Journal of Volcanology and Geothermal Research 175 (2008) 120–132

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Journal of Volcanology and Geothermal Research

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j vo l g e o r e s

Magma degassing process during the eruption of Mt. Unzen, Japan in 1991 to 1995:
Modeling with the chemical composition of volcanic gas
Takeshi Ohba a,⁎, Jun-ichi Hirabayashi a, Kenji Nogami a, Minoru Kusakabe b, Minoru Yoshida c
a
Volcanic Fluid Research Center, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-8551, Japan
b
Korea Polar Research Institute, Songdo Techno Park, 7-50, Songdo-dong, Yeonsu-gu, Incheon, 406-840, South Korea
c
1-5-16 Mama, Ichikawa, Chiba 272-0826, Japan

A R T I C L E I N F O A B S T R A C T

Article history: During the dome-forming eruption in 1991 to 1995 at Mt. Unzen, Japan high temperature volcanic gases were
Accepted 24 March 2008 sampled from fumaroles located at the western basement of the dacitic lava dome. Comparing the
Available online 23 April 2008 composition of volcanic gas, the volatile in the pre-eruptive melt of magma and the groundmass of lava, we
propose that the volatile in magma was liberated through three different gas separation steps. The first gas
Keywords:
separation happened at depth deeper than 3.9 km. The liberated gas traveled along the conduit then
volcanic gas
chemical composition
discharged as the observed fumarolic gas. The second gas separation took place beneath the lava dome. The
degassing of magma liberated gas was discharged on the top of lava dome. The third gas separation occurred near surface in a so
Mt. Unzen called “open system degassing” process. The large variation in the CO2/H2O ratio of fumarolic gas could be
explained by the variation of the bubble fraction in the pre-eruptive melt of magma chamber before the gas
separations. The estimated bubble fraction in the melt was less than 1.7 vol.%. Such a low fraction of bubbles
in the magma chamber of Mt. Unzen would be one of the reasons why the eruption was non-explosive. The
fumarolic gas in the later stage of eruption was enriched in HCl and HF due to the effect of open system
degassing of magma, although the gas contained CO2 and H2S with high concentrations. The CO2 and H2S
would be derived from a vapor phase of hydrothermal system developed around the conduit.
© 2008 Published by Elsevier B.V.

1. Introduction degassing inside the dome. Hammouya et al. (1998) monitored a

Volcanic gases contain volatiles dissolved in the pre-eruptive magma.
The degassing of volatiles is the driving force of magmatic eruptions. The
observation of volcanic gas is important to further our understanding of
magmatic eruptions and the prediction (e.g., Gerlach, 1986).
Noguchi and Kamiya (1963) found a significant increase in the S/Cl
ratio prior to the basaltic magma eruption at Izu-Ohshima volcano.
Hirabayashi et al. (1986) detected a positive correlation between the
number of vulcanian eruptions of Sakurajima volcano and the HCl/SO2
ratio of volcanic gas diffused in ambient air. Stoiber et al. (1986) observed
the composition of gas from Masaya volcano, where a lava lake had been
sustained at the bottom of the crater. The observed change in the S/Cl
ratio was attributed to the change in the supply rate of magma to the lava
lake. Taran et al. (2002) observed periodically a high temperature
fumarolic gas prior to the eruption of Volcán de Colima in 1998. They
detected an increase in the S/Cl ratio prior to the eruption.
Symonds et al. (1996) reviewed the results of long-term volcanic
gas surveillance carried out at Mt. Showa-Shinzan. They recognized a
gradual decrease in the C/S and S/Cl ratios over a 20-year period after
the emplacement of a lava dome, suggesting a persistent magma
hydrothermal fumarolic gas located 1 km far from the lava dome vent
on Mt. Soufrière Hills. The S/C ratio increased prior to the lava dome
extrusion and syn-eruptively increased after the extrusion. Edmonds
et al. (2003a) proposed a degassing model for the eruption of Mt.
Soufrière Hill based on intense measurements of SO2 flux. In their
model, a gas phase separated from magma at a certain depth ascended
along the conduit. The discharge rate of volcanic gas was controlled by
the permeability of a shallow structure beneath the lava dome.
Aiuppa et al. (2004) observed the chemical composition of volcanic
gas that diffused in ambient air around Mt. Etna during the series of
eruptions in 2002 to 2003. They found a gradual increase in the S/Cl ratio
prior to the resumption of strombolian eruption. The increase was
attributed to the ascent of the degassing depth of magma. Allard et al.
(2005) measured the chemical composition of volcanic gas associated
with the lava fountain at Mt. Etna by means of FT-IR remote sensing. The
CO2/S ratio of volcanic gas ranged from 7 to 10, which was much higher
than the pre-eruptive concentration in magma, suggesting the forma-
tion of a CO2-enriched gas phase in advance within magma chamber.
2. Eruption of Mt. Unzen

⁎ Corresponding author. The dacitic dome-forming eruption of Mt. Unzen in 1990 to 1995
E-mail address: ohba@ksvo.titech.ac.jp (T. Ohba). was not explosive, except for a few vulcanian-type explosions that

0377-0273/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.jvolgeores.2008.03.040
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
Fig. 1. Distribution of fumaroles and lava on Mt. Unzen, Japan. A, B and C: Fumaroles.
D: Table of lava fragments. E: Jigokuato crater. F and G: Lava lobe in the early and late
stages of eruption, respectively. S: Lava spine. The fumaroles (A and B), Jigokuato crater
(E) and the lava lobe-F were buried beneath the table of lava fragment (D) and the lava
lobe-G. The topographic features of D, E, F and G are based on Nakada et al. (1999). The
inserted figure indicates the location of Mt. Unzen in Japan.
occurred in 1991 (Nakada et al., 1999). The non-explosibility of silicic
dome-forming eruptions was explained by an effective escape of
volatiles in magma (Eichelberger et al., 1986). The observation of
volcanic gas emitted during the eruption will provide direct evidence
to investigate non-explosive eruptions. In this study, we sampled high
temperature fumarolic gas during the dome-forming eruption of Mt.
Unzen, Japan (Fig. 1).
The lava effusion started in May 1991 at Mt. Unzen. The lava flux
reached about 4 × 105 m3m3 day− 1 in Sep. 1991 (Nakada et al., 1999) as
the first maximum (Fig. 2). The lava flux linearly decreased and
reached to zero in Dec. 1992. The lava effusion resumed in Feb. 1993.
The flux increased quickly, reaching the second maximum in Jul. 1993.
The flux at the second maximum was 2 × 105 m3 day− 1, half of the first
maximum. After the second maximum, the flux decreased gradually
and the effusion substantially stopped in Feb. 1995.
The SO 2 flux from Mt. Unzen was measured by COSPEC
(Hirabayashi et al., 1995). The temporal change in the SO2 flux was
almost proportional to the lava flux. The flux was maximized to
230 × 103 kg day− 1 in Dec. 1991. In Dec. 1992, when the lava effusion
had stopped, SO2 flux decreased to 50 × 103 kg day− 1. A continuous low
frequency (LF) earthquakes under the lava dome at depths of less than
1 km continued even in Dec. 1992 (Nakada et al., 1999). The occurrence
of the LF earthquakes was attributed to the collapse of a foamed
Fig. 2. Change in the volatile molar ratio to H2O and isotopic composition of fumarolic gas. L: Lava flux. R: Magma supply rate to chamber. The lava flux and magma supply rate are
calibrated on the left y-axis. C1 on the right y-axis is 0.03, 0.03, 0.02, 0.002 and 7 for CO2/H2O, S/H2O, Cl/H2O, F/H2O and δ34S in ‰, respectively. C0 on the right y-axis is 0, 0, 0, 0 and
3 for CO2/H2O, S/H2O, Cl/H2O, F/H2O and δ34S in ‰, respectively.
121
magma (Nakada and Motomura, 1999). Those observations suggested
that the intrusion of magma sustained even in Dec. 1992.
Nishi et al. (1999) detected a pressure source in the crust around
Mt. Unzen by means of GPS observation. The pressure source was
recognized to be a magma chamber responsible for the eruption in
1991 to 1995. The detected pressure source was −11 km deep and 6 km
west of Mt. Unzen's summit. Nishi et al. (1999) compared the temporal
change of crustal deformation with the lava effusion rate, and
suggested that magma supply to the chamber continued even in
Dec. 1992 when the effusion of lava had stopped.
3. Sampling and analysis of volcanic gas
3.1. Volcanic gases
Three types of volcanic gases possessing different appearances were
observed at Mt. Unzen. The first was a fumarolic gas that was discharged
beside the basement of lava dome during eruption. The gas produced the
noise similar to a jet engine exhaust, because the discharging pressure of
the gas was high. The color of the gas was pale and white after diffusion
in ambient air, due to the presence of sulfuric acid mist. The location of
the fumarolic gas is shown in Fig. 1. A lava “lobe” was formed on the east
flank of the volcano, and fumaroles were located at the opposite side of
the dome. We were able to sample the fumarolic gas beside the lava
dome during eruption. The collapse of the lava dome at the west side
was limited, allowing the safe sampling of fumarolic gas.
The second gas was a white steam discharged from the top of lava
dome. The gas could not be sampled directly. The gas was sampled by
a remote controlled airship, although the sampled gas was diluted
with air extensively.
The third gas was sampled after the cease of lava effusion. As the final
stage of eruption, a lava spine was built on the summit. A fumarolic gas
was sampled at the root of the lava spine in 1995.
3.2. Fumarolic gas sampling and analysis
A quartz glass tube was inserted into the outlet of fumarole. The
quartz glass tube was connected to a 200 ml volumetrically calibrated
glass syringe via a rubber tube. The fumarolic gas was absorbed by
20 ml of 5 M KOH solution in the glass syringe. The major components
in the fumarolic gas were determined by the analysis of the KOH
solution along Ozawa (1968). The concentration of HF in the KOH
solution was determined along Tsuchiya et al. (1985). For the
determination of δD and δ18O of H2O in gas, volcanic gas was sampled
as condensate. For the δD measurement, the condensed water was
converted into H2 gas with heated metallic uranium (Bigeleisen et al.,
122 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132

Table 1
Chemical compositions of fumarolic gas from Mt. Unzen. nd: not detected. ⁎: The location of fumarolic gas is indicated in Fig. 1

Date Location⁎ Temp. H2O CO2 SO2 H2S HCl HF H2 CO CH4 N2 O2

(C ) (μmol/mol) (μmol/mol) (μmol/mol) (μmol/mol) (μmol/mol) (µmol/mol) (μmol/mol) (μmol/mol) (μmol/mol) (μmol/mol) (μmol/mol)
1992/5/12 A 818 955,000 27,000 4370 2430 2430 180 7740 278 ud 457 119
1992/5/12 B 809 953,000 27,600 4840 1650 3200 141 8680 344 ud 437 126
1992/7/21 A 801 968,000 15,100 4510 2080 2500 128 6450 158 2.06 772 229
1992/9/21 A 810 972,000 12,900 5010 1960 1880 112 5890 127 ud 149 79.3
1992/9/21 B 720 973,000 12,300 4240 2240 2160 135 5710 124 ud 128 62.6
1992/12/19 A 808 968,000 17,000 3520 1540 2370 128 4740 142 ud 2000 535
1992/12/19 B 778 968,000 17,200 3710 1440 1890 128 6030 179 ud 1150 289
1993/2/15 B 773 965,000 20,400 4520 1680 1930 105 5830 232 1.15 246 65
1993/10/10 A 535 963,000 18,200 7440 5880 3960 566 722 5.04 0.285 197 27.2
1993/10/10 B 364 956,000 15,900 9940 7350 10,300 114 217 1.59 0.509 76.9 5.03
1995/12/1 C 560 982,000 nd nd nd 15,700 1740

1952). Some δD of condensate in this study have been reported by type” magmas have been produced contemporaneously (Kita et al.,
Scott et al. (1993). The δ18O of the condensate was measured by mass 2001). As the WP-type magma is originated in a partially melted
spectrometer after the treatment of the conventional CO2–H2O upper mantle, the primary magmatic water could be included in the
equilibrium method (Epstein and Mayeda, 1953). For the determina- magma of Mt. Unzen.
tion of δ34S, a part of the KOH solution was oxidized. The dissolved The δ13C of CO2 was −6.3 and −6.4‰ for the fumarolic gas in May
sulfur species in the solution were converted to BaSO4 precipitate. The 1992. The values were close to −5.5‰ reported for the high tempe-
precipitate was converted to SO2 gas for the isotope measurement by rature volcanic gas sampled at Satsuma-Iwojima volcanic island, Japan
mass spectrometer (Yanagisawa and Sakai, 1983). (Sakai and Matsubaya, 1977).
According to Taylor (1986), the δ34S ranges from +4 to +12‰ for
3.3. Gas sampling by use of an airship the sulfur in high temperature volcanic gases which were sampled
from island arc volcanoes. The observed δ34S of fumarolic gas was
On 12th Mar. 1992, a volcanic gas uprising from the top of lava included in the range except the gas in Oct. 1993.
dome was sampled by use of a remote controlled airship. The shape of Only the Cl/S weight ratio was determined for the gas sampled by
the airship was similar to a rugby ball. The length of airship and the airship. Four cruises of samplings were successful. The determined Cl/S
diameter at the center of body were 12 and 3 m respectively. Beneath weight ratio was 6.1, 8.9, 5.5 and 1.8.
the belly of airship, an evacuated empty Pyrex glass bottle of 5 l was Except for the sample in Oct. 1993, the S/H2O, HCl/H2O and
installed. A thin glass needle had been connected to the evacuated HF/H2O ratios of fumarolic gas were stable (Fig. 2). In Oct. 1993,
bottle. The end of the glass needle had been welded and sealed. The the S/H2O, HCl/H2O and HF/H2O ratios were significantly in-
top of the glass needle was broken by remote control when the airship creased, and the δ34S decreased largely. The CO2/H2O ratio varied
was exposed by volcanic gas. After the return of airship, several ml of significantly during May 1992 to Feb. 1993. The pattern of the CO2/
5 M KOH solution was introduced into the evacuated bottle. The inside H2O ratio is similar to that of lava flux (Fig. 2), namely, the ratio was
of the bottle was washed well with the solution. The concentration of high when the lava flux was high and vice versa. However, the
S and Cl absorbed in the KOH solution was determined as same as the minimized CO2/H2O ratio anticipated the minimum of lava flux.
analysis of fumarolic gas. The frequency of gas sampling was much less compared with
measurements of the lava flux. Although the exact time of the
4. Results minimum CO2/H2O ratio could not be determined, the CO2/H2O
ratio would be minimized between Jul. 1992 and Dec. 1992. Ac-
The chemical and isotopic compositions of fumarolic gas and its cording to Ohta (1993), the effusion of lava stopped in the middle of
outlet temperature are listed in Tables 1 and 2, respectively. The Dec. 1992 and resumed on 2th Feb. 1993. Therefore, the minimum
fumarolic gas temperature was 535 to 818 °C at fumarole A, 364 to CO2/H2O ratio in gas anticipated the lava effusion minimum at least
809 °C at fumarole B, and 560 °C at fumarole C. Fumarolic gas one month.
contained acidic gases, such as SO2 and HCl with the concentration up The chemical composition of fumarolic gas sampled beside the lava
to 9940 and 15,700 µmol/mol, respectively. The “δ34S” in Table 2 spine had a unique feature, that is, although the δD and δ18O of H2O
means the isotopic ratio combining SO2 and H2S.
The δD and δ18O of H2O in Table 2 were definitely higher than
those of the local meteoric water around Mt. Unzen, which was
Table 2
approximately −40 and −6‰ to SMOW, respectively (Mizota and Isotopic compositions of fumarolic gas from Mt. Unzen
Kusakabe, 1994). The averaged δD was −31.8 ± 2.7 (1σ) ‰. The δ18O of
Date Locationa Temp. δδDSMOW δ18OSMOW δ34SCDT δ13CPDB
H2O was +7.4 to +10.0‰, much higher than the local meteoric water,
(C) (‰) (‰) (‰) (‰)
suggesting little contamination of meteoric water. As a general feature
1992/5/12 A 818 − 32 7.8 6.0 −6.3
of H2O vapor in high temperature fumarolic gases from the volcanoes
1992/5/12 B 809 −35 7.7 5.3 −6.4
located on subduction zone, the δD of H2O ranges from −30 to −10‰ 1992/7/21 A 801 − 28 9.5 5.4
(Taran et al., 1989). Those H2O in volcanic gas has been called as 1992/9/21 A 810 − 30 7.4 5.5
“andesitic water”. Based on the Table 2 in Giggenbach (1992), δD of the 1992/9/21 B 720 − 29 9.0 5.6
1992/12/19 A 808 −35 7.4 5.1
andesitic water is −19.9 ± 6.3 (1σ) ‰ which is the average for gases
1992/12/19 B 778 − 36 7.5 5.1
with the δ18O of H2O higher than 7.0‰. The δD of gases from Mt. 1993/2/15 B 773 −31 8.4 5.1
Unzen was lower than the andesitic water, possibly due to the 1993/10/10 A 535 − 30 8.9 3.8
inclusion of the “primary magmatic water” (Taylor, 1986), the δD of 1993/10/10 B 364 3.2
which ranges from −80 to −40‰. The Mt. Unzen is located on 1995/12/1 C 560 − 32 10

Shimabara peninsula where “Within-plate (WP) type” and “Island-arc a

The location of fumarolic gas is indicated in Fig. 1.
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
were magmatic, CO2 and sulfur-containing gases (SO2 or H2S) were
not detected.
Oxygen gas was detected in all of the fumarolic gases. The O2
originates in a contaminated air, and volcanic gases generally contain
the magmatic N2 gas, therefore the N2/O2 ratio should be higher than
3.73, which is the ratio of normal air. The N2/O2 ratio of several gases in
Table 1 is lower than 3.73. The depletion in N2 would be due to the
formation of NH3 along the reaction.
1=2N2 þ 3=2H2 ¼ NH3 :
The equilibrium constant on the above reaction (Giggenbach, 1987)
gave the equilibrated NH3 concentration. The estimated concentration
was 190 to 840 µmol/mol for the gases higher than 500 °C in Table 1,
assuming the total pressure of gas was 1 bar. If rocks act as a catalyst
for the above reaction, the N2 could be converted to NH3 gas, resulting
in the N2 depletion.
5. Discussion
5.1. Pre-eruptive volatile in magma
The non-explosive eruption with lava dome formation is a
consequence of the effective escape of volatiles from magma
(Eichelberger et al., 1986). As the first working hypothesis, we assume
that the observed fumarolic gas represents a gas phase that separated
from magma with one step degassing. In order to determine the
chemical composition of volcanic gas based on this hypothesis, we
review the concentrations of volatiles in the pre-eruptive melt of
magma and the groundmass of erupted lava.
The H2O content of the pre-erupted melt in magma was estimated
to be 6 wt.% by Kusakabe et al. (1999) as a concentration appropriate to
their degassing model developed for δD of H2O. Holtz et al. (2005)
suggested that the H2O concentration in the pre-eruptive melt of
magma was 6 ± 1 wt.% based on the mineral phase diagram. Nishimura
et al. (2005) analyzed melt inclusion in quartz and plagioclase. The
H2O concentration in the melt inclusion was 5.1 to 7.2 wt.%. Con-
sidering the above studies, we assumed that H2O concentration in the
pre-eruptive melt of magma was 6 wt.%.
Sulfur concentration in magma was estimated to be 210 ± 90 mg/kg by
Hirabayashi et al. (1995), who compared sulfur-containing gases (SO2
and H2S) flux with lava effusion rate. The obtained concentration
corresponds to the bulk concentration in magma, however the above
estimation did not include the sulfur fraction remained in erupted lava.
According to Yamaguchi (1997), the lava of Mt. Unzen included sulfur
bearing minerals such as pyrrhotite. Uchikawa (1993) obtained 40 mg/kg
for the bulk S concentration of the lava. The sulfur content determined by
Uchikawa (1993) could be due to a fraction of sulfur bearing minerals. As
the sulfur bearing minerals was not involved in the sulfur budget during
degassing, we omit the sulfur content in erupted lava. Assuming that the
averaged phenocryst volume content was 25 vol.% (Nakada and
Motomura, 1999), and assuming that S was exclusively contained in
the melt of magma, the S concentration was calculated to be 290 ±
120 mg/kg based on the estimation by Hirabayashi et al. (1995). Satoh
et al. (2003) analyzed the melt inclusion in phenocryst in lava and
estimated that the pre-eruptive S concentration was 220 ±120 mg/kg.
Botcharnikov et al. (2004) experimentally obtained 200 to 250 mg/kg for
the solubility of sulfur in silicate melt, the composition of which was
approximated to the groundmass of lava from Mt. Unzen. Considering
the above studies, we assumed that the upper and lower limits of S in the
pre-eruptive melt of magma were 250 and 100 mg/kg, respectively.
Yamaguchi (1997) obtained 825 ± 25 mg/kg for the Cl concentration
in the pre-eruptive melt based on the melt inclusion analysis. Carbon
dioxide and F concentrations in the pre-eruptive melt have not been
determined so far. The volatile concentrations in the pre-eruptive melt
in magma are summarized in Table 3.
123
Table 3
Concentrations of volatiles in pre-eruptive melt of magma and groundmass of erupted
lava
H2O S Cl F
(mg/kg) (mg/kg) (mg/kg) (mg/kg)
Pre-eruptive magmatic melt 60,000 175 ± 75 825 ± 25 –
Groundmass of lava 2600 51 ± 13 377 ± 67 352 ± 16
5.2. Volatiles in lava
Kusakabe et al. (1999) analyzed the groundmass of lava that erupted
from Mt. Unzen in 1991 to 1995. The H2O concentration was 2600 mg/
kg in average. Uchikawa (1993) analyzed the erupted lava for S, Cl and F
concentrations. The bulk concentrations of S, Cl and F in the lava were
38± 10, 283 ± 50 and 264 ± 12 mg/kg, respectively. Assuming that the
averaged phenocryst volume content was 25 vol.% (Nakada and
Motomura, 1999), and that S, Cl and F were exclusively contained in
the groundmass of lava, the S, Cl and F concentrations in the ground-
mass were calculated to be 51 ± 13, 377 ± 67, and 352± 16 mg/kg,
respectively. As mentioned earlier, the S in the erupted lava would be
attributed to a fraction of S bearing minerals. The concentrations of
volatiles in the groundmass of lava are summarized in Table 3.
5.3. Estimated gas composition
Based on the working hypothesis, the S/H2O and Cl/H2O ratios of
gas exsolved from the pre-eruptive melt are given by
Mip  Mig
Fi ¼ 1000 ð1Þ
M0p  M0g
where Fi is the S/H2O or Cl/H2O weight ratio of exsolved gas (g/kg). Mip
and Mig are the concentration of S or Cl in the pre-eruptive melt (mg/kg)
and the groundmass of lava, respectively. As the S concentration in lava
could be due to a sulfur bearing mineral fraction, Mig for S was assumed
to be zero. The M0p and M0g are the H2O concentrations (mg/kg) in the
pre-eruptive melt and the groundmass of lava, respectively. The “A” in
Fig. 3 indicates the calculated Fi values.
The representative S/H2O or Cl/H2O ratio for fumarolic gas in Fig. 3
(FG) excluded the gases in Oct. 1993 and in 1995 for averaging, because
they were markedly different from the previous gases. In Fig. 3, the S/H2O
ratio by Eq. (1) was only one fourth of the ratio for fumarolic gas. The Cl/
H2O ratio by Eq. (1) was twice of the ratio of fumarolic gas. Those definite
differences violated the working hypothesis. In the following sections,
we propose another model to explain fumarolic gas composition.
5.4. Multi-steps degassing model
We propose a multi-steps magma degassing model to explain the
chemical composition of fumarolic gas. In the model, we assume three
major gas separation steps. The first is a separation under deep
ground, the second is a separation beneath lava dome and third is a
separation near surface. This model is consistent to the observed three
types of volcanic gases. The first gas was a pale white fumarolic gas
that was discharged at the base of the lava dome, the second was a
white gas that was diffusively discharged from the lava dome, and the
third was a gas sampled beside of lava spine. The outline of the multi-
steps degassing model is described in Fig. 4.
In the multi-steps magma degassing model, the gas separated from
magma at a deep underground ascends along the conduit. A similar gas
behavior was proposed for the dome-forming eruption at Soufrière
Hills volcano (Edmonds et al., 2003a). A magma with high viscosity,
such as that of Mt. Unzen, suffered a strong shear stress at the conduit
wall during the ascent. The stress might prompt the fragmentation of
magma and the escape of gas through the cracks on the conduit wall
124 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
Fig. 3. S/H2O and Cl/H2O weight ratios of fumarolic gas and the estimated gas phase. A: S/H2O and Cl/H2O ratios given by Eq. (1)). FSG-96 and -150: Gas phase at the first gas separation
under 96 and 150 MPa, respectively. The open circles: S/H2O and Cl/H2O ratios of fumarolic gas. The broken lines: S/Cl ratio of gases sampled by airship. FG: Averaged S/H2O and Cl/H2O
ratios of fumarolic gas until Feb.1993. SGS: Gas phase at the second gas separation. OSD: Gas phase emitted under open system degassing. The vertical and horizontal bar of FSG-96, -150
and A indicate the range of ratios between the upper and lower limits. The vertical and horizontal bars of FG indicate the ±1σ range centering the averaged Cl/H2O and S/H2O ratios.
(Gonnermann and Manga, 2003). Moreover, Sato et al. (1999) and
Noguchi et al. in (2008-this issue) gave petrological evidence for the
degassing of magma under high pressure at Mt. Unzen. Based on the
analysis of microlite in the groundmass of erupted lava, Noguchi et al.
(2008-this issue) suggested that the magma started to degas at
150 MPa. Sato et al. (1999) also suggested that the degassing of the
magma was completed before the pressure of magma decreased to
70 MPa, based on the Cl content of pargasite in the groundmass of lava.
Assuming that the density of crust was 2500 kg m− 3, 150 and 70 MPa
correspond to the depths of 6.1 and 2.9 km, respectively.
5.5. Parameters for multi-steps degassing model
The physical and chemical parameters are necessary for a
quantitative degassing model. The temperature of the magma was
Fig. 4. Multi-steps degassing model. MC: Magma chamber. L: Lava. V1 and V2: Gas
separated at the first and second gas separation steps, respectively. V3: Gas emitted
from magma under open system. HS: Hydrothermal system developed around the
conduit. M: Volatile concentration in the melt of magma. F: Volatile to H2O weight ratio.
D: Distribution coefficient between gas and melt. The first and second gas separation
steps are assumed to occur under closed system.
assumed to be 900 °C based on the thermometry by use of Fe–Ti-oxide
minerals in lava (Venezky and Rutherford, 1999; Nakada and Moto-
mura, 1999). The composition of groundmass was rhyolitic (Nakada
and Motomura, 1999). The depth of the main magma chamber was
estimated to be −11 km based on the ground surface inflation around
Mt. Unzen (Nishi et al., 1999). The lithostatic pressure of the magma
chamber was 269.5 MPa assuming that the density of crust was
2500 kg m− 3. The lower limit of pressure at the first gas separation was
estimated to be 96 MPa. The derivation for the lower limit of gas
separation pressure will be described in the later section.
Kusakabe et al. (1999) suggested that the magma of Mt. Unzen lost
the dissolved H2O under closed system until the H2O content decreased
to 0.5 wt.%. In their model, when the H2O content reached 0.5 wt.%, the
gas phase was separated from magma. After the separation, the
remained H2O in magma was further lost under open system. The
rhyolitic melt with 0.5 wt.% of H2O produces 2.3 MPa of saturation
pressure at 900 °C (“VolatileCalc” by Newman and Lowenstern, 2002).
The second gas separation was assumed to take place at 2.3 MPa. The
pressure was equivalent to the lithostatic pressure at −96 m.
The hypocenters of low frequency (LF) earthquakes were distributed
at the depth shallower than −500 m (Nakada et al., 1999). The LF
earthquakes were generated by a collapse of foamed magma (Nakada
et al., 1999). The collapse of foamed magma liberated the gas phase. The
shallow degassing process suggested by Kusakabe et al. (1999) is
consistent to the observation on LF earthquakes. The physical para-
meters for the multi-steps degassing model are summarized in Table 4.
5.6. Bubbles in melt
As shown in Fig. 2, the S/H2O, Cl/H2O and F/H2O ratios were stable
over the period from May 1992 to Feb. 1993. This behavior may lead
that H2O, S, Cl and F concentrations in the pre-eruptive magma were
Table 4
Physical parameters for the modeling of magma degassing at Mt. Unzen
Value Unit
Temperature of magma 900 °C
Depth of magma chamber − 11 km
Crustal density 2500 kg m− 3
Pressure at magma chamber 269.5 M Pa
Pressure at the first gas separation 96–150 M Pa
Pressure at the second gas separation 2.3 M Pa
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
Fig. 5. Bulk CO2/H2O and S/H2O molar ratios in melt as a function of bubble fraction. Two different distribution coefficients (D) were applied for the calculation of the S/H2O ratio. The
dissolved H2O, CO2 and S concentrations in the melt were fixed.
nearly constant and the degassing condition, namely, the pressure of
degassing, was also constant. By contrast, the CO2/H2O ratio in fuma-
rolic gas varied largely. The pattern of variation is similar to that of the
lava effusion rate.
According to Nakamura (1995), Venezky and Rutherford (1999), the
magma of Mt. Unzen was a mixture of aphyric mafic magma and a
crystal rich felsic magma. Nakada and Motomura (1999) proposed
another model for magma genesis in which the melt in magma was
generated with the interaction between a hot mafic magma and a cold
solidified rhyodacitic magma. The solidified magma was underplated by
the hot mafic magma resulting in a partial melting. The composition of
groundmass of lava was quite stable during eruption, suggesting the
fraction of mafic magma in the mixed magma was almost constant
(Nakada and Motomura, 1999). Therefore, the CO2 variation cannot be
directly connected to the change in the mixing fraction of mafic magma.
The fumarolic gas composition only constrains the relative
abundance of volatiles in the pre-eruptive magma. Theoretically, the
increase in CO2/H2O ratio with constant S/H2O, Cl/H2O and F/H2O
ratios could be equivalent to a constant CO2 concentration with
coordinated H2O, S, Cl and F decreases in the pre-eruptive melt.
However, a simple and straightforward explanation is the standalone
CO2 increase in melt with the constant H2O, S, Cl and F.
The standalone increase in “bulk CO2 concentration” can be brought
by a variation of bubbles fraction in melt. Here, “bulk CO2 concentra-
tion” means the total abundance of CO2 per unit volume of melt in
which the volume fraction of gaseous bubbles is included. Fig. 5
demonstrates the effect of bubbles in the melt. We assume that
bubbles are incorporated in the rhyolitic melt in magma chamber at
900 °C and 269.5 MPa. The melt was saturated in terms of H2O and CO2.
The H2O concentration in melt was fixed at 6.0 wt.%, and CO2
concentration was calculated to be 354 mg/kg by VolatileCalc (New-
man and Lowenstern, 2002). The CO2/H2O molar ratio of gas phase in
bubble was calculated to be 0.25 by VolatileCalc.
The S concentration in the melt was assumed to be 175 mg/kg. As
reviewed in the later section, the experimental distribution coefficient
of S between gas and melt phases was not preciously determined. The
distribution coefficient D is defined to be,
F which is the maximum of the observed fumarolic gases. In summary, a
D¼ 1000
M melt contains 6.24 wt.% of H2O and 1819 mg/kg of CO2 as the bulk
where F is the S/H2O weight ratio in gas phase (g/kg), and M is the S
concentration in melt (mg/kg).
We used 855 and 319 for the upper and lower limits of D based on
the experiment by Botcharnikov et al. (2004). Under the above-
125
mentioned conditions, the bulk CO2/H2O molar ratio proportionally
increased with the bubble fraction in the melt (Fig. 5). By contrast, the
increasing rate in the bulk S/H2O molar ratio is relatively slow. As the D
of Cl and F were much smaller than that of S, the bulk Cl/H2O and F/H2O
molar ratios substantially do not depends on bubble fraction. In sum-
mary, the standalone variable CO2 content in magma can be brought by
the change in bubbles fraction of melt.
The bubble formation in the magma chamber produces “over
pressure”, triggering magmatic eruption (Blake, 1984; Woods and
Cardoso, 1997; Wallace, 2001). The volume fraction of bubbles is
important to clarify why the eruption of Mt. Unzen was non-explosive.
In the multi step degassing model, the observed fumarolic gas repre-
sents a gas phase separated from magma under high pressure. The
model will be examined in the later section quantitatively. Here, the
bubble volume fraction in magma chamber is estimated based on the
CO2/H2O ratio of fumarolic gas.
In Fig. 6, thin solid lines indicate the solubility of H2O and CO2 in
rhyolitic melt at various pressures. The melt at the point-a in Fig. 6a,
contains 6.24 wt.% of H2O and 1819 mg/kg of CO2.
The melt at the point-a is decompressed. We assume no bubbles at
the point-a. Along the decompression, bubbles are generated and
grew in melt. The gas phase in bubbles and melt are equilibrated in
terms of H2O and CO2 distribution under closed system. The path of
H2O and CO2 concentration brought by decompression was calculated
by use of VolatileCalc (Newman and Lowenstern, 2002) and drew as
the curve A. The melt composition become 6.0 wt.% of H2O and
354 mg/kg of CO2 at the point-c where the saturation pressure is
269.5 MPa, equals to the pressure of magma chamber. At the point-c,
some amounts of bubble are generated in melt. A further decompres-
sion drives the melt to the point-d, where 3.65 wt.% of H2O and 17 mg/
kg of CO2 are left in melt.
At the point-d, the gas in bubbles is assumed to be separated from
melt. The saturation pressure at the point-d is 96 MPa. As it will be
discussed in the later section, this pressure is the lower limit of the
first gas separation. The separated gas would travel along the conduit
and it was discharged as the observed fumarolic gas. The CO2/H2O of
the separated gas corresponds to the slope of the line connecting the
points-a and -d. The slope of the line is 0.0286 in CO2/H2O molar ratio,
ð2Þ
concentration can separate a gas phase at 96 MPa, the CO2/H2O ratio of
which is 0.0286.
The melt at point-a is virtual. The introduction of the virtual melt is
convenient to distinguish the results brought by the decompressed
melts with different H2O and CO2 concentration.
126 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132

Fig. 6. H2O and CO2 concentrations in rhyolitic melt. A and B: Changes during the decompression down to 96 MPa (a) and 150 MPa (b) at 900 °C under closed system. Thin lines:
Saturation in terms of H2O and CO2 at various pressure. Broken lines: CO2/H2O molar ratio of fumarolic gas. The bulk H2O and CO2 concentrations in melt on the curves A and B are
shown in the parenthesis. The left and right values in the parenthesis are the H2O and CO2 concentration in wt.% and mg kg− 1, respectively. The H2O and CO2 concentration in melt at
269.5 MPa was 6.0 wt.% and 354 mg kg− 1 common to the curves A and B.

The bubble volume fraction in melt at the point-c can be estimated
in Fig. 5. The bulk CO2/H2O molar ratio in melt on the curve A is 0.012,
which is calculated from 6.24 wt.% of H2O and 1819 mg/kg of CO2. In
Fig. 5, the bulk CO2/H2O molar ratio gives 1.73 vol.% for the bubble
fraction at the pressure on point-c. As same as the above estimation,
the minimum CO2/H2O molar ratio in fumarolic gas (=0.013) gives
6.07 wt.% of H2O and 779 mg/kg of CO2 in melt (the point-b in Fig. 6a).
The bulk CO2/H2O ratio on the curve B is 0.00525, resulting in 0.67 vol.
% of bubble in melt at the point-c.
The bubble volume fraction in melt also depends on the separation
pressure of gas. As shown in Fig. 6b, an increased separation pressure
requires the suppressed H2O and CO2 concentration in melt. Noguchi
et al. (2008-this issue) suggested that the magma of Mt. Unzen started
the degassing at 150 MPa. We employed this value for the upper
limiting pressure of gas separation. At 150 MPa, 4.78 wt.% of H2O is left
in melt. The H2O and CO2 concentrations of melt at the point-a in Fig.
6b are 6.10 wt.% and 922 mg/kg, respectively. The bulk CO2/H2O molar
ratio of the melt on the curve A is 0.00619. In Fig. 5, this bulk ratio
gives 0.77 vol.% for the volume fraction in the melt at the point-c.
Similarly the bubble fraction on the curve B is given to be 0.09 vol.% at
the point-c in Fig. 6b.
The estimated bubble fraction in magma chamber was less than
1.73 vol.%. Bubbles in melt could not be separated from melt at such a low
volume fraction. The bubble formation in magma chamber is a degassing
process on the viewpoint of melt in magma. However, this degassing
process did not accompany the separation of gas phase (Fig. 4).
The bubble fraction, 1.73 vol.% equivalent to 0.39 wt.%, is much
smaller than 6 and 3.6 wt.% that were estimated in the magma
chamber at the Bishop Tuff eruption of 0.73 Ma and Mt. Pinatubo
eruption in 1991, respectively (Wallace and Gerlach, 1994; Wallace
et al., 1995). The both of eruptions were explosive. The small bubble
fraction in the magma chamber at Mt. Unzen could be one of the
reasons why the eruption of Mt. Unzen was non-explosive.
5.7. Variation in bubble fraction
According to Nakada and Motomura (1999), a mostly solidified
cold magma was underplated by a hot mafic magma. By the heat of
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132 127

mafic magma, the cold magma was partially melted and a magma
with rhyolitic melt was generated. The cold magma would be a
remnant magma stored in the chamber before the eruption in 1991
(Nakamura, 1995). As CO2 is a component easily degassed from
magma, the CO2 in gas should originate in the mafic magma rather
than the low temperature magma.
Before the eruption, bubbles in mafic magma would be accumu-
lated beneath the cold magma due to the buoyancy (Fig. 7a). The
bubbles in mafic magma were incorporated into the rhyolitic melt.
According to Venezky and Rutherford (1999), the magma of Mt.
Unzen was lifted 7 km within 11 to 30 days. The CO2/H2O ratio of
fumarolic gas reflected the bubble fraction in magma about one
month behind. The CO2/H2O ratio in fumarolic gas was highest in May
1992. The situation of Fig. 7a represents the magma chamber before
Apr. 1992.
The continuous discharge of lava consumed the bubble rich layer in
mafic magma, resulting in the decreased CO2/H2O ratio of the
separated gas (Fig. 7b). The situation corresponds to the period in
Jun. 1992 to Aug. 1992. Nishi et al. (1999) suggested that the magma
recharge to chamber continued even in the period with no lava
effusion in Dec. 1992 (Fig. 2). The amount of mafic magma would
increase temporarily in magma chamber, leading a bubble accumula-
tion again beneath the roof of mafic magma (Fig. 7c). The CO2/H2O
ratio of fumarolic gas increased in Dec. 1992, then the enrichment of
bubble would start in Nov. 1992.
The CO2, S, Cl or F weight ratio to H2O (mg kg− 1) of the gas phase is
expressed as Fix. The meaning of the subscripts on F is common to
those on M. The volatile distribution between gas and melt phases is
expressed as the distribution coefficient, Dix. Dix is defined to be,
Fix
Dix ¼ 1000 ð3Þ
Mix
where the meaning of the subscripts on D is the same as those on M
and F.
Before the separation of gas phase, the equilibrated distribution of
volatiles between the gas phase and the melt was assumed to be
maintained (Sparks, 1978). After a sufficient growth of bubbles, a
connection between bubbles would be established, resulting in the
formation of a path, through which gas in the bubbles can be escaped.
We treat the gas phase and the melt as a closed system, namely, the
conservation of species and the equilibrated distribution between gas
and melt phases hold at the separation of gas. The conservation of
species “i” is expressed to be,
Mi0  Mi1 ¼ Fi1 ðM00  M01 Þ103 ð4Þ
The left hand side of the equation indicates the amount of volatiles
(mg) exsolved from 1 kg of melt, and the right hand side of the
equation indicates the amount of volatiles (mg) in the evolved gas
phase. Combining Eqs. (3) and (4), we have,

Mi0
5.8. First gas separation (FGS) Mi1 ¼ ð5Þ
1 þ Di1 ðM00  M01 Þ106
We define the notations for the concentrations of volatiles in melt and
and fluid phases as follows. The concentration of species “i” in melt is
defined to be Mix, which is the amount of “i” (mg) in 1 kg of silicate Di1 Mi0 103
melt excluding volatiles. The volatile species H2O, CO2, S, Cl and F are Fi1 ¼ ð6Þ
1 þ Di1 ðM00  M01 Þ106
indexed to be 0, 1, 2, 3 and 4 for i, respectively. The second digit of the
subscript “x” indicates the state of the melt, where 0, 1, 2 and 3 express
the melt at pre-degassing, at the first gas separation, at the second gas For the evaluation of Mi1 and Fi1, D is necessary. The D for S (=D21)
separation and at the final degassing, respectively. was experimentally determined by Scaillet et al. (1998), who found a

Fig. 7. Model for the variable CO2/H2O ratio in fumarolic gas. (a): Period until Apr. 1992 with high CO2/H2O ratio in the fumarolic gas brought by the accumulation of CO2-rich bubbles
in the upper part of mafic magma due to the buoyancy of bubbles. (b): Period from Jun. 1992 to Aug. 1992, when the most of the CO2-rich bubbles were consumed. (c): Period after
Nov. 1992 when the supply of mafic magma overcame the discharge rate of magma resulting in the accumulation of bubble. In the periods of (a) and (b), the magma chamber was
deflated due to magma discharge from chamber. In the period (c), magma chamber was inflated.
128 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132

strong dependence on oxygen fugacity (fO2). The D value was lower
than 10 at fO2 less than +1 log unit relative to the NNO buffer. The D
value jumped to 1000 at fO2 higher than +1.5 log unit relative to the
NNO buffer. According to Venezky and Rutherford (1999), fO2 of the
lava from Mt. Unzen was approximately +1 log unit higher than that of
the NNO buffer at 900 °C. Therefore, D21 would be 10 to 1000. Keppler
(1999) also experimentally obtained the D. It ranged from 47 to 137
when the temperature was 750 to 850 °C, the pressure was 50 to
200 MPa, and the fO2 was +0.5 log unit higher than NNO buffer.
Recently, Botcharnikov et al. (2004) carried out S distribution ex-
periments for a silicate melt, the composition of which was appro-
ximated to the groundmass of Mt. Unzen's lava at 850 °C at 200 MPa.
Although they did not indicate the D value explicitly, we evaluated the
D value based on the Fig. 4 in their paper. The evaluated D value was
319 to 855. As the evaluated D was consistent to the previous studies,
we employed this D value for model calculation.
Webster and Holloway (1988) experimentally determined the
distribution of Cl between fluid and rhyolitic melt phases at various
temperatures and pressures. At 100 MPa and 725 to 797 °C, D was 2.7
to 5.2. The D value depended on the temperature. As the dependence
of D on temperature was 2 for 100 °C increase, at 100 MPa and at 825
to 897 °C, the D value was expected to be 4.7 to 7.2. The dependence
on pressure was low (Webster and Holloway, 1988). Botcharnikov
et al. (2004) obtained D at 850 °C and 200 MPa by use of a silicate melt
the composition was approximated to the groundmass of lava from
Mt. Unzen. We evaluated the D value to be 10 for the D based on the
Fig. 3 in their paper. Considering the above studies, we assumed that
4.7 and 10 was the lower and upper limit of D31, respectively.
Villemant and Boudon (1999) estimated the distribution coeffi-
cient of F with an empirical method. They analyzed volcanic clasts
from the Mt. Pelée eruption to determine the concentrations of H2O
and F. They compared the analytical values with an open degassing
model in terms of F concentration. They obtained the appropriate D
value for the degassing model, which was less than unity. Webster
(1990) experimentally determined the distribution coefficient of
fluoride between fluid and rhyolitic melt of 900 °C, which was 0.15
to 0.30 under the pressure between 50 to 200 MPa. We used those
values for D41.
The results of model calculation are listed in Table 5, where the
pressure of first gas separation was assumed to be 96 or 150 MPa. The
S/H2O (F21) and Cl/H2O (F31) ratios in fluid at FGS (first degassing step)
are plotted in Fig. 3. Especially F21 has a large extension due to the
uncertainly in D21 and M20. Nevertheless, the range of F21 at 150 and
96 MPa overlapped to the observed fumarolic gas composition. F31
(=Cl/H2O) at 150 and 96 MPa was also consistent with the observed
fumarolic gas composition. The overlapping of F21 and F31 with the
observed fumarolic gas composition is the evidence that the observed
fumarolic gas represented a gas phase separated at high pressure.
The F21 is sensitive to the gas separation pressure. The lower
pressure brings smaller F21. The minimum gas separation pressure
allowing the overlap between F21 and the S/H2O of fumarolic gas was
96 MPa. On the other hand, the upper limit of pressure at FGS could
not be constrained, because even if we increased the pressure up to
269.5 MPa, F21 overlapped with the observed fumarolic gas composi-
tion. In summary, the minimum gas separation pressure at FGS was
estimated to be 96 MPa and the corresponding depth is 3.9 km.
The volume fraction of bubbles that developed in the melt
obviously controls the separation of gas phase. Employing the
equation of state by Holloway (1977) for the gas phase, the volume
fraction of bubbles in the melt is described in Fig. 8 as a function of
pressure. To calculate the specific volume of gas, the effect of bubbles
existing in the pre-eruptive degassing melt was considered. Two
volume fraction curves were drawn where the amount of bubbles
were maximum and minimum. In the cases of maximum and mini-
mum, the volume fraction at 96 MPa was 24 and 22 vol.%, respectively.
This volume fraction is slightly lower than 30%, the theoretical thre-
shold at which the connection of bubbles become effective (Rintoul
and Torquato, 1997).
5.9. Second gas separation (SGS)
At FGS, bubbles in magma were once expelled from magma. On the
way to surface, the magma would be oversaturated again in terms of
H2O, and the bubbles would be generated in magma again. We assume
that the second gas separation (SGS) happened at 2.3 MPa following
the degassing model by Kusakabe et al. (1999), in which H2O degassed
under closed system until the H2O content decreased to 0.5 wt.%. The
H2O saturation pressure of rhyolitic melt with 0.5 wt.% of H2O at
900 °C is given to be 2.3 MPa by VolatileCalc (Newman and
Lowenstern, 2002). Employing the equation of state by Holloway
(1977) for the gas phase, the volume fraction of bubbles in melt was
calculated to be 95% at 2.3 MPa if the H2O content was 3.65 wt. % at

Table 5
Model calculation for the two step degassing of S, Cl and F. ⁎: LL and UL are the lower and upper limits, respectively. ⁎⁎: The unit is (mg kg− 1)/(mg kg− 1). ⁎⁎⁎: F concentration before the
degassing was backward-estimated assuming that the F concentration in the groundmass of lava was equal to M42. Melt and fluid composition were calculated in two cases where the
pressure of first gas separation was 150 MPa (1) and 96 MPa (2). M11 was calculated by use of VolatileCalc

i=0 i=1 i=2 i=2 i=3 i=3 i=4 i=4

H2O CO2 S-LL⁎ S-UL⁎ Cl-LL⁎ Cl-UL⁎ F-LL⁎ F-UL⁎

(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)
Mi0 Before the gas separation 60,000 354 100 250 800 850 (1) 351 385 ⁎⁎⁎
(2) 348 382 ⁎⁎⁎
Mi1 At the first gas separation (1) 47,840 24 20 22 757 758 350 384
Mi1 At the first gas separation (2) 36,500 17 12 12 720 688 347 379
Mi2 At the second gas separation (1) 5000 0.0036 2.6 2.8 570 571 336 368 ⁎⁎⁎
Mi2 At the second gas separation (2) 5000 0.0035 2.0 2.0 581 555 336 368 ⁎⁎⁎

CO2/H2O S/H2O-LL S/H2O-UL⁎ Cl/H2O-LL⁎ Cl/H2O-UL⁎ F/H2O-LL⁎ F/H2O-UL⁎

(g/kg) (g/kg) (g/kg) (g/kg) (g/kg) (g/kg) (g/kg)

Fi1 At the first gas separation (1) 28.4 6.54 18.8 3.56 7.58 0.053 0.115
Fi1 At the first gas separation (2) 14.9 3.75 10.1 3.39 6.88 0.052 0.114
Fi2 At the second gas separation (1) 0.56 0.42 0.45 4.36 4.37 0.336 0.368
Fi2 At the second gas separation (2) 0.54 0.31 0.31 4.44 4.24 0.336 0.368

D1 D2-LL⁎ D2-UL⁎ D3-LL⁎ D3-UL⁎ D4-LL⁎ D4-UL⁎

(⁎⁎) (⁎⁎) (⁎⁎) (⁎⁎) (⁎⁎) (⁎⁎) (⁎⁎)

Di1 At the first gas separation 319 855 4.7 10 0.15 0.3
Di2 At the second gas separation 155,000 159 159 7.65 7.65 1.00 1.00
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
FGS. The escape of gas from such a significantly foamed magma seems
to be reasonable.
The volatile concentrations in melt and fluid at SGS are given by,
Mi1
Mi2 ¼
1 þ Di2 ðM01  M02 Þ106
and
Di2 Mi1 103
Fi2 ¼
1 þ Di2 ðM01  M02 Þ106
The distribution coefficients for S, Cl and F have not been obtained
experimentally at the pressures as low as 2.3 MPa. Giggenbach (1996)
empirically estimated the Henry's constant of S, Cl and F dissolved in
andesitic magma at 1.2 MPa by comparing the volcanic gas and melt
inclusion composition. For the species i, the distribution coefficient Di
is derived from Henry's constant (Hi) by,
 
MWi 106
Di ¼
18 PH2 O Hi
where MWi and PH2O are the molecular weight (g mol ) and the −1
saturation pressure (M Pa) of H2O over melt. The Henry's constant
estimated by Giggenbach (1996) was 4.8 × 103, 1.1 × 105 and 4.5 × 105
(mg kg− 1 MPa− 1) for S, Cl and F, respectively. With 2.3 MPa in PH2O, Di
was given to be 159, 7.65, 1.00 for S, Cl and F, respectively. We used
those values for D at SGS.
The results of calculation by Eqs. (7) and (8) are shown in Table 5.
One evidence supporting the occurrence of SGS is the Cl left in the
groundmass of lava. Fig. 9 shows the changes of volatiles concentration
in melt along the progress of the gas separation steps. The calculated Cl
concentration in the melt after SGS was close to the Cl concentration in
groundmass of lava. As will be discussed in later section, the Cl left at
SGS was further reduced at the final degassing step at near surface.
Another evidence supporting SGS is the Cl/S ratio of gas sampled
by airship. The observed Cl/S ratios are close to the Cl/S ratio of gas
phase of SGS (Fig. 3), although the ratio of one sample was
exceptionally low. The exceptionally low Cl/S ratio may be due to
the involvement of fumarolic gas representing the gas phase of FGS.
5.10. Final degassing
The gas sampled at the root of the lava spine was significantly
different from the previous gases (Table 1). Although the δD and δ18O
Fig. 8. Volume fraction of bubbles in melt under decompression. The curve “a” corresponds to the curve A in Fig. 6a. The curve “b” corresponds to the curve B in Fig. 6b. The vertical
dotted line shows the lower limit of pressure at the first gas separation (96 MPa). The volume fraction at 96 MPa is 24 and 22% for the curves “a” and “b”, respectively.
129
of H2O in the gas were magmatic, the gas did not contain detectable
CO2, SO2 or H2S. The HCl and HF concentrations were much higher
than those of previous gases. In Fig. 10, the ternary molar composi-
tions of gases are plotted in terms of H2O, HCl and HF. The gases before
Feb. 1993 converged at a region near H2O apex. The composition is
ð7Þ
close to the gas phase of FGS estimated at 96 or 150 MPa. The gas
phase of SGS is enriched in F relative to the gas of FGS. The
composition of gas from the fumarole A in Oct. 1993 and the gas in
Dec. 1995 are much H2O depleted relative to SGS. The composition of
ð8Þ gas at the fumarole B in Oct. 1993 is significantly depleted in HF
relative to the gas from fumarole A in Oct. 1993.
For the interpretation of H2O left in lava from Mt. Unzen, Kusakabe
et al. (1999) applied an open system model. Villemant and Boudon
(1999) also applied an open system degassing model to interpret the
concentration of H2O, Cl and F left in lava from Mt. Pelée. Here we try
to explain the chemical composition of gas in Oct. 1993 and Dec. 1995
with the open degassing model.
The change in gas composition under the open system degassing is
described by the following Rayleigh's equation (e.g., Aiuppa et al., 2002).
ð9Þ
   H0 
X3g H0 M32 1
¼ f H3 ð10Þ
X0g H3 M02
X0g and X3g is the molar concentration of H2O and HCl in gas,
respectively. The f is the fraction of H2O left in the melt, which is
defined to be,
M03
f ¼ ð11Þ
M02
where M02 and M03 is the H2O concentration in melt at the start and
end of open system degassing, respectively. The concentration of Cl
left in melt is given by,
  H0 
M33 M32 1
¼ f H3 ð12Þ
M03 M02
An equation similar to Eqs. (10) and (12) can be written for S or F,
where X3, H3, M32, M33 (for Cl) are substituted by X2, H2, M22, M23 (for S)
or X4, H4, M42, M43 (for F), respectively. We employed the empirical
Henry's constant given by Giggenbach (1996), which was 4.8 × 103,
1.1 × 105 and 4.5 × 105 (mg kg− 1 MPa− 1) for S, Cl and F, respectively. The
Henry's constant of H2O was estimated to be 2.14 × 103 (mg kg− 1 MPa− 1)
at 900 °C by use of VolatileCalc. With Eq. (10), the ternary composition of
gas emitted from the magma was calculated (Fig. 10). The gases from
130 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132

Fig. 9. Estimated volatile concentration in the melt of magma with the analyzed concentration in lava. The number 0, 1, and 2 on x-axis means the state of melt at the pre-degassing,
the first gas separation and the second gas separation, respectively.

fumarole A in Oct. 1993 and the gas in Dec. 1995 were plotted along the
curve representing the gas phase.
The change in the volatile concentration in melt is shown in Table 6.
Along the progress of open system degassing, the concentration of H2O
and S in melt is reduced quickly, on the other hand the decreases in Cl
and F are limited, resulting in the increased Cl/H2O, F/H2O and Cl/S
ratios of gas phase and in melt.
The ash leachate has been used as a proxy of volcanic gas (e.g.,
Edmonds et al., 2003b). One evidence for the open degassing is
brought by the Cl/S ratio of water-soluble components leached from
the ash. Nogami et al. (2001) observed a high Cl/S weight ratio in the
leachate of ash derived from the pyroclastic flow at Mt. Unzen. The Cl/
S ratio extended to 33 to 48 in Jul. and Aug. 1991. The Cl/S ratio is much
higher than the Cl/S ratios of fumarolic gas (ca. 0.4) and the estimated
gas phase of SGS (ca. 10). If the degree of open degassing proceed to
the state where H2O in melt is reduced to tenth (f = 0.1 in Table 6), the
Cl/S ratio of gas phase can be increased to 30. The high Cl/S ratio of ash
leachate suggests that the occurrence of open system degassing at the
final degassing process of lava from Mt. Unzen.
The gas from fumarole B in Oct. 1993 was significantly depleted in
HF relative to the gas from fumarole A. The similar HF depletion is also
found in the gases sampled by Shinohara et al. (2008-this issue) which
is plotted around the region close to the apex of Cl in Fig. 10. The
temperature of the gas from fumarole B in Oct. 1993 was lower than
fumarole A. The H2 and CO concentrations in the gas from fumarole B
were much lower than those in fumarole A. The decrease in H2 and CO
concentrations was due to a retrograde reaction among gas species
during cooling (Ohba et al., 1994). The temperature of the gas from
fumarole B was less than 400 °C. A brine can coexist with vapor phase
at the temperature lower than 400 °C (Giggenbach, 1987). The HF in
gas phase might be preferentially absorbed by a brine generated in the
retrograde process of cooling volcanic gas.

5.11. Hydrothermal system

The estimated CO2/H2O ratio in gas phase at SGS was only 0.55 (g/kg).
The gas emitted from magma after SGS should has a CO2/H2O ratio lower
than the gas at SGS. The CO2/H2O ratio of gas from fumarole A and B in
Oct. 1993 was 46.2 and 40.7 (g/kg), respectively. Shinohara et al. (2008-
this issue) found that the gases sampled in 1999 to 2001 included much
CO2 although the gas showed the enrichment in HCl and HF similar to
the fumarolic gases in Oct.1993. The CO2 in the fumarolic gas in Oct.1993
may be due to the contamination of a fluid enriched in CO2.
The δ34S of “total sulfur” of fumarolic gas decreased significantly in
Oct. 1993. Here, total sulfur means the combination of SO2 and H2S in
fumarolic gas. The fumarolic gases in Oct. 1993 contained much H2S
relative to SO2. The total S to H2O ratio of the fumarolic gas in Oct. 1993
was much larger than that of fumarolic gas before Feb. 1993 (Fig. 3).
The decrease in the total δ34S could be the contamination of a fluid
enriched in H2S with low δ34S.

Table 6
Open system degassing of magma from Mt. Unzen

Fig. 10. H2O–Cl–F ternary molar composition of fumarolic gas. Circles: Fumarolic gas. f M0 (H2O) M2 (S) M3 (Cl) M4 (F) F2 (S/H2O) F3 (Cl/H2O) F4 (F/H2O)
Rectangles: Estimated gas composition at the first and second gas separations. Solid (mg/kg) (mg/kg) (mg/kg) (mg/kg) (g/kg) (g/kg) (g/kg)
curve: Estimated composition of gas emitted from magma under open system
1.0 5000 2.4 570 350 0.38 4.4 0.35
degassing. Crosses: Fumarolic gases sampled around the lava spine in 1999 to 2001
0.5 2500 1.8 562 349 0.56 8.6 0.70
by Shinohara et al. (2008-this issue). f: Fraction of H2O left in melt under open system
0.1 500 0.9s 545 346 1.37 41.7 3.47
degassing.
 T. Ohba et al. / Journal of Volcanology and Geothermal Research 175 (2008) 120–132
As the candidate for the origin of contaminants, the vapor phase in a
hydrothermal system surrounding the conduit is possible (Fig. 4). The
involvement of a hydrothermal system is supported by the CH4/CO2
ratio in the fumarolic gases, which was 1.6 × 10− 5 to 1.4 × 10− 4. This ratio
was higher than 1 × 10− 6, the upper limit of equilibrated CH4/CO2 ratio
at magmatic temperature and pressure (Giggenbach, 1997). The typical
ratio of the gas phase in hydrothermal system is 10− 2 (Giggenbach,
1997). The observed CH4/CO2 ratio suggests the contamination of a
vapor phase derived from a hydrothermal system.
6. Conclusions
The chemical composition of fumarolic gas sampled at the basement
of the growing dacitic lava dome at Mt. Unzen suggested the separation
of gas from magma at a pressure higher than 96 MPa. The corresponding
depth of separation is deeper than 3.9 km. The separated gas traveled
along the conduit and discharged as fumarolic gas.
The variable CO2/H2O ratio of fumarolic gas can be explained by the
change in the bubble fraction in the pre-eruptive melt of magma. The
estimated range of bubble fraction was 0.90 to 1.73 vol.%. The cor-
responding weight % of the bubbles ranged from 0.20 to 0.39%. The
above weight % of the bubbles is much lower than 6.0 and 3.6%
estimated for the explosive eruptions of 0.73 Ma Bishop Tuff and Mt.
Pinatubo in 1991, respectively (Wallace et al., 1995). The low fraction
of bubbles in the magma chamber at Mt. Unzen may be one of the
reasons why the eruption was non-explosive.
The variation of bubble fraction in the magma chamber would be
controlled by the balance between a mafic magma supplied to magma
chamber and the dacitic magma discharged from the chamber. When
the discharge of magma was suppressed, bubbles in a mafic magma
accumulated at the boundary between the rhyodacitic magma and
mafic magmas.
The composition of gas in 1995 was explained by an open system
degassing model. The HCl enrichment in the gas of Oct. 1993 was also
attributed to the open system degassing effect, although the gases
contained CO2 and H2S with high concentrations. The CO2 and H2S
would be derived from the vapor phase of a hydrothermal system
which developed around the conduit.
Acknowledgements
We thank the researchers and staffs of Institute of Seismology and
Volcanology, Faculty of Science, Kyushu University for their support at
the sampling of volcanic gases.
We thank Dr. D. Rouet for his detailed reviewing and constructive
comments on the manuscript. We also thank an anonymous reviewer
who suggested the use of new data on distribution coefficient bet-
ween gas and melt, which was critically important for the degassing
model.
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