alkali rhyolite dikes from
Height of absorbance band was used to calculate water concentration
British Columbia, and Watkins et al. (2009) describe small
in glass samples
(millimeter scale) spherulites in a rhyolitic vitrophyre from
Tequila volcano in Western Mexico, to which the Deccan
controlled growth) have been presented (Castro et al. 2008; ones (e.g., Fig. 2a) are comparable in size and appearance.
Watkins et al. 2009). Watkins et al. (2009) present a model Whereas most described North American spherulites are
of temperature-dependent growth rates, such that spheru- from millimeters to a few centimeters in size, so-called
574
megaspherulites are also known: megaspherulites from
Steens Mountain rhyolite in Oregon have diameters of up
to 91 cm (Fuller 1931), those in a vitrophyric welded tuff at
Klondyke, Arizona, have diameters of up to 183 cm
(Simons 1962), those from an ash flow tuff in Jalisco,
Mexico have diameters of 61 to 335 cm (Stirling 1969), and
those found in a rhyolitic vitrophyre at Silver Cliff,
Colorado, have diameters of 30 cm to as much as 366 cm
(Cross 1896; Lofgren 1971; Smith et al. 2001). The last are
not single spherulites but compound, and comprise multiple
cones or fan-shaped spherulites, each radiating from a
single point and made up of very fine to fine sanidine and
quartz. The megaspherulites are surrounded by a thin
sanidine-quartz rind and an alteration layer containing
mordenite and montmorillonite.
Smith et al. (2001) ascribed the Silver Cliff megaspher-
ulites to sparse heterogeneous nucleation in a vitrophyre
with high dissolved H2O (5–7 wt.%), and therefore
emplaced at some depth, without vesiculation. The highly
dissolved H2O lowered magma viscosity and aided ele-
mental diffusion required for spherulite growth. Once a few
spherulites had formed, further nucleation occurred on the
existing growth cones (made up of very fine sanidine fibrils
and intrafibrillar quartz), and therefore only a small number
of megaspherulites formed. According to Smith et al.
(2001), crystallization of sanidine and quartz, both anhy-
drous phases, led to expulsion of a water-rich residual fluid
from the spherulites, which was enriched in Ca, Mg, and Fe
and depleted in Si, K, and Na. This fluid was concentrated
at the spherulite–vitrophyre boundary and led to hydrother-
mal alteration of the host vitrophyre forming an alteration
layer; the Ca and Mg required in the alteration clay
minerals likely came from circulating groundwater. The
fine sanidine fibers (a few microns wide) indicate rapid
crystallization from a melt or glass at large (at least 245–
350°C) ΔT (Lofgren 1971; Fenn 1977; Swanson 1977).
Thus, Silver Cliff megaspherulite crystallization probably
occurred below the glass transition temperature (Lofgren
1971; Smith et al. 2001).
The Bhaguda-Longdi thundereggs: lava bombs
and pyroclastic volcanism?
Misra (1999) described the Bhaguda-Longdi thundereggs
as “lava bombs of fine-grained rhyolite embedded in the
obsidian flow.” He wrote that the “bombs” were generally
spherical, though some had spindle shape. Their “blistery
surfaces” suggested to him bombs falling in molten lava. He
also mentioned “highly angular bombs” of almost all sizes.
He considered and rejected the possibility that these
objects were spherulites, writing that: “The important
differences between the spherulites described by Lofgren
(1971) and volcanic bombs of Longdi-Bhaguda area are
Bull Volcanol (2012) 74:559–577
that, these bombs are present even within fresh glass, are of
much larger sizes, have blistery surfaces and do not show
radiating internal structure.” He offered no thin section
observations. There is no reason why spherulites should not
occur within fresh glass, and many spherulites—all primary
ones formed by rapid undercooling—do. The sizes we have
found, of up to 10 cm, and by Misra (1999) of 15 cm, albeit
large, are still small compared to those of megaspherulites.
We have found neither highly angular nor spindle shaped
bombs and no “blistery” surfaces.
It is the lack of a radiating internal structure in the
Bhaguda-Longdi objects as recognizable by the naked eye,
and supported by our thin section observations, that we
consider atypical of spherulites (a few spherulites without
radial structure are reported by Davis and McPhie (1996)
but are unusual and uncommon). It is because of this lack
of radial structure, and the secondary silica-filled cores and
fractures in these objects (Fig. 2h), that we consider them to
be thundereggs. Misra (1999) considered the thunderegg
twins or triplets (Fig. 2g) to be “fused lava bombs.” He also
claimed faults cutting the thundereggs, which we have not
observed, and in our view, the twins and triplets are
lithophysae that started to grow by vapor-phase crystallization
on nearby nuclei and in the process intergrew and coalesced.
Misra (1999) also illustrated an outcrop (his figure 3e)
allegedly showing “parallel alignment of volcanic bombs
along flow layering.” No locality information was given, but
the outcrop appears similar to the Kagvadar outcrop
illustrated in our Fig. 2b, c, which we interpret very
differently: spherulitic obsidian indeed develops in spatially
restricted zones as dictated by the thermal profile of the
magma body (Manley and Fink 1987). In a rock body,
spherulites may be randomly distributed and completely
isolated, or nucleate preferentially to form clusters or trains
(Davis and McPhie 1996). Spherulite textures and relation-
ships vary widely with variables such as emplacement
temperature, flow depth, cooling rate, and surface
hydrology (Manley 1992). Even post-eruption, structure-
controlled hydration can also produce features interpreted
by Misra (1999) as lava bombs aligned along flow layers.
Misra (1999) not only misidentified the Bhaguda-Longdi
thundereggs as lava bombs, and as evidence for pyroclastic
activity, but also stated that the Bhaguda-Longdi area was
the best locality to study explosive volcanism in the Deccan
Traps. We find no trace of pyroclastic activity in these
outcrops and suggest below that these rocks are not even
extrusive.
Emplacement environment and style
Because of the low magmatic water contents and non-
vesicular nature of the rhyolites and pitchstones of the
Bull Volcanol (2012) 74:559–577
Bhaguda-Longdi-Kagvadar area, we consider them to be
subvolcanic intrusions. The high volatile concentrations
required to form the lithophysae (now thundereggs)
probably result from second boiling (see also Tuffen and
Castro 2009) and do not require volatile-rich magmas.
Misra’s (1999) statement that the “lava bomb”-bearing
pitchstone of Bhaguda-Longdi is seemingly a vertical sheet-
like body with horizontal columnar jointing (a possible
magma conduit or dike in our view) is in support of this
interpretation. The interpretation is also supported by the
regional geological context of the Saurashtra region, which
abounds in subvolcanic intrusions (e.g., Sheth et al. 2011a).
We also interpret the Borivli trachytic pitchstone, almost
totally without vesicles, as a shallow-level intrusion. Subvol-
canic intrusions of trachyte outcrop along the Mumbai coast,
only a few kilometers west of this pitchstone (Lightfoot et al.
1987; Zellmer et al. 2011). On the other hand, the Osham Hill
pitchstones are lavas (Sheth et al. 2011b). The Deccan
pitchstones are good analogs of the subvolcanic pitchstone
intrusions (dikes and cone sheets), as well as pitchstone lavas,
mapped in the Scottish Hebrides, a part of the Palaeogene
North Atlantic igneous province (Tyrrell 1926; Drysdale
1979; Hatch et al. 1983; Emeleus and Bell 2001).
Recognition of the Bhaguda-Longdi-Kagvadar pitch-
stone ridges as shallow-level subvolcanic intrusions helps
address a broader issue in Saurashtra Deccan geology. A
very notable geomorphic feature of the southern and
southeastern Saurashtra region, such as around Rajula and
Dedan (Fig. 1), is the hundreds of linear and parallel
topographic ridges that rise tens of meters above flat plains
of the basalts. The ridges are composed of rhyolite,
pitchstone, dacite, trachyte, basalt, dolerite, and picrodoler-
ite (Krishnamacharlu 1972; Chatterjee and Bhattacharji
2001). Figure 12 shows one such prominent ridge of
Fig. 12 View, roughly along strike, of the prominent ridge of
porphyritic brown rhyolite sampled at Barman Mota village near
Rajula town (sample SS1). The ridge rises several tens of meters
above the plains formed by basalt flows. It trends NE–SW and dips
SE. Note the classical cuesta morphology with steep escarpment on
the northwest and gentler dipslope on the southeast. We interpret this
as a cone sheet
575
rhyolite, several kilometers long, at Barman Mota village
near Rajula (Fig. 1). These topographic ridges have been
interpreted as dikes (Auden 1949) and as tilted lava flows
(Misra 1999). Elsewhere in the Deccan Traps, tholeiitic
dikes are known to form prominent ridges over surrounding
weathered basalts (e.g., Ray et al. 2007). Dike ridges in the
Deccan, however, usually show equal slopes on either side
of the ridge crests (Auden 1949; Ray et al. 2007), due to the
dikes usually being vertical. The Rajula-Dedan area ridges
have strongly asymmetric cross-profiles and cuesta mor-
phology with gentle (15–20°) dipslopes.
Interestingly, the NE–SW trend of the southern Saurashtra
cuesta ridges swings to become ENE–WSW in southeastern
Saurashtra (Misra 1999; see Fig. 1), forming an overall
arcuate trace in plan. Based on (1) this arcuate trace,
convexity to the north, (2) the subvolcanic environment
inferred for the Kagvadar and Bhaguda-Longdi pitchstone
suites, and (3) the fact that the dips of these sheet-like bodies
are gentle (of 15–20°) and due south (Fig. 12), we interpret
these tabular intrusions as cone sheets, emplaced from a
plutonic center which now lies submerged beneath the
Arabian Sea. The location of this proposed plutonic center
is in an area of significant post-Deccan downfaulting and
subsidence, including the Gulf of Cambay (along which runs
the Cambay Rift) (e.g., Ramanathan 1981). Strong structural
and compositional parallels between Saurashtra and the
Palaeogene Scottish Hebrides (e.g., the central complexes)
have been noted by Sheth et al. (2011a, b), and the Scottish
central complexes are famous for their abundant cone sheet
intrusions (Tyrrell 1926; Hatch et al. 1983; Hall 1987;
Emeleus and Bell 2001).
Conclusions
In this first report of spherulites and thundereggs in
rhyolitic (and a few trachytic) pitchstones of the Deccan
Traps, India, we describe their field and petrographic
features and major and trace element bulk-rock geochem-
istry. We have also determined low contents of magmatic
water (0.21–0.38%) in them using FTIR spectroscopy. The
spherulites and thundereggs we have observed range in size
from microscopic size, through 0.5–1 mm, to a few
centimeters, the largest being ~10 cm in diameter. The
previous identification by Misra (1999) of the thundereggs
from Bhaguda-Longdi (in southeastern Saurashtra) as
rhyolitic lava bombs, representing pyroclastic volcanism,
is incorrect. Various evidence supports the contention that
the spherulite-bearing pitchstones of Osham Hill (western
Saurashtra) are lava flows, whereas the pitchstones of three
other localities studied here, containing spherulites and
thundereggs, represent subvolcanic intrusions. The struc-
tural pattern of the sheet intrusions of southern Saurashtra,
576
some of them studied here, suggests to us that they are not
all dikes or tilted lava flows as perceived by previous
workers, but several may be cone sheets emplaced from a
plutonic center later downfaulted and submerged beneath
the Arabian Sea. This plausible interpretation further
reinforces the great similarities in magmatic style between
the Saurashtra region of the Deccan Traps and the Scottish
Hebrides, part of the North Atlantic Tertiary Igneous
Province.
Acknowledgements This work was supported by the Department of
Science and Technology (DST) grant SR/FTP/ES-19/2007, as well as
the Industrial Research and Consultancy Centre (IIT Bombay) grant
09YIA001, to Sheth. The latter grant also supported Mohite for a 3-
month period. Kshirsagar and Shaikh were supported by Ph.D. and M.
Tech. studentships, respectively, from IIT Bombay. Seaman acknowl-
edges support from the U.S. National Science Foundation (grant EAR-
0549637) which funded the purchase of the FTIR spectrometer and
microscope at the University of Massachusetts. We thank Dipak
Gosain for valuable help during field work, the friendly children of
Bhaguda village for showing us some of the thundereggs, Sudeshna
Bhattacharyya and Shilpa Netrawali for laboratory assistance, and
George Mathew, Kanchan Pande, and Liz Johnson for helpful
discussions and comments. The manuscript greatly benefitted from
careful, critical reviews by Jonathan Castro and an anonymous
reviewer, the editorial handling of Donald Dingwell, as well as
comments from James White.
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