JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 109, B08201, doi:10.

1029/2003JB002721, 2004

Cooling process recorded in subglacially erupted rhyolite glasses:

Rapid quenching, thermal buffering, and the formation of meltwater
Martin C. Wilding,1 John L. Smellie,2 Sally Morgan,3 C. E. Lesher,1 and Lionel Wilson4
Received 1 August 2003; revised 6 March 2004; accepted 25 May 2004; published 11 August 2004.

[1] The thermal histories of two subglacial rhyolite glasses from Torfajokull complex of

south central Iceland have been determined from changes in the relaxation of enthalpy in
the calorimetric glass transition interval. Heat capacity measurements of bulk glass
samples from Rau*ufossafjoll (sample number JS.1.1) and Blahnukur (sample number
JS.2.1) by differential scanning calorimetry show marked differences in the temperature of
the onset of glass transition (Tg) on reheating. The average Tg is 750 K for JS.1.1, whereas
it is 850 K for JS.2.1. These differences in the onset of Tg are related to quench rate
through considerations of the activation energy and timescales for structural relaxation
modeled, using the Kohlrausch-Williams-Watt function. Multiple glass samples from the
two Torfajokull locations recover different average values and distributions of a fictive
temperature, Tf, which we interpret in terms of differences in the thermal histories of the
glasses. In both glass samples the range of fictive temperatures and, by implication,
apparent cooling rates, is lower than those estimated for a glass rapidly quenched by
contact with cold (glacial melt) water and requires that the glass was annealed at
temperatures in the glass transition interval associated with relaxation times of the order of
100010,000 s. The complex cooling histories of the Torfajokull samples show that the
products of subglacial eruptions may be held at elevated temperatures for several hours
and, as a result, may drive vigorous convection in the ice-bound vaults above erupting
INDEX TERMS: 8429 Volcanology: Lava rheology and morphology; 8494
rhyolite deposits.
Volcanology: Instruments and techniques; 8499 Volcanology: General or miscellaneous; KEYWORDS: cooling,
glass, relaxation
Citation: Wilding, M. C., J. L. Smellie, S. Morgan, C. E. Lesher, and L. Wilson (2004), Cooling process recorded in subglacially
erupted rhyolite glasses: Rapid quenching, thermal buffering, and the formation of meltwater, J. Geophys. Res., 109, B08201,
doi:10.1029/2003JB002721.

1. Introduction
1.1. Subglacial Volcanism
[2] Subglacial volcanic eruptions involve the rapid,
focused delivery of geothermal heat to a glacier base,
typically generating and ultimately releasing large volumes
of meltwater in a dramatic and potentially hazardous
discharge into preexisting drainage networks [Bjornsson,
1988]. The generation of large volumes of meltwater
reflects the rapid rate at which ice melts during an eruption
and is a function of magma discharge rate, duration, and
temperature [Allen, 1980; Hoskuldsson and Sparks, 1997;
Smellie, 2000]. There is no simple method of correlating
the magnitude and timing of the meltwater discharge with
eruption conditions because most subglacial eruptions are
1
Department of Geology, University of California at Davis, Davis,
California, USA.
2
British Antarctic Survey, High Cross, Cambridge, UK.
3
School of Earth Sciences, University of Leeds, Leeds, UK.
4
Environmental Science Department, Institute of Environmental and
Natural Sciences, Lancaster University, Lancaster, UK.

Copyright 2004 by the American Geophysical Union.

0148-0227/04/2003JB002721$09.00

largely obscured by ice, particularly in the early stages, and

thus cannot be observed directly. Interpreting the thermal
history and evolution of subglacial eruptions thus relies
mainly on interpreting the volcanic lithofacies formed
during such eruptions [Gudmundsson et al., 1997; Jones,
1969, 1970; Skilling, 1994; Smellie, 2001; Smellie and Hole,
1997; Smellie et al., 1993] or by applying thermodynamic
models [Allen, 1980; Hoskuldsson and Sparks, 1997].
[3] Most subglacial eruptions take place either within
water-filled, ice-constrained vaults or, when breakthrough
occurs, in englacial lakes [Bjornsson, 1988; Smellie, 2000].
Both situations are characterized by specific associations of
lithofacies, lithofacies architecture, and landforms [Skilling,
1994]. Eruptions beneath relatively thick ice typically create
ridged or flat-topped landforms, the latter typically but not
always caused by the lateral progradation of the edifice by
lava-fed (subaerial) deltas [LeMasurier, 2002; Skilling,
2002; Smellie, 2000; Tuffen et al., 2002a]. Lavas in contact
with surface water, including those emplaced in subglacial
vaults, experience rapid quenching caused by contact with
the water, and they show fractures diagnostic of that
interaction [Degraff et al., 1989; Lescinsky and Fink,
2000; Long and Wood, 1986]. The spacing and geometry
of those fractures correlates, qualitatively, with the cooling

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rate. The development of polygonal fractures during

quenching will greatly increase the surface area of hot lava
available to transfer heat conductively to the surrounding
water. However, empirical calculations suggest that the
process may be counteracted by the decrease in convective
flux resulting from the development of a thick glass rind
[Tuffen et al., 2002b]. Therefore there is no simple correlation between the development and density of fractures in
lavas in subglacial volcanic landforms, overall heat flux,
and ice melting rate.
[4] Thermodynamic models can be used to evaluate the
mechanism of emplacement of subglacial volcanic deposits
and to estimate the melting rate of ice [Hoskuldsson and
Sparks, 1997; Tuffen et al., 2002b]. Wilson and Head [2002]
developed a model for the emplacement of subglacial
basalts which emphasizes the influence of dissolved volatiles in controlling the eruption style. According to that
model, at the rapid strain rates expected during melt
propagation in a fracture, basaltic magma may either intrude
the overlying ice as a dyke or else spread sideways as a sill
at the rock-ice interface. The precise emplacement style is
probably affected by a combination of the magma chamber
pressure gradient and magma buoyancy. For rapid emplacement rates of
1 m s1 [Wilson and Head, 2002], there is
little time for much melting of the surrounding ice, and the
dyke is briefly supported. Extensive melting follows very
shortly afterward, however, and the now unsupported dyke
collapses as a rubble pile within an ice-confined void that
fills with water and becomes the locus of the continuing
eruption. If the magma is emplaced as a sill, the lateral
movement of magma can result in more efficient melting of
the surrounding ice because the extremely thin (subcentimeter) initial layer of magma can transfer heat more effectively to the overlying ice via intervening meltwater. In both
dyke and sill eruptions the eruptive style may change
dramatically if the vault becomes hydraulically connected
to the atmosphere, perhaps via subglacial tunnels connected
to a nearby ice margin. The confining pressure over the vent
will thus drop rapidly to atmospheric, i.e., much less than
the volatile saturation pressure of the magma (
3 MPa for
typical basalt water contents [Wilson and Head, 2002]).
Volatiles (H2O and CO2) are then explosively exsolved,
causing magma disruption and fire fountain activity. In that
event, ice would be expected to melt rapidly; blocks of ice
may even become entrained in the magma column, potentially precipitating more violent phreatomagmatic eruptions
and brittle collapse of the ice vault roof.
[5] The generation of meltwater during subglacial eruptions can be modelled using versions of the Carslaw and
Jaeger [1959] model for the conduction of heat in two
infinite half spaces. This model can be used to calculate the
thickness of chilled crust generated on the surface of the
erupted magma and also to calculate the heat flux through
that surface as a function of time. It is straightforward to
further calculate the thermal energy released and the amount
of ice that can be conductively melted around the magma.
The rates of meltwater generation in subglacial eruptions
have been estimated by two versions of the Carslaw and
Jaeger [1959] model, that of Hoskuldsson and Sparks
[1997], and also that of Wilson and Head [2002], although
the consequences of meltwater generation are addressed
differently in the two models. The melting rates were

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estimated to be as high as 1 40 m day1. However, these

rates are much slower than those observed in recent eruptions (e.g., Gjalp, Iceland, in 1996 [Gudmundsson et al.,
1997] and Deception Island, Antarctica, in 1969 [Smellie,
2002]). Gudmundsson et al. [1997] and Gudmundsson
[2004] appealed to fragmentation of magma to increase
the rapidity of the thermal flux between magma and water/
ice, whereas Smellie [Smellie, 2002; Tuffen et al., 2002b]
invoked a role for juvenile gases and steam generated from
groundwater. The two mechanisms are not mutually exclusive and may operate within the same eruption. What is
required is an independent method of testing the published
thermal models to assess why natural eruptions seem to be
associated with the unusually rapid and more complete
release of thermal energy from the magma than can currently be predicted theoretically. It is difficult to determine
the cooling history of a subglacial volcanic edifice, as there
can be no preserved record of any hot gases, and there are
no published descriptions of the volcanic products (fragmented magma or intact lava pillows) formed over the vent
in the earliest stages of an eruption. Conversely, the
quenched glass structure can retain evidence of its thermal
history and potentially can be used to extract a numerical
value of cooling rate if the structural relaxation of the
glass can be modelled [Gottsmann and Dingwell, 2001;
Gottsmann et al., 2002; Wilding et al., 2000; Wilding et al.,
1996a; Wilding et al., 1996b]. It is the purpose of this
paper to demonstrate that sensible values of the thermal
history of subglacial volcanic rocks can be derived using
quenched glass structure and that the data can be used to
calibrate and test the published thermal models.
1.2. Structural Relaxation and Fictive Temperature
[6] Any natural or synthetic glass retains a record of its
thermal history in the quenched structure [Dingwell, 1995;
Moynihan, 1995; Scherer, 1990]. The quenched structure is
resolved by analyzing any structurally dependent property,
such as the volume or enthalpy, and the most convenient
way of doing this is to introduce the concept of a fictive
temperature (Tf) [Moynihan et al., 1991; Narayanaswamy,
1971, 1988; Tool, 1946]. Fictive temperature relates any
structure-dependent physical property (e.g., enthalpy) to a
temperature at which that property would be in equilibrium
and has units of temperature (K). Fictive temperature is thus
a proxy for the equilibrium temperature of a structural
configuration and will differ from the ambient temperature
in the glassy state [Tool, 1946]. The fictive temperature is
used to extract the thermal history by observing the structural relaxation to a new equilibrium as the glass is reheated.
If the fictive temperature is equated with enthalpy (H), then
the relaxation process can be observed directly through
differential scanning calorimetry (DSC) measurements,
where the first temperature derivative of enthalpy, heat
capacity at constant pressure (Cp), is used. Such calorimetry
measurements, applied to volcanic glasses, show a large
range of apparent cooling rates from a few degrees per day
to more rapid rates of up to 25 K s1 [Wilding et al., 2000,
1996a]. The more rapid rates are consistent with rates
derived from other geospeedometry methods and also
from rates estimated from simple thermal models.
[7] In this contribution we use a series of DSC experiments on two rhyolitic glasses from two subglacial edifices

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Figure 1. (a) Evolution of fictive temperature with

temperature. The fictive temperature (structure) of three
glasses is shown for three different cooling rates. The
departure from the equilibrium liquid (Tf = T ) occurs at
higher temperatures for rapid cooling rates, and the frozen
values of fictive temperature are higher for more rapidly
cooled glass. The relaxation paths for glasses reheated, at
5 K min1, through the glass transition temperature to the
stable liquid field (dotted lines) are also shown. (b) The
evolution of derivative fictive temperature on reheating. For
the same three samples in Figure 1a the reheating paths are
shown with derivative fictive temperature, DTf/DT, if Tf is
equated with enthalpy. These curves are the same as those
that would be obtained from DSC measurements if the heat
capacity were normalized. Dashed line denotes glass cooled
at 2.5 K min1.
in Iceland in order to evaluate their thermal history, correlate
their cooling rate with a surface flux, and assess the
potential effect on the generation of meltwater. To constrain
the thermal history of the two glass samples, a large number
of repeated calorimetry measurements were made on
aliquots from them, so that the distribution of fictive
temperatures in the relatively small glass samples could
be evaluated. These data are used to evaluate the contribu-

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tions of different cooling processes to the overall thermal

history which have been shown to be complex [Tuffen et al.,
2002b].
[8] The concept of fictive temperature and the related
structural relaxation time is used in the classic description of
glass formation. The liquid state is defined as a regime
where any structural response to temperature is rapid,
reflecting a short relaxation time. A glass state is where
the structure responds more slowly (i.e., the structural
relaxation time is long) and may never achieve equilibrium.
From this definition the fictive temperature is dependent on
the structural relaxation time (t), which is the ratio of the
elastic bulk modulus (G) to the shear viscosity [Dingwell,
1995; Dingwell and Webb, 1990], or the Maxwell relation
[Maxwell, 1867]. The elastic bulk modulus remains constant
for silicate liquids [Webb and Dingwell, 1995], and so the
structural relaxation time of silicate liquids is proportional
to shear viscosity [Dingwell and Webb, 1990]. At high
temperatures the relaxation time is rapid, and the response
of the liquid to fluctuations in temperature is an equilibrium
one defining a stable liquid field by Tf = T; that is, the
liquid structure is in equilibrium with the ambient temperature (Figure 1). When the glass-forming liquid is cooled,
the structural relaxation time, t, increases and the liquid
structure (Tf) falls out of the Tf = T equilibrium (Figure 1).
The liquid can still partly relax (t > t), however, but not to
an equilibrium structure. This departure from Tf = T depends
on cooling rate and occurs at a higher temperature for
rapidly quenched liquids. Continued decrease in the ambient temperature results in progressively longer relaxation
times until a temperature is reached when fictive temperature can no longer change (t  t). This final value of fictive
temperature is that frozen into the quenched glass
(Figure 1) [Moynihan, 1995].
[9] The fictive temperature and relaxation time are intimately related. To derive the thermal history of any glass,
the fictive temperature and relaxation time must be measured together, since it is the relaxation of fictive temperature that is characteristic of the cooling process. Enthalpy
(H) is directly related to fictive temperature, and the
relaxation process can therefore be investigated through
DSC. The first temperature derivative of the fictive temperature corresponds to the normalized heat capacity,
Cp

DH DTf
:

DT
DT

[10] The frozen thermal history of the glass is evaluated

by reheating the glass at a known heating rate. This process
is also shown in Figure 1. As the glass is reheated, the
relaxation time (t) becomes shorter relative to observation
time until a temperature is reached at which the structure
can begin to relax to a new, lower temperature equilibrium
value. The new equilibrium is not reached, however,
because the relaxation time is still long (Figure 1). As
temperature is increased further, the relaxation time
becomes shorter, while the temperature of the new structural
equilibrium (Tf = T ) also increases. At a point where the
equilibrium Tf exceeds that of the partly relaxed sample, the
Tf relaxes toward a higher fictive temperature (Figures 1
and 2). This hysteresis in Tf versus T evolution depends on
the prior cooling rate and the heating rate. The relaxation of

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a glass passing into the liquid field is modelled using the

Kohlrausch-Williams-Watt (KWW) function:
tb
P P0 exp
:
t

[11] Here t is the characteristic relaxation time, t is time

and b is a constant (0 < b < 1) that reflects the nonlinear and
nonexponential relaxation process [Moynihan, 1995;
Scherer, 1990]. P is any macroscopic physical property that
evolves from an initial value P0. The KWW function can be
modified to include structure-dependent terms and an
Arrhenian expression of relaxation time [Debolt et al.,
1976; Moynihan, 1995; Moynihan et al., 1991, 1976,
1974; Scherer, 1990]. A modified version of the KWW
function has been used successfully to evaluate the thermal
history of a variety of volcanic glasses [Gottsmann and
Dingwell, 2001; Gottsmann et al., 2002; Wilding et al.,
2000, 1996b, 1995]. The basis for these fictive temperature
studies is the so-called Tool-Narayanaswamy model of the
KWW [Crichton and Moynihan, 1988; Moynihan et al.,
1991] in which four kinetic parameters are required to
model the relaxation of enthalpy. The four parameters are
the activation energy for relaxation (H) and the preexponential factor (t0) for structural relaxation time, and two
additional parameters, X, a measure of the temperature
dependence of structure, and b, the parameter that describes
the spectrum of relaxation times in the KWW function
[Crichton and Moynihan, 1988; Moynihan, 1995; Scherer,
1990].

2. Sample Descriptions and Volcanic Setting

[12] Both samples are rhyolite glasses of Quaternary age.
They were obtained at Rau*ufossafjoll (sample JS.1.1) and
Blahnukur (Sample JS.2.1), two rhyolite edifices within the
Torfajokull rhyolite complex in south central Iceland. The
following descriptions of the outcrops are based on the more
detailed descriptions by Tuffen et al. [2001, 2002a].
2.1. Sample JS.1.1
[13] The Rau*ufossafjoll center is a subglacial to emergent rhyolite tuya (table mountain) with a volume of
1 km3
that was probably erupted through a former glacier >350 m
thick. It comprises a very poorly exposed pedestal mainly
composed of massive, poorly sorted phreatoplinian ash
erupted within a moist but drained englacial vault and a
flat-topped subaerial rhyolite lava cap. At least three additional coeval rhyolite lavas are also present and exposed
mainly on a low platform on the east side of the main massif
(lavas C, D, and E from Tuffen et al. [2002a]; Figure 3).
Lava D comprises three lava bodies, which share similar
lithological characteristics and were probably coerupted.
They occupy a prominent north-south trending break in
slope formed by flow-banded obsidian lava with a subaerial
carapace of pumiceous and obsidian breccia. Sample JS.1.1
was obtained at the eastern margin of a prominent columnar
jointed obsidian lava lobe within lava D [Tuffen et al.,
2002a]. The precise position of the original outer surface of
the lava lobe in relation to the sample is unknown, but it is
likely to be within a few to several decimeters of the
sampling position. The obsidian lava was possibly separated

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from the enclosing ice walls by a fragmental layer, not now

preserved. The sampled lobe consists of dark grey perlitized
flow-banded obsidian, which makes up the bulk of the
exposure. The obsidian contains up to 80% bead-like relicts
of black glass set in altered pale grey glass. The upstanding
morphology of the columnar jointed obsidian lobe is interpreted to be an original ice contact feature, with the rhyolite
magma chilling rapidly against former ice walls of the
enclosing glacier that dipped steeply east away from the
edifice. Abundant meltwater probably caused the pervasive
perlitic alteration, most likely while the lava was still hot.
2.2. Sample JS.2.1
[14] The outcrop at Blahnukur represents a much smaller
volume (<0.1 km3) eruption of largely degassed rhyolite
magma, emplaced beneath a glacier possibly >400 m thick
[Tuffen et al., 2001]. It comprises a basal glacial sedimentary unit overlain by a variety of monomict juvenile breccias
that include numerous irregular columnar jointed lava lobes
and cogenetic feeders. Unlike the Rau*ufossafjoll outcrop,
there is no evidence that the Blahnukur volcano was ever
subaerial during its eruption. There is no subaerial lava
cap and the outcrop lacks a flat top; it is thus not a rhyolite
tuya. Glassy juvenile fragments in the breccias were formed
roughly in situ, mainly by water quenching of the volatilepoor magma, but large sections of the edifice were
remobilized by a variety of mechanisms, mainly gravitational collapse of the growing volcanic pile, with evidence
for both hot and cold emplacement. Like Rau*ufossafjoll,
the englacial vault was probably drained but moist, with
abundant meltwater. The lava lobes are thought to have
been injected into and molded and chilled in contact with
the overlying glacier. They are characterized by thick,
obsidian surfaces that enclose massive microcrystalline
rhyolite interiors; perlitization is largely confined to the
lobe bases. Sample JS.2.1 was obtained from a columnar
jointed lava lobe at the base of a stream section in Grnagil
[Tuffen et al., 2001]. The lobe is part of a large-scale breccia
unit interpreted to have formed by brittle failure and mass
slumping of a cold section of the edifice. The sample is a
flow-banded obsidian obtained
10 cm within the columnar
jointed outcrop. The lobe is apparently in (obscured) contact
with dense obsidian breccia. Because the lobe has been
displaced from its original position during slumping, it is
unclear how close the sample site was located to the original
lobe surface, although they were probably not separated by
more than a few decimeters.

3. Experimental Methods
[15] Heat capacity data were used to establish the first
temperature derivative of fictive temperature, approximated
to DTf /DT (Figure 1b). Heat capacity data were collected
using a Setaram DSC111 differential scanning calorimeter.
Samples (200 mg) of glass were placed in platinum boats
and heated to 983 K at rates of 5 20 K min1. An empty
platinum boat was placed in the reference position, and the
instrument was calibrated using a-Al2O3 powder. The heat
capacity curves for a-Al2O3 (National Institute of Standards
and Technology) were used to calculate sensitivity curves
for each scan rate. Corrections for the heat capacity of the
platinum boats were made by heating empty boats for the

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Table 1. Kinetic Parameters, Modeled Quench Rate, and Fictive Temperatures for JS.1.1
Run Number

Log10t0/s 0.5

DH/(kJ mol1) 5

X 0.05

b 0.05

jqj/(K min1)

Tf /K 0.5

71
73
75
77
79
81
83
85
87
89
91
93
95
97
99
101
103
105
107
109

16
16
16
16
16
16
16
16
17
16
16
16
16
16
16
16
16
16
16
17

330
330
330
328
333
328
326
325
353
330
329
330
325
324
330
325
324
328
337
358

0.55
0.65
0.63
0.6
0.55
0.57
0.7
0.7
0.55
0.68
0.73
0.68
0.55
0.60
0.55
0.6
0.6
0.55
0.6
0.5

0.7
0.7
0.63
0.7
0.75
0.73
0.54
0.55
0.6
0.65
0.53
0.68
0.75
0.76
0.73
0.78
0.78
0.75
0.6
0.5

0.04
0.08
0.50
0.06
0.08
0.15
0.05
0.07
0.06
0.06
0.06
0.08
0.18
0.25
0.13
0.11
0.01
0.50
0.02
0.02

856.6
832.6
909.6
862.9
873.7
880.6
851.3
855.0
878.9
869.0
889.4
898.9
887.7
881.7
882.5
865.9
850.4
896.7
858.2
851.3

same sequence of scan rates. Heat capacity curves were then

calculated using these corrections. According to the fictive
temperature concept, the liquid field is defined by DTf /DT =
1 and the glass field DTf /DT = 0 (Tf = constant; Figure 1).
The heat capacity curves are normalized by fitting linear
curves to the glass and liquid portions of the heat capacity
trace so that the same relations apply.
[16] In typical DSC experiments the sample size is
200 mg, a very small fraction of a typical volcanic deposit.
This implies that, potentially, each glass sample can have a
different thermal history. Accordingly, in this study we
report the results of a series of heat capacity experiments,
on 200 mg aliquots from each of the two rhyolite obsidian
samples. Multiple (18 and 20) measurements from each
specimen were taken, and the distribution of fictive temperatures for each glass has been used to establish the influence
of annealing on the frozen structure retained in the
quenched products.
[17] In previous studies, sets of kinetic parameters have
been obtained for individual samples [Wilding et al.,
1996a, 1996b]. In this study we have not used separate
sets of parameters for each aliquot measurement, but we
have slightly modified this approach to take account of the
minimal compositional differences within the sample subsets. There are 18 20 subsets of each bulk composition
(JS.1.1 and JS.2.1), and the relaxation process of each, as
described by equation (2), will be similar. Therefore only
two sets of kinetic parameters, one for JS.1.1 and one for
JS.2.1, are required. The extraction of fictive temperature
for the 20 subset samples of JS.1.1 and JS.2.1 can be
accomplished more efficiently by modifying the calibration
step. The specific kinetic parameters for each of the two
bulk compositions JS.2.1 and JS.1.1 were obtained by
more extensive thermal treatments [Wilding et al., 1995] at
cooling rates of 5, 10, 15, and 20 K min1. Once these
parameters were derived, subsequent measurements of
each composition required only two heating steps; one
was the initial reheating to determine the fictive temperature of the naturally cooled sample, and the other followed
a controlled cooling at 10 K min1 for calibration. These
modified measurements were made with reheating rates of

10 K min1. An example of the quality of fit is shown in

Figure 4.

4. Results
[18] The fictive temperatures modelled from the heat
capacity measurements for the 20 aliquots from JS.1.1 range
from 833 to 910 K, equivalent to apparent cooling rates of
0.016 0.5 K min1. The ranges of kinetic parameters
associated with this glass composition are shown in
Table 1. The sample has a relatively high glass transition
temperature and an activation energy for viscous flow of
330 kJ mol1. A consequence of the high activation energy
is that the enthalpy release on structural relaxation is quite
small, as is the associated calorimetric signal. The values of
fictive temperature modeled for the 20 glass aliquots from
JS.1.1 are skewed toward higher values of fictive temperature reflecting faster quench rates (Figure 5a).
[19] The glass transition temperature for sample JS.2.1 is
much lower than that for JS.1.1. The onset is at
750 K,
and the mean value of fictive temperature is 745 K (Table 2).
The activation energy for viscous flow, determined from the
thermal treatments of these glass samples, is 299 kJ mol1.
The differences between the activation energies of the two
samples indicate a difference in the temperature dependence
of viscous relaxation, consistent with minor compositional
differences between the two samples [Gottsmann et al.,
2002; Martens et al., 1987; Stevenson et al., 1995]. The
distribution of fictive temperatures for sample JS.2.1 is
more symmetrical about the mean value (Figure 5b). The
range in fictive temperature is from 722 to 769 K, equivalent to apparent quench rates of 0.0035 to 0.065 K min1
(Table 2).

5. Discussion
[20] The maximum quench rate for subglacial volcanism
can be estimated from the classic models of conduction in
infinite half spaces [Carslaw and Jaeger, 1959]. In this type
of analysis the solution to the conduction problem yields the
temperature as a function of time and distance from the

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Table 2. Kinetic Parameters, Modeled Quench Rate, and Fictive Temperatures for JS.2.1
Run Number

Log10t0/s 0.5

DH/(kJ mol1) 5

X 0.05

b 0.05

jqj/(K min1)

Tf /K 0.5

35
37
39
41
43
45
47
49
51
53
55
57
59
61
63
65
67
69

16.4
16.4
16.4
16.4
16.4
16.4
16.2
16.4
16.4
16.4
16.4
16.4
16.4
16.4
16.4
16.5
16.4
16.4

297
297
297
297
297
297
297
298
300
297
295
297
295
297
299
297
297
300

0.65
0.7
0.65
0.65
0.65
0.65
0.65
0.65
0.65
0.65
0.73
0.65
0.75
0.75
0.65
0.73
0.68
0.65

0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7
0.7

0.004
0.015
0.09
0.02
0.015
0.04
0.015
0.015
0.008
0.008
0.035
0.035
0.006
0.024
0.003
0.018
0.065
0.07

722.6
745.9
773.2
749.2
752.2
760.3
751.9
744.6
742.4
738.2
754.9
759.3
731.8
752.2
725.2
745.7
769.0
740.4

water-lava interface [Hoskuldsson and Sparks, 1997; Wilson

and Head, 2002]. Values of thermal diffusivity (2.88
106 m2 s1) and eruption temperature (1323 K) appropriate for rhyolite, and a water temperature of 273 K, are used
to calculate the temperature profile as a function of depth
and time. The temperature in the first 1.5 cm of the lavawater interface will fall below the value of the calorimetric
glass transition during the first 60 s of contact. The
instantaneous quench rate calculated at the interface
depends on both temperature and time. At the interface
itself the quench rates are, as expected, very rapid (of the
order of 1 200 K min1) and are much faster than those
previously reported for natural glasses, even though the
DSC-based technique is robust enough to record such high
fictive temperatures. Further from the interface, within the
first few centimeters, the quench rates are more moderate
and range between 10 and 30 K min1. These values are

Figure 2. The modification of fictive temperature by

isothermal annealing processes. A glass cooled at 25 K
min1 has a fictive temperature of 853 K and is modified to
a glass with a fictive temperature of 810 K (equivalent to a
5 K min1 cooling rate) following the path shown. A glass
with a fictive temperature of 768.9 K (a cooling rate of
0.25 K min1) is shown modified to the same fictive
temperature, 810 K.

Figure 3. Locations of rhyolite samples obtained from the

Rau*ufossafjoll center and the Blahnukur locality within
the Torfajokull rhyolite complex. (top) View looking south
at a large upstanding obsidian lava lobe attached to the
eastern margin of lava D, Rau*ufossafjoll [Tuffen et al.,
2002a]. Sample JS.1.1 was obtained at the lower left margin
of the outcrop shown. (bottom) View of a columnar jointed
lava lobe in Grnagil stream valley, Blahnukur. Sample
JS.2.1 was obtained from the steep, dark-colored obsidian
surface to the left of the two people.

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Figure 4. Measured and modeled heat capacity curve for

JS.2.1. This heat capacity curve is produced by the first
heating through the glass transition interval, and the shape
of the normalized curve reflects the relaxation of the frozen
fictive temperature. The modeled normalized heat capacity
curve is based on the kinetic parameters derived from the
calibration run performed after this first heating step. The
experiment is matched to a cooling rate of 0.017 K min1
(Tf = 746 K). For reference, two other curves are shown,
which have cooling rates of 0.05 K min1 (Tf = 763 K) and
0.005 K min1 (Tf = 727 K).

more consistent with those of rapidly cooled glass fragments (
25 K min1; [Wilding et al., 1996a]). The eruption
temperature has limited influence on the cooling rate
determined in this way, and so this maximum cooling rate
is equally applicable to basaltic and rhyolitic glass compositions [Wilding et al., 2000].
[21] The minimum expected value of quench rate is
determined from a critical quench rate that avoids crystallization. This value can be determined from classic nucleation
theory [Debenedetti, 1996], in which a temperature-timetransformation (TTT) envelope is constructed (Figure 6).
The temperature-time-transformation envelope is a plot of
the structural relaxation time (t1) and the time taken to
crystallize a given volume fraction (t2), both of which are
plotted as a function of temperature. The value of the
relaxation time is again proportional to the shear viscosity,
as described by the Maxwell relation. The time taken to
crystallize a given volume fraction is determined by the
degree of undercooling (i.e., the ratio of ambient temperature
to fusion temperature), the heat of fusion, and the liquid
viscosity. This means that viscous liquids with low heats of
fusion can be cooled relatively slowly without crystallization, whereas rapid quench rates are necessary for lowviscosity liquids with a high heat of fusion. In Figure 6 the
TTT envelope for albite is shown using available heat-offusion data and viscosity data [Cranmer and Uhlmann,
1981; Stebbins et al., 1983] to estimate the approximate
critical quench rates expected for rhyolites. These data
suggest a rate of 0.05 K s1, yet the fictive temperatures
obtained for the glasses sampled as part of this study yield
values even lower than this minimum quench rate; for JS.1.1
the lowest quench rate is 0.0005 K s1, whereas for JS.2.1,
the value is 0.00005 K s1. These data suggest that the

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apparent cooling rates recorded in the glass samples do not

reflect the simple quenching of hot volcanic material in
contact with cold water or even ice but have thermal histories
that involve modification of the fictive temperature by an
annealing process.
[22] The modification of a glass structure by annealing is
easily demonstrated from the models of fictive temperature
as shown in Figure 2, which uses the Tool-Narayanaswamy
model [Crichton and Moynihan, 1988; Moynihan et al.,
1991; Narayanaswamy, 1971, 1988]. The modification of
structure involves an isothermal dwell at a temperature
within the glass transition where the relaxation time is short
enough to allow modification. If the dwell temperature is
too low, however, then no effective modification will occur.
For example, in Figure 2, if the dwell temperature were to
be 600 K, then the relaxation time values would be 3.5
107 s, and they would be even longer at room temperature
(4.5 1025 s). The original fictive temperature would be
modified by isothermal annealing following paths similar to
those shown in Figure 2, depending on whether the dwell
temperature was above or below that of the rapidly
quenched glass (Figures 3 and 4).
[23] The distributions of fictive temperatures reported
here for two rhyolite samples are assumed to reflect the
sampling of the annealing path for the modification of an

Figure 5. (a) Distribution of fictive temperature for JS.1.1

samples. The fictive temperatures for the 20 JS.1.1 glass
samples have a minimum at 832.6 K and maximum value of
909.6 K. The mean value is 872.9 K, and the distribution
is skewed to higher values. (b) Distribution of fictive
temperature for JS.2.1 samples. The 20 glass samples for
JS.2.1 are shown with values between 722.6 and 773.2 K;
the distribution is more symmetrical about the mean value
of 747.7 K. The fictive temperature and glass transition for
this sample are much lower for compositional reasons. In
both JS.1.1 and JS.2.1 the uncertainty in fictive temperature
values is 0.5 K.

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Figure 6. Temperature-time-transformation envelope for a glass-forming liquid. Classical nucleation

theory is used to plot the time taken to crystallize a given volume fraction (t2) as a function of
temperature. Also plotted is the structural relaxation time (t1) obtained by the Maxwell relation. The
modification of a fictive temperature from Tf 1 to Tf 2 is also shown (compare to Figure 2).

initially rapidly quenched value of fictive temperature.

The distribution of fictive temperatures will reflect the
characteristic form of the annealing curve and will depend
on both the kinetic parameters and dwell temperature.
This is modelled by assuming that the initial fictive
temperature is fixed by a 25 K min1 quench rate, with
different values of fictive temperature determined by the
kinetic parameters established for each individual composition. As the glass is modified, we make the assumption
that some portions of the sample are isolated from further
relaxation, and we simulate this by selecting 20 random
samples from the time-dependent annealing curve. This
results in a distribution of values reflecting the progression toward a final value of fictive temperature. The
lowest value of fictive temperature for each of the two
samples is assumed to represent the dwell temperature
and, using the constraints of dwell temperature, initial Tf
[Crichton and Moynihan, 1988; Moynihan et al., 1991],
and kinetic parameters (Tables 1 and 2), the time taken to
modify the glass structures can be calculated.
[24] For JS.1.1 the lowest value of fictive temperature
determined is 832 K. The approach to this value, plotted
as a function of time, shows that it would take 8 hours
at 832 K to achieve the modified value of fictive
temperature (Figure 7a). The distribution of fictive temperatures for 20 random samples (Figure 7b) based on
this simple annealing process does not correspond with
the distribution of 20 samples reported from the DSC
measurements (Figures 5a and 6). The distribution of 20
random samples taken for a single modification of fictive

temperatures is skewed toward low values, as shown

in Figure 7b when the annealing path comprises a
single step. The measured fictive temperatures for
JS.1.1 (Figure 5) are skewed toward higher Tf values
and suggest a more complex annealing process. A
multiple annealing step path with a series of isothermal
steps each 20 min long (Figure 7a) and with the
temperature reduced from 895 to 880 K by 20 K
increments results in the distribution of values shown
in Figure 7c. This distribution is more consistent with
that obtained from the DSC data (Figure 5a) and implies
a more complicated annealing process.
[25] The distribution of fictive temperatures for sample
JS.2.1 is approximately symmetrical about the mean
value of 745 K (Figure 5b). The mean value of fictive
temperature is much lower than the minimum value
obtained for sample JS.1.1. This may reflect either
compositional differences between the two glasses or
differences in their thermal histories. As in sample
JS.1.1 a single annealing step for the minimum value
of fictive temperature (740 K) does not result in the
distribution of fictive temperatures recorded in the glass
(Figures 8a and 8b), and we assume that there are
multiple annealing steps and a gradual reduction in dwell
temperature. The distribution of fictive temperatures
reported from the DSC experiments (Figure 5b) could
be achieved if the glass was held isothermally first at
755 K for 3.33 hours (Figure 8a) and subsequently at
750, 745, 740, and 735 K for the same time increment.
This more complicated annealing path would take

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Figure 7. Modification of the fictive temperature for JS.1.1 glass by both single and multiple annealing
steps. (a) Annealing modeled following an initial, rapid cooling step of 25 K min1, using the kinetic
parameters for this sample (Table 1). (b) Distribution of fictive temperatures, skewed toward a value of
840 K, if a single annealing step at 835 K is assumed. (c) Distribution of Tf, if an additional annealing
step is introduced (similar to that in Figure 5a).

16.5 hours, but the fictive temperatures recorded in the

glass would have a distribution (Figure 8c) similar to that
obtained from the DSC measurements.
[26] Comparison of the modified paths for fictive temperature and the DSC data suggests that the studied subglacial rhyolite glasses were held at elevated temperatures
for periods of up to 16.5 hours. This means that the surface
heat flux for these erupted materials remained high for
extended periods, with consequences for the water temperature surrounding these volcanic deposits. For many erupted
igneous rocks, including subglacial volcanic deposits, the
Carslaw and Jaeger [1959] model has been used to estimate
surface fluxes and thicknesses of cooled crust. For erupted
rhyolites [Wilson and Head, 2002] these calculations indicate that a crust 0.4 m thick would develop within 8 hours

and the surface flux would decrease from
10 6 to

104 W m2 s1. These values can be used in combination
with the thermal parameters for water and ice to calculate
the thickness of ice melted, the temperature of the resulting
meltwater, and the possibility of convection within the icebound vaults [Hoskuldsson and Sparks, 1997; Tuffen et al.,
2002b]. The estimates for the temperature of water [Wilson
and Head, 2002] and the thickness of ice melted suggests
that a thickness of ice
8 times that of the cooled crust
could melt during eruption and high water temperatures
could be maintained. The glass thermal histories suggest a
slow overall cooling dominated by isothermal dwells. This
overall cooling is much slower than that obtained by the
conductive model, although the values of surface heat
flux are initially comparable with those calculated from

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Figure 8. Modification of fictive temperature for JS.2.1 glass by single and multiple annealing
processes. (a) Isothermal annealing process for a glass cooled at 25 K min-1, modified with a single
annealing step (a decrease to 730 K), using the kinetic parameters in Table 2. (b) Histogram of fictive
temperatures, showing values are skewed toward higher values of fictive temperature. (c) A more
complicated, multiple annealing step process resulting in a distribution of Tf more consistent with the
measured values.

the Carslaw and Jaeger treatment [Roshenow et al., 1998].

The analysis of the glass fictive temperatures suggest
that the surface heat flux remains higher for longer for
these subglacial rhyolites and that high melting rates
(0.15 mm s1) would persist (Figure 9). These estimates
for surface heat flux model are much greater than those
suggested for rhyolites by Hoskuldsson and Sparks [1997],
even though the same parameters are used.

[27] Our interpretation of the thermal history of the

rhyolites therefore suggests that large volumes of ice could
be melted very rapidly, particularly in the earliest stages of
eruption (Figure 9), and will cause a corresponding rapid
rise in the buildup (and likely subsequent discharge) of
meltwater in a subglacial vault. This conclusion is supported
by both the models using isothermal spheres and also from
our calculations based on the conductive model.

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Figure 9. Surface flux for rhyolite calculated using Carslaw and Jaeger [1959] model with an eruption
temperature of 1173 K. The melting rates of ice for convective flux at different water temperatures,
calculated according to Hoskuldsson and Sparks [1997], are shown. These suggest rapid initial melting of
the ice surrounding subglacial rhyolites.

[28] The persistence of elevated temperatures in the

obsidians suggests that meltwater might be maintained in
an ice-bound vault at relatively elevated temperatures,
sufficient to drive vigorous convection prior to vault draining. If these results are applicable to subglacial eruptions
generally, the present approach has the potential to provide
detailed information on the rate at which the vault grew by
ice retreat and drained through preexisting subglacial tunnels [Smellie, 2000]. For example, melting by warm meltwater may be an order of magnitude more rapid than
melting caused solely by mechanical energy of flowing
water at the pressure melting point [Clarke, 1982]. The
surface heat flux from the simple thermal model of Carslaw
and Jaeger [1959] suggests melting rates of ice consistent
with the values of 1 40 m per day obtained by Hoskuldsson
and Sparks [1997]; however, these values are smaller
than those observed from field observations of basaltic
eruptions. For example, in the Gjalp eruption in 1996 it
took
30 hours to melt a 500 700 m thick ice sheet
[Gudmundsson et al., 1997].
[29] Thus we suggest that rhyolites may remain hot for
longer than a simple conduction model suggests, and the
most obvious possible contribution to this extended
thermal history is the release of the latent heat of
crystallization. There is evidence for such a contribution
from basaltic eruptions, in which high internal temperatures and even temperature increases have been measured in studies of advancing pahoehoe lava flows
[Keszthelyi, 1995; Keszthelyi and Denlinger, 1996]. This
suggestion is strongly supported by field evidence from
the Blahnukur center, in which the lava lobes have
thick obsidian glass rims enclosing microcrystalline
rhyolite [Tuffen et al., 2001]. Similar microcrystalline
rhyolite cores are not described from lava D in the
Rau*ufossafjoll outcrop [Tuffen et al., 2002a]. However,

our results suggesting multiple isothermal dwells and

enhanced surface heat flux imply that microcrystalline
rhyolite may be present in lava D but is presumably
hidden at the current level of exposure. Additional studies
of other subglacial volcanic centers are required before
we will understand better the role of the latent heat of
crystallization in the cooling history of subglacial volcanoes. Ideally, these studies should include independent
observations of indicators of cooling rate, such as the
distribution and density of lava surface fractures [Tuffen
et al., 2002b].

6. Conclusions
[30] Relaxation geospeedometry has been used to estimate the thermal histories of two rhyolitic obsidian samples. A series of 20 aliquots from each of the bulk samples
was used to establish the range of apparent cooling rates
by modeling the relaxation of enthalpy through differential
scanning calorimetry (DSC) measurement. The cooling
rates range from 0.5 to 0.08 K min1 for the sample with
the higher glass transition temperature (Tg; sample JS.1.1)
and are between 0.065 and 0.0035 K min1 for the lower
Tg sample (JS.2.1). These cooling rates are much slower
than the estimated critical quench rates for rhyolitic liquids
and therefore cannot reflect the simple quenching of
erupted material in cold water. The fictive temperature
can be modified by any process that allows the partial
relaxation of glass structure, and the distribution of fictive
temperatures for the rhyolite obsidian samples investigated
suggests such a structural modification.
[31] The distribution of the retained fictive temperatures
for the obsidian samples indicates a modification of previously rapidly quenched glass. The initial quench rate
estimated from simple conduction models is
35 K min1.

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Modification of this initial value is obtained by maintaining

the glass at a fixed temperature for short time intervals.
These isothermal dwells are used to estimate the distribution
of fictive temperatures sampled by the calorimetry measurements, assuming a series of random samples along the
annealing path. Surprisingly, the glass samples do not show
evidence for a single annealing step but are apparently
cooled in a series of steps. On the basis of the calorimetric
and model results of this study the fictive temperature for
glass JS.1.1 could be explained if, on eruption, the magma
initially cooled to a glass at 35 K min1, after which point,
cooling was arrested at
885 K for a short time (
0.5 hours),
at which point temperature continued to fall slowly. By
comparison, JS.2.1 appears to have cooled more gradually
following an initial dwell at 750 735 K. The temperature is
reduced by a 5, 10, 15, and finally 20 K increment before
the annealing is arrested. The annealing totals 16.5 hours.
Although the cooling histories of samples JS.1.1 and JS.2.1
show annealing of rapidly quenched samples, they do not
represent components of a similar overall cooling trend. The
cooling histories are very different, although the reasons for
these differences are not yet apparent.
[32] Acknowledgments. We are grateful to Hugh Tuffen, Dave
McGarvie, and Jennie Gilbert for introducing the outcrops to JS and,
together with Bruce Houghton, for creating fruitful discussion on subglacial
eruptions of rhyolite magmas. DSC measurements were made in the
thermochemistry facility of the University of California at Davis.

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C. E. Lesher and M. C. Wilding, Department of Geology, University of

California at Davis, Room 4440, One Shields Avenue, Davis, CA 95616,
USA. (lesher@geology.ucdavis.edu; mcwilding@ucdavis.edu)
S. Morgan, School of Earth Sciences, University of Leeds, Leeds LS2
9JT, UK. (enquiries@earth.leeds.ac.uk)
J. L. Smellie, British Antarctic Survey, High Cross, Madingley Road,
Cambridge CB3 0ET, UK. (jlsm@bas.ac.uk)
L. Wilson, Environmental Science Department, Institute of Environmental and Natural Sciences, Lancaster University, Lancaster LA1 4YQ,
UK. (L.Wilson@lancaster.ac.uk)

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