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Surface area, porosity and water adsorption properties of fine volcanic ash
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DOI: 10.1007/s00445-004-0370-x

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Bull Volcanol (2005) 67:160–169
DOI 10.1007/s00445-004-0370-x
RESEARCH ARTICLE
Pierre Delmelle · Fr
d
ric Villi
ras · Manuel Pelletier
Surface area, porosity and water adsorption properties
of fine volcanic ash particles
Received: 14 March 2003 / Accepted: 19 April 2004 / Published online: 10 July 2004

Springer-Verlag 2004
Abstract Our understanding on how ash particles in vol-
canic plumes react with coexisting gases and aerosols is
still rudimentary, despite the importance of these reac-
tions in influencing the chemistry and dynamics of a
plume. In this study, six samples of fine ash (<100 mm)
from different volcanoes were measured for their specific
surface area, as, porosity and water adsorption properties
with the aim to provide insights into the capacity of sil-
icate ash particles to react with gases, including water
vapour. To do so, we performed high-resolution nitrogen
and water vapour adsorption/desorption experiments at
77 K and 303 K, respectively. The nitrogen data indicated
as values in the range 1.1–2.1 m2/g, except in one case
where a as of 10 m2/g was measured. This high value is
attributed to incorporation of hydrothermal phases, such
as clay minerals, in the ash surface composition. The data
also revealed that the ash samples are essentially non-
porous, or have a porosity dominated by macropores with
widths >500 . All the specimens had similar pore size
distributions, with a small peak centered around 50 .
These findings suggest that fine ash particles have rela-
tively undifferentiated surface textures, irrespective of
the chemical composition and eruption type. Adsorption
Editorial responsibility: J. Gilbert
P. Delmelle ())
Unit des sciences du sol,
Universit catholique de Louvain,
Croix du sud 2/10, B-1348 Louvain-la-Neuve, Belgium
e-mail: pdelmell@ulb.ac.be
Tel.: +32-2-650-2246
Fax: +32-2-650-2243
F. Villiras · M. Pelletier
Laboratoire Environnement et Minralurgie,
Ecole Nationale Suprieure de Gologie,
UMR 7569 INPL & CNRS,
BP 40, F-54501 Vandoeuvre-ls-Nancy Cedex, France
Present address:
P. Delmelle, Department of Earth & Environmental Sciences,
Universit Libre de Bruxelles,
Ave. F. Roosevelt 50, B-1050 Brussels, Belgium
isotherms for water vapour revealed that the capacity of
the ash samples for water adsorption is systematically
larger than predicted from the nitrogen adsorption as
values. Enhanced reactivity of the ash surface towards
water may result from (i) hydration of bulk ash con-
stituents; (ii) hydration of surface compounds; and/or (iii)
hydroxylation of the surface of the ash. The later mech-
anism may lead to irreversible retention of water. Based
on these experiments, we predict that volcanic ash is
covered by a complete monolayer of water under ambient
atmospheric conditions. In addition, capillary condensa-
tion within ash pores should allow for deposition of con-
densed water on to ash particles before water reaches
saturation in the plume. The total mass of water vapour
retained by 1 g of fine ash at 0.95 relative water vapour
pressure is calculated to be ~102 g. Some volcanic im-
plications of this study are discussed.
Keywords Volcanic ash · Specific surface area ·
Porosity · Nitrogen adsorption · Water vapour adsorption ·
Volcanic plume
Introduction
Volcanic plumes in the atmosphere are heterogeneous
environments in which gases, aerosols and silicate ash
particles can coexist and interact in various ways. While
considerable progress has been made over the last 10
years in understanding the physics of these plumes (see
Sparks et al. 1997), it is only recently that chemical
models have been developed to investigate the fate of
volcanic gases (Tabazadeh and Turco 1993, Herzog et al.
1998, Textor et al. 2003). The incentive came from the
growing awareness that several gases and aerosols present
in erupting and non-erupting plumes can affect the at-
mosphere’s composition, climate and environment (Graf
et al. 1998, Robock 2000). These simulations have al-
ready provided fascinating results, but concurrently they
also highlight the need for observational and experimental
data.

Among the numerous reactions occurring in a volcanic
plume, those involving silicate ash particles appear to be
important. Several studies have revealed that ash particles
have a significant potential for scavenging sulphur and
halogen gases from the plume (e.g., Rose 1977, Oskars-
son 1980, Varekamp et al. 1984). The main evidence for
this comes from leachate studies, which indicate that ash
from fall deposits contains various amounts of sulphur,
chlorine and fluorine in the forms of soluble salts. Ash
particles in volcanic plumes are also thought to be coated
with a film of condensed water well below 100% relative
humidity due to the presence of hygroscopic compounds
on their surface. This property enhances ash aggregation
processes, which in turn influence sedimentation of par-
ticles from the plume (Gilbert and Lane 1994).
The presence of water and soluble salts on the ash
surface is certainly of importance, because these com-
pounds directly affect the surface properties of the ash,
and hence its capacity to react with other plume compo-
nents. The necessity of incorporating the reactivity of ash
towards water vapour (the most abundant gas in volcanic
emissions) in plume chemistry models has been empha-
sized recently (Textor et al. 2003). There is also a human
health aspect to consider with water-coated ash, since
soluble metals that can be associated to it may contribute
to cell injury and inflammatory changes in the lung (Costa
and Dreher 1997, Ghio and Devlin 2001).
Quantification of the capacity of volcanic ash particles
to react with gases and water vapour in the eruption plume
is difficult, since it depends on several physico-chemical
variables. It is generally admitted that the key parameters
that determine the capacity of a solid to react with a gas
are its textural properties, namely the specific surface area,
as, or surface area per unit mass, and porosity (Gregg and
Sing 1982). While techniques based on the physical sorp-
tion of gases (such as nitrogen, argon, krypton) are rou-
tinely used in the field of material sciences to characterize
the as and porosity of finely divided solids (Gregg and
Sing 1982), they have been rarely applied to the study of
volcanic ash particles. In fact, the as of ash is typically
derived from geometric considerations (e.g., Armienta et
al. 2002), although the method does not account for the
contribution of surface topography and porosity (Papelis et
al. 2003). Only a few published works have reported on
direct as measurements of volcanic ash (e.g., Rothenberg
et al. 1988, Horwell et al. 2003a), and data on porosity are
virtually lacking. Similarly, the water adsorption potential
of volcanic ash has never been investigated.
This research was undertaken to determine the as and
pore size-distribution of fine (<100 mm) volcanic ash
particles, and to quantify the amount of water molecules
that can be adsorbed by them by measuring high resolu-
tion nitrogen and water vapour adsorption/desorption
isotherms. Samples were chosen to represent various bulk
chemical compositions and types of production. While
Heiken and Wolhetz (1985) generated a remarkable com-
pendium of volcanic ash chemical composition and mor-
phology using scanning electron microscopy, the present
study aims at contributing to a better characterization of
161
volcanic ash by the analysis of their surface properties
(e.g., Horwell et al. 2003a).
Materials and methods
Volcanic ash samples
In this study the term ash is used for silicate fragments <2 mm
which have been erupted (in the liquid or solid state) by a volcano
and subsequently deposited on the ground. Ash from six volcanoes,
including El Chichn (EC), Hekla (HE), Mt. St. Helens (MSH),
Pinatubo (PIN), San Cristobal (SC) and Soufrire Hills (SH) were
studied. EC, HE, MSH and PIN corresponded to fall deposits from
Plinian and/or coignimbrite clouds derived from magmatic (PIN) or
phreatomagmatic (EC, HE, MSH) eruptions. The SH ash was col-
lected after a lava dome had collapsed at the summit of the volcano.
Except the PIN sample, the ash had not been exposed to rain prior
to collection. A brief description of the ash specimens is given in
Table 1.
Prior to analysis, bulk samples were dry-sieved to a particle size
<100 mm. This particle size was chosen to minimize the influence
of large particles having low as. Ash particles <100 mm may re-
present a substantial contribution (>40%) to tephra deposits from
explosive volcanic eruptions (Zimanowski et al. 2003). Fine ash
can also be lifted to high altitudes and can remain suspended for
several days in the atmosphere before sedimenting (Sparks et al.
1997). The surface and bulk chemistry of the ash samples will be
reported elsewhere. Briefly, they vary in composition from basaltic
to dacitic, with a SiO2 content ranging from ~55 to 66 weight %.
The dominant crystalline mineral assemblage of the ash samples, as
determined by X-ray diffraction (XRD), consists of plagioclases,
feldspars and sometimes quartz. Anhydrite (CaSO4) was identified
in the EC ash and is one of the magmatic microphenocrysts (Luhr et
al. 1984, Varekamp et al. 1984). Anhydrite was also present in the
SC ash, but its origin is probably hydrothermal, as suggested by
subsequent scanning electron microscopy observations which re-
vealed large crystals and altered surface patterns. In support of a
hydrothermal contamination of the surface of SC ash, XRD features
typical of clay minerals were also observed for this sample. The
ubiquitous presence of an amorphous phase in the ash was sug-
gested by a XRD broad band around 3 . However, the relative
proportion of this material varied from one sample to another: high
in HE, intermediate in EC, MSH and PIN, and low in SC and SH.
The low content of amorphous material detected in the SH sample
is consistent with its dome origin (Horwell et al. 2003b).
Nitrogen adsorption-desorption at 77 K
Nitrogen adsorption-desorption isotherms (i.e., volume of nitrogen
adsorbed at 77 K vs. relative pressure P/P0, where P is the equi-
librium pressure of the adsorbing gas at that temperature and P0 is
the vapour saturation pressure) were performed using a step-by-step
automatic setup built in the Laboratoire Environnement et Min
r-
alurgie. Pressure measurements were recorded using two Baratron
type pressure sensors (0–103 and 0–105 Pa). A similar type of
sensor (0–105 Pa) recorded nitrogen saturation pressures. All ex-
Table 1 Description of the volcanic ash samples used in this study
Sample name Volcano and location Eruption date
EC El Chichn, Mexico Apr. 1982
HE Hekla, Iceland May 1970
MSH Mt. St. Helens, USA May 1980
PIN Pinatubo, Philippines Sept. 1990
SC San Cristobal, Nicaragua Febr. 2000
SH Soufrire Hills, Montserrat Oct. 1999
162
periments were carried out with ultra-pure nitrogen (>99.9995%).
Prior to each experiment, about 1 g of ash was outgassed in situ
overnight at 120C at a residual pressure <0.1 Pa.

Water vapour adsorption-desorption at 303 K

Since water vapour is not an ideal gas, its adsorption cannot be

studied by the classical volumetric techniques. Water vapour ad-
sorption-desorption isotherms were performed in a continuous
gravimetric apparatus built around a Seratam MTB 10–8 symmetric
balance. Pressures were measured with a Pirani gauge for the 0.01–
10 Pa range and a Texas fused silica Bourdon tube automatic gauge
for the 1–65103 Pa range. Prior to each experiment, about 1 g of
ash was outgassed in situ overnight at 120C at a residual pressure
<0.1 Pa. Water vapour is supplied to the adsorption cell from a
source kept at 41C at a slow flow rate through a Grandville-Philips
leak valve. The adsorption isotherms (i.e., volume of water ad-
sorbed at 303 K vs. P/P0) were recorded directly on an X-Y re-
corder. Desorption isotherms were obtained by connecting the
balance and the vacuum pumps to the leak valve. Adsorption-de-
sorption isotherms were obtained for 0.005<P/P0<0.98.

Results and discussion

Surface area measurement

Nitrogen adsorption-desorption isotherms for the six ash

samples are presented in Fig. 1. The EC, HE, PIN and SH
ash samples showed type II isotherm in the Brunauer
classification (Brunauer et al. 1938) which is the normal
form of isotherm obtained with a nonporous or macrop-
orous adsorbent (Gregg and Sing 1982). It represents
unrestricted monolayer-multilayer adsorption, and sug-
gests a material whose pores and voids communicate with
the surface of the particle (Gregg and Sing 1982). An
ideal type II isotherm is presented in Fig. 2. MSH and SC
depart from this behaviour, because they both exhibited a
well-defined adsorption/desorption hysteresis (where vol-
ume of gas adsorbed at a given relative pressure is not
equal during adsorption and desorption), which is gener-
ally associated with capillary condensation taking place in
slit-like mesopores (20–500 ) at a certain relative pres-
sure (Gregg and Sing 1982). Capillary condensation oc-
curs when the nitrogen multilayer begins to behave like
normal liquid and fills pores. The hysteresis closure point
corresponds to P/P0
0.45, and this value is thought to be
almost independent of the nature of the adsorbent but is a
characteristic for nitrogen at its boiling point (Sing et al.
1985). Besides the structural heterogeneity of ash, com-
plex pore networks, with narrow links connecting larger
pores (Mason 1982) also may be responsible for the
hysteresis noted for MSH and SC.
The nitrogen adsorption data were modeled using the
two-parameter BET analysis (Brunauer et al. 1938) to cal-
culate the as (m2/g) of the ash according to:
V m NA s
as ¼ ð1Þ
22:414
In Eq. 1, Vm is the volume necessary to cover the
surface of the ash with a complete monolayer of gas mol-
ecules; NA is the Avogadro number, s is the cross-sec-
Fig. 1 Volume of gas (at STP) sorbed during nitrogen adsorption
and desorption at 77 K plotted vs. relative pressure P/P0 for El
Chichn (EC), Hekla (HE), Mt. St. Helens (MSH), Pinatubo (PIN),
San Cristobal (SC) and Soufrire Hills (SH) ash (<100 mm)
tional area of the probe molecule (s=16.2 2/molecule for
nitrogen, Sing et al. 1985) and 22.414 is the molar volume
of gas at standard temperature and pressure (STP). The
value of Vm is obtained from application of the BET
equation in the relative pressure range 0.05<P/P0<0.15:
Vm C PP
0
V ¼   ð2Þ
1  PP 1  PP þ C PP
0 0 0
where V is the volume of gas adsorbed at equilibrium
pressure and C is related exponentially to the enthalpy of
adsorption in the first adsorbed layer. For the studied
solids, the error on as determination is estimated to be
€ 0.2 m2/g.
The experimental values of as, Vm and C for the ash are
compiled in Table 2. The ash specimens had similar as
values of ~1–2 m2/g, except SC which displayed a sig-
nificantly higher as of ~10 m2/g. For comparison, reported
 163

samples displayed relatively low C values (Table 2) as

Fig. 2 Ideal type II isotherm showing the different adsorption
steps: a Adsorption of the first layer and filling of the micropores. b
Second layer adsorption and filling of intermediary pores. c Mul-
tilayer adsorption and filling of mesopores. d Three-dimensional
condensation on macropore surfaces and into macropores
compared to other mineral surfaces (Bardot 1998, Cha-
merois 2000). Whitham and Sparks (1986) also reported
low BET C values of 15–48 for three pumices from
plinian deposits. In contrast, SH and SC showed signifi-
cantly higher C values of 94 and 112, respectively.
The nitrogen data indicated that C tends to decrease in
ash with relatively high amounts of amorphous material
(i.e., EC, HE, MSH and PIN) as estimated semi-quanti-
tatively by XRD. This may simply reflect the low surface
energy of amorphous silicates (Legrand et al. 1990, Vil-
liras et al. 2002) relative to crystallized silicates, in-
cluding phyllosilicates (Berend 1991, Bardot 1998, Cha-
merois 2000). The association of anhydrite and clay min-
erals with the SC ash may result in the high C value
obtained. For SH ash, the high C value probably relates to
its low concentration in amorphous silicate material.

as values for fly ash produced from coal-fired power
plants are in the range ~1–40 m2/g (e.g., Rothenberg
1980, Praharaj et al. 2002) and as<10 m2/g were measured
for Mt. St. Helens ash particles with aerodynamic diam-
eters <7.5 mm (Rothenberg et al. 1988). In another study,
Horwell et al. (2003a) found that respirable ash from
Soufrire Hills volcano had as ranging from 2.8 to 7.5
m2/g, with the highest value observed for a mixed ash
sample that had been leached and weathered.
The high as value (~10 m2/g) measured for SC may
be due to the presence of clay minerals, which typically
develop large as. Alternatively, it may reflect that the
grain size distribution of this ash sample was dominated
by very fine particles with comparatively high as. Based
on geometric considerations and assuming that the ash is
spherical with density of ~2.5–3.0106 g/m3, we calcu-
lated that particles with diameter 0.1 mm are required to
produce as values on the order of 10 m2/g. Even if pres-
ent, particles in this range are not thought to constitute the
bulk of SC ash, and the high as is preferentially attributed
to clay minerals.
The value of the parameter C in Eq. 2 is assumed to
give an indication of the magnitude of the adsorbent-
adsorbate interaction energy (Sing et al. 1985). EC, HE,
MSH and PIN have low energy surfaces because these
Porosity measurement
According to the IUPAC (1972) convention, pores are
characterized by their diameters, where micro- (<20 ),
meso- (20–500 ) and macropores (>500 ) are identi-
fied. The total mesopore volume in the ash can be derived
from the amount of nitrogen vapour adsorbed at P/
P0=0.95 by assuming that the pores are filled with con-
densed nitrogen in the normal liquid state (Gregg and
Sing 1982). This volume is converted into a geometric
volume, VP, value using the density of liquid nitrogen at
77 K (0.808 g/cm3). As shown in Table 2, VP did not
exceed a few mm3/g in all ash samples, except SC
(VP=19 mm3/g). In addition, the value of VP was roughly
proportional to that of as. This simply suggests that ni-
trogen adsorption through capillary condensation is of
minor importance, leaving multilayer adsorption on the
ash surface as the dominant process.
Combinations of different pore types can make inter-
pretation of isotherm shape difficult. For example, Gregg
and Sing (1982) pointed out that an adsorbent featuring a
Type II isotherm can still have microporosity. The t-plot
method and its extensions (de Boer et al. 1966) provide a
simple means to document the presence of porosity from
nitrogen adsorption data. Application of this method to

Table 2 Experimental parame- EC HE MSH PIN SC SH

ters for the six ash samples as
derived from the nitrogen and Nitrogen
water vapour adsorption iso- Vm (cm3/g) 0.35 0.26 0.37 0.48 2.2 0.47
therms C 62 50 69 43 112 94
as (m2/g) 1.5 1.1 1.6 2.1 9.7 2.0
VP, 0.95(mm3/g) 4.4 3.3 4.1 4.9 19.0 4.7
Water vapour
Vm (cm3/g) 1.29 1.31 2.1 1.86 4.93 1.38
C 43 72 20 20 35 31
ass=10.6 (m2/g) 3.7 3.7 6.0 5.3 14.0 3.9
ass=14.8 (m2/g) 5.1 5.2 8.3 7.4 19.6 5.5
VP,0.95 (mm3/g) 13.0 14.0 10.9 5.5 20.6 8.7
as: specific surface area; C : BET constant Vm: volume necessary to cover the surface of the ash with a
complete monolayer of gas molecules.; VP: geometric pore volume
164

Fig. 3 Pore-size distribution for the six ash samples studied as

calculated using the Barrett-Joyner-Halenda procedure (Barrett et
al. 1951). All samples show a similar distribution. SC ash (dashed
curve) differs from the other samples in that it has a significantly
higher number of pores

the isotherms obtained for the six ash samples sup-

ports the result that there was no detectable micropores.
Thus, fine ash particles are essentially non-porous, or
have a porosity dominated by macropores with diameters
>500 .
Pore size distributions for volcanic ash can be calcu-
lated from the nitrogen adsorption by inferring pore ge-
ometry and using the Barrett-Joyner-Halenda proce-
dure (Barrett et al. 1951). This model assumes a cylin-
drical pore model and accounts for capillary condensation
in the pores using the classical Kelvin equation. Pore
size distribution is represented by the derivative dV/dD
(1010 m/) as a function of pore diameter, D (). As
shown in Fig. 3, the six ash samples had similar pore size
distributions, with a small peak centered around 50  and
comparatively low amounts of pores of higher diameter. Fig. 4 Volume of vapour (at STP) sorbed during water adsorption
and desorption at 303 K plotted vs. relative pressure P/P0 for El
However, SC ash exhibited significantly higher pore Chichn (EC), Hekla (HE), Mt. St. Helens (MSH), Pinatubo (PIN),
numbers (Fig. 3). This feature probably contributes to the San Cristobal (SC) and Soufrire Hills (SH) ash (<100 mm)
high as measured for this sample.

shape of these water isotherms also could reflect existence

Water adsorption measurement
Fig. 4 shows the water vapour adsorption/desorption
isotherms on the ash samples at 303 K. The MSH, PIN,
SC and SH isotherms were relatively common for water
adsorption. Again, SC was distinct from the other samples
because it had a far greater adsorption of water. The rapid
increase in the amount of water adsorbed in the high
relative pressure range (i.e., P/P0>0.6) suggests that de-
position of liquid water occurred before the saturation
point. This probably accounts for capillary condensation
whereby multilayer vapour adsorption proceeds to the
point at which pore spaces are filled with liquid separated
from the gas phase by menisci. EC and HE displayed
more complex isotherms than the other samples, and their
adsorption curves share some similarities with those ob-
tained for water adsorption on swelling clay minerals,
with several adsorption steps (Villiras et al. 1997). The
of pores of well-defined sizes (Gregg and Sing 1982).
As usually observed with water, all isotherms featured
a hysteresis loop between adsorption and desorption
which persisted to low pressure. The amount of water
present on the desorption branch was roughly twice that
on the corresponding adsorption branch. In addition, ir-
reversible water retention (i.e., all adsorbed water is not
desorbed at the lowest attainable pressures) occurred in
the cases of PIN ash, and to a lesser extent in EC ash.
Potential causes of hysteresis are discussed later in this
section.
A BET treatment (Eq. 2) can also be applied to the
water isotherm data in the relative pressure range 0.05<P/
P0<0.15. This yielded values for the C parameter in
the range of ~20–72 (Table 2). The ash samples have
C values that tend to be higher than those common-
ly reported for adsorption of water on clay minerals
(C<20, Berend 1991, Bardot 1998). Values of C above 40

in clay minerals are typically associated with microp-
orosity and/or with surface hydration phenomena (Sau-
zat 1998). Since the ash samples were shown to be non-
microporous, this result suggests that the ash surface is
reactive towards water molecules.
The volume of water adsorbed as a monolayer on the
ash surfaces ranged from about 1.3 to 4.9 cm3/g (Table 2).
These values are 2 to 6 times higher than those obtained
for nitrogen adsorption. Accordingly, water molecules
also probed comparatively high as for the ash samples,
with values ranging from 3.7 to 14.0 m2/g, or from 5.1 to
19.6 m2/g (Table 2), depending on the s value chosen for
describing the mode of water packing on the mineral
surface (i.e. s(H2O)=10.6 2/molecule, or s(H2O)=14.8 2/
molecule; Hagymassy et al. 1969). Thus, the capacity of
volcanic ash for water adsorption is larger than its ca-
pacity for nitrogen adsorption. Small discrepancies be-
tween nitrogen and water adsorption data are usually
noticed for silica-containing materials. In fact, compara-
tively low water adsorption has been observed on low
energy solid surfaces such as amorphous silica (Legrand
et al. 1990, Chamerois 2000). Thus, the experimental
water adsorption data revealed that water molecules are
able to interact strongly with the surface of the ash.
Water differs from nitrogen in that it can be bound
chemically to mineral surfaces, and even reacts with the
bulk of minerals and causes a change in their crystalline
structures and compositions. Increased amount of water
adsorption on solids has been evidenced in the case of
specific hydration of bulk constituents. Silicate minerals
such as smectite clays and lamellar silica are known to
exhibit distinct water adsorption and swelling properties
in relation to hydration of interlamellar cations (Berend
1991, Berend et al. 1995, Cases et al. 1992, Eypert-
Blaison et al. 2001). Hydration reaction of calcium within
poorly organized solids (e.g., cements and corresponding
amorphous calcium-silicate hydrates) also may result in a
dramatic increased in water adsorption (Sauzat 1998,
Baroghel-Bouny et al. 1999). It is known that fine vol-
canic ash sometimes exhibits hydraulic (self-cementing)
properties and behaves as natural pozzolans (Shi 2001).
Hydration of surface compounds (ionic species, hygro-
scopic salts) is another mechanism that may lead to in-
creased reactivity of the ash surface towards water (Gilber
and Lane 1994). Finally, hydroxylation of the silicate
surface with formation of silanol groups following dis-
sociation of adsorbed water molecules also may result in
increased reactivity of ash towards water (Legrand et al.
1990).
Identification of the dominant cause of enhanced water
adsorption for each ash sample is difficult. Insights may
be obtained by comparing the ash mesopore volume
probed by nitrogen with that probed by water. Similar to
nitrogen data, the amount of water adsorbed at P/P0=0.95
gives an estimate of the total volume of accessible pores
in the ash. The geometric pore volume probed by water,
VP(H2O), ranged from 5 to 21 mm3/g. In the cases of EC,
HE and SH, the VP(H2O) /VP(N2) ratio was significantly
greater than one, suggesting that water probed additional
165
Table 3 Comparison between nitrogen and water vapour specific
surface areas and geometric pore volumes for the six ash samples
studied
EC HE MSH PIN SC SH
as(H2O, s=10.6) /as(N2) 2.5 3.4 3.8 2.5 1.4 2.0
as(H2O, s=14.8) /as(N2) 3.4 4.7 5.2 3.5 2.0 2.8
VP(H2O) /VP(N2) 3.0 4.2 2.7 1.1 1.1 1.9
voids (internal and trapped porosity), which were not
accessible to nitrogen. Convincingly, the as(H2O)/as(N2)
and VP(H2O) /VP(N2) ratios of each ash display similar
values, within the range defined by the 10.6 and 14.8 2
cross-sectional areas for adsorbed water molecules. Dif-
fusion of water molecules in swelling clay minerals and/
or calcium-silicate hydrates (e.g., Bihannic 1998, Sauzat
1998) present on/in the ash may well account for these
results. The textural properties of the EC, HE and SH ash
appear to depend, at least partly, on relative humidity. In
the case of EC, hydration of anhydrite present as phe-
nocrysts also should contribute to enhance water adsorp-
tion.
In contrast to the EC, HE and SH ash samples, the PIN
and SC specimens showed VP(H2O) /VP(N2) ratios close to
one, indicating that water and nitrogen probed the same
volume of pores, and in turn that water diffusion in clay
minerals and/or calcium-silicate hydrates did not affect
the ash’s water adsorption potential significantly. The
water-derived as values obtained for these two samples
may therefore mainly reflect hydration of surface ionic
compounds and/or hydroxylation of the silicate surface.
Since the surface of the PIN ash sample studied was
shown to be almost devoid of adsorbed soluble com-
pounds (A. Bernard, personal communication 2003), hy-
droxylation may be the prevalent process occurring dur-
ing water adsorption. This is not true for SC ash, for
which soluble anhydrite was ubiquitous on the ash sur-
face. In this case, the water adsorption potential is best
explained in terms of hydration reactions. Based on the
VP(H2O) /VP(N2) and as(H2O) /as(N2) ratio values obtained for
SC (Table 3), one may infer that such reactions were
predominant over water diffusion in clay minerals. This
would also explain why, opposite to EC, the SC sample
did not display a complex isotherm shape upon water
vapour adsorption, despite the presence of clay phases.
MSH ash had an intermediate behaviour upon water ad-
sorption, suggesting occurrence of both specific and
structural hydration phenomena.
Appearance of an adsorption/desorption hysteresis at
all water vapour relative pressures also revealed the tex-
tural properties of volcanic ash. While the causes for
hysteresis are difficult to identify definitively, several
factors may be proposed. The presence of adsorbates can
sometimes induce swelling of adsorbents which leads to
low-temperature hysteresis as new surface sites open up
during desorption (Tvardovski et al. 1997). For silica-
containing solids, water desorption hysteresis at low rel-
ative pressure can result from differences in the energy of
hydration and dehydration of surface compounds such as
166
swelling clay minerals, lamellar silica and non-swelling
minerals exchanged with various cations (e.g., Cases et al.
1992, Berend et al. 1995, Bardot 1998; Eypert-Blaison et
al. 2002). Increased hydration of the solid surface at high
relative water vapour pressure also may produce a hys-
teresis (Sauzat 1998). Irreversible hydroxylation of sur-
faces certainly can cause hysteresis across the relative
pressure range (Gregg and Sing 1982, Legrand et al.
1990, Chamerois 2000). Finally, both positive and nega-
tive hysteresis may result from dissolution of the solid
surface, depending on whether adsorption sites are cre-
ated or destroyed by water-solid interaction.
Based on previous findings, the origin of hysteresis for
the EC, HE, SC and SH samples may be linked to the
presence of swelling mineral phases and/or to surface
hydration at high relative pressure. In contrast to the other
specimens, the PIN and EC samples showed excess water
that persisted when relative pressure decreased to zero.
Infrared spectroscopy was used to investigate the pres-
ence of chemisorbed water on the solid surface of the ash
after the adsorption/desorption experiment. These data
(not shown) revealed a significant increase in the intensity
of the O-H stretching broad band region near 3590 cm1
only for PIN ash, thus supporting the previous assumption
that irreversible hydroxylation affected its surface. For the
EC sample, the lack of inception point for the hysteresis
(the low pressure limit of the hysteresis loop) may ten-
tatively be attributed to trapping of water by bulk anhy-
drite.
Volcanic implications
With one exception (SC), the as, pore size distribution
and pore amounts were remarkably constant across the
volcanic ash samples studied (Table 2, Fig. 3), and
therefore there seems to be no correlation between the
ash textural properties and surface chemical composition.
Our results also suggest that fine ash particles produced
by phreatomagmatic (e.g., EC) and magmatic (e.g., PIN)
eruptions have relatively undifferentiated surface tex-
tures, although different magma fragmentation regimes
(and hence energies) are involved in such eruptions
(Wohletz 1983). By contrast, disruption of hydrother-
mally altered and weathered country rocks during vol-
canic eruptions is expected to produce ash with com-
paratively large as and high porosity (e.g., SC).
There is growing concern in the volcanological com-
munity about the adverse respiratory effects of human
exposure to volcanic ash (Baxter et al. 1999, Horwell et
al. 2003a, 2003b). This has been heightened by the long-
lived and ongoing eruption of Soufrire Hills volcano. In
general, medical studies have shown that as plays a con-
siderable role in determining the bio-reactivity of respi-
rable mineral particles in the lung (e.g., Fubini et al. 1999,
Hetland et al. 2001, Tran et al. 2000). Our results suggest
that ash containing a hydrothermal component develop a
higher as than the other ash samples. Therefore, the risk of
toxicity may be enhanced upon exposure to such ash
particles. The likely presence in this hydrothermally-al-
tered ash of the silica polymorph cristobalite (a mineral
that can cause silicosis and which is a common product of
alteration of volcanic rocks by hydrothermal fluids) adds
to the adverse effects (Baxter et al. 1999). In general, the
health hazard potentially associated with this ash material
should be limited in time, since it is usually erupted at the
beginning of a more violent explosive event. Neverthe-
less, a chronic and local health hazard may exist if the
volcanic activity consists of small ash eruptions occurring
over periods of several months. This may be the case for
volcanoes that host an active hydrothermal system at their
summit. For example, the last ash event at San Cristobal
lasted a few months and affected several villages and
towns downwind (Smithsonian Institution 2000a, 2000b).
The total mass of water vapour that can be uptaken by
ash particles was estimated from the value of VP(H2O) at P/
P0=0.95 (Table 2). According to Eq. 2, this amount of
water vapour should be temperature dependent, since
C
eDE/RT (where DE is the difference between the heat
of condensation in the first layer and the heat of con-
densation for the second and subsequent layers). How-
ever, at P/P0 approaching unity, Eq. 2 becomes inde-
pendent of C, and consequently temperature-independent.
Such conditions occur when water in the plume starts to
condense, i.e., at an altitude several kilometers above the
vent depending on initial atmospheric humidity and
eruption parameters (Tabazadeh and Turco 1993, Herzog
et al. 1998). Based on the experimental data reported in
Table 2 (excluding SC), the average mass of water re-
tained by 1 g of ash <100 mm is about 102 g. For smaller
grain sizes, the amount of water that can be adsorbed
should be higher, since the as of low-porosity particles
increases as particle diameter decreases. Conversely, the
water adsorption potential should diminish with increas-
ing grain size. In the case of the eruption of El Chichn,
which produced 0.3 km3 (dense rock equivalent at
2.6106 g/m3) of ash (Varekamp et al. 1984), about
7.8 Tg of water may have been retained at the surface of
ash. This mass of water corresponds to about 1% of the
estimated total amount of water erupted (~600 Tg, J.
Luhr, personal communication 2003).
Although the total amount of water adsorbed on to ash
particles in a volcanic plume appears to be relatively
small, it certainly plays a significant role in various phys-
ical and chemical processes. For example, deposition of
liquid water on to the surface of ash can occur due to
capillary condensation before water vapour in the plume
reaches the saturation point. Furthermore, water conden-
sation at low relative humidities will be facilitated by the
presence of many hygroscopic compounds in volcanic
plumes (e.g., Rose 1977, Gilbert and Lane 1994). The
presence of condensed water on the ash surface will en-
hance scavenging of HCl and HF from the plume due to
enhanced acid dissociation kinetics. It should also facili-
tate the catalyzed conversion of SO2 to sulfate (Eatough
1994). In turn, acid uptake by the wetted ash should lead
to low interfacial pH values, possibly causing partial

dissolution of the glass and silicate minerals of the ash
surface (Rose 1977, Spadaro et al. 2002).
Dust particles, in general, do not make good ice nuclei
(Bacon and Sarma 1991) and volcanic ash probably be-
haves similarly (Gilbert and Lane 1994). However, there
is evidence for occurrence of ash particles encased with
ice in volcanic clouds (Rose et al. 1995). Adsorption of
water vapour and capillary condensation on the surfaces
of ash provide a mechanism by which ash particles may
become coated with ice as the temperature in the rising
eruption column decreases. The temperature at which
freezing of the water film coating occurs is not known,
since it depends on the concentrations of dissolved salts in
the adsorbed water. The dynamics and kinetics of gas
(SO2, HCl and HF) uptake by, and subsequent release
from volcanic ash particles coated with ice is poorly
constrained, but these processes may be essential to de-
scribe volcanic inputs into the troposphere and strato-
sphere accurately (e.g., Textor et al. 2003).
Water condensation on ash also may affect the air-
borne lifetime of particles. A direct effect of adsorbed
liquid water is to increase ash density, and thus the ter-
minal fall velocity of particles. Gilbert and Lane (1994)
demonstrated that liquid-coated ash is able to collide and
coalesce with small dry and wet particles, thereby form-
ing accretionary lapilli. This aggregation process strongly
dictates sedimentation of fine particles from volcanic
plumes and is responsible for simultaneous deposition of
a wide range of particle sizes. The fact that liquid water
may exist on the surfaces of ash particles before water
starts to condense in the eruption column also supports the
idea that aggregation may occur within eruption columns
(Gilbert and Lane 1994).
Conclusion
The as of the sub-100 mm fraction of six volcanic ash
samples was determined by applying a BET treatment to
nitrogen adsorption isotherms. Five of the six samples
studied showed a low as in the range 1.1–2.1 m2/g, which
is essentially due to external surface topography. For
these specimens, porosity measurements indicated that
the area contributed by ash pores is not significant, i.e.,
the ash samples are essentially non-porous, or have a
porosity dominated by macropores. Apparently, the tex-
tural properties of the ash do not depend on the bulk
chemistry, nor on the eruption style. Rather, the small
variations observed may relate to differences in the
crystallo-chemical composition of the surface of the ash.
One ash sample (SC) was notably different from
the others in that it exhibited a significantly higher as
(~10 m2/g) and had a larger number of pores, although
its pore size distribution was similar. These differences
are attributed to the nature of the ash surface, which has
probably been altered by hydrothermal fluids, and con-
ois M, Uriot JP, Michot L, Masion A,
tains phases such as clay minerals and anhydrite. Never-
theless, like the other samples, SC ash is not microporous.
167
Comparison of the nitrogen and water adsorption data
revealed that the standard BET as cannot be used directly
to predict relative capacities of ash for water adsorption.
In general, the ash showed an enhanced reactivity towards
water molecules. This may result from (i) hydration of
bulk ash constituents; (ii) hydration of surface com-
pounds; and/or (iii) hydroxylation of the surface of the
ash. The total mass of water vapour retained by 1 g of fine
ash averaged to ~102 g. It is likely that ash particles
spend a substantial part of their airborne lifetime coated
with liquid condensate.
The experimental data presented here offer new in-
sights for better modelling physico-chemical processes in
a volcanic plume, including formation of hydrometeors,
uptake of sulphur and halogens by ash and aggregation of
silicate particles. They are also anticipated to contribute
to a better assessment of the environmental and health
hazards posed by ash fall deposits. To fully reach these
goals, future studies should focus on the dependence of
the textural and hydration properties of volcanic ash on
particle size, morphology and crystallo-chemical compo-
sition.
Acknowledgements P.D. gratefully acknowledges the financial
support of the Fonds National de la Recherche Scientifique
(F.N.R.S.). The authors thank N. Oskarsson (Nordic Volcanic In-
stitute), J.C. Varekamp (Wesleyan University), A. Bernard (Uni-
versit Libre de Bruxelles) and S. Young (Montserrat Volcano
Observatory) who kindly supplied some of the ash samples. C.
Horwell and S. Lane provided a critical and constructive review of
this paper.
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