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Geochemical evidence of magma intrusion inferred from diffuse CO2

emissions and fumarole plume chemistry: The 2010-2011 volcanic unrest at
Taal Volcano, Philippines

Article  in  Bulletin of Volcanology · October 2013

DOI: 10.1007/s00445-013-0747-9

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Geochemical evidence of magma intrusion
inferred from diffuse CO2 emissions and
fumarole plume chemistry: the 2010–
2011 volcanic unrest at Taal Volcano,
Philippines
Mª Carmencita Arpa, Pedro
A. Hernández, Eleazar Padrón, Paolo
Reniva, Germán D. Padilla, Ericson
Bariso, Gladys V. Melián, et al.
Bulletin of Volcanology
Official Journal of the International
Association of Volcanology and
Chemistry of the Earth`s Interior
(IAVCEI)

ISSN 0258-8900
Volume 75
Number 10

Bull Volcanol (2013) 75:1-13

DOI 10.1007/s00445-013-0747-9

1 23
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1 23
 Author's personal copy
Bull Volcanol (2013) 75:747
DOI 10.1007/s00445-013-0747-9

RESEARCH ARTICLE

Geochemical evidence of magma intrusion inferred

from diffuse CO2 emissions and fumarole plume chemistry:
the 2010–2011 volcanic unrest at Taal Volcano, Philippines
Mª Carmencita Arpa & Pedro A. Hernández & Eleazar Padrón & Paolo Reniva &
Germán D. Padilla & Ericson Bariso & Gladys V. Melián & José Barrancos &
Dácil Nolasco & David Calvo & Nemesio M. Pérez & Renato U. Solidum Jr.

Received: 24 February 2013 / Accepted: 9 July 2013 / Published online: 27 September 2013
# Springer-Verlag Berlin Heidelberg 2013

Abstract We report herein significant increases in the diffuse
CO2 emission through the lake and soils of the Taal Volcano
Main Crater (Philippines), during a volcano-seismic unrest
period in April 2010–June 2011. Monitoring of CO2 emis-
sions from the Taal Main Crater Lake and soils in the fumarole
areas started in 2008 with a collaborative project between
ITER and PHIVOLCS. In August 2010, the total diffuse
CO2 emission from the Taal Main Crater Lake increased
almost three times from a previously measured baseline emis-
sion value ∼1,000 t day−1 to 2,716±54 t day−1. This increase
occurred during anomalous seismic activity which started in
April 2010. The highest CO2 emission value in the crater lake
was measured in March 2011 at 4,670±159 t day−1 when the
volcano was still showing signs of unrest. Significant changes
in the CO2/SO2, CO2/H2O, and SO2/H2S ratios in the fuma-
role gases suggest the occurrence of a magmatic injection
several weeks before the onset of the volcano-seismic unrest
Editorial responsibility: S. Calvari
M. C. Arpa (*) : P. Reniva : E. Bariso : R. U. Solidum Jr.
Philippine Institute of Volcanology and Seismology (PHIVOLCS),
Diliman, Quezon City, Philippines
e-mail: macar2n@yahoo.com
P. A. Hernández : E. Padrón : G. D. Padilla : G. V. Melián :
J. Barrancos : D. Nolasco : D. Calvo : N. M. Pérez
Environmental Research Division, Instituto Tecnologico y de
Energias Renovables (ITER), 38611 Granadilla de Abona, Teneri-
fe, Spain
P. A. Hernández : E. Padrón : G. D. Padilla : G. V. Melián :
J. Barrancos : D. Nolasco : D. Calvo : N. M. Pérez
Instituto Volcanológico de Canarias (INVOLCAN), Antiguo Hotel
Taoro, Parque Taoro, 22, 38400 Puerto de La Cruz, Tenerife, Spain
period. These observed changes in the CO2 emission rate and
the fumarole gas composition as the result of magmatic activ-
ity were likely caused by magma moving from a deep reser-
voir to a shallow reservoir.
Keywords Magma intrusion . Diffuse CO2 . Taal Volcano
Introduction
Monitoring the chemical composition and discharge rates of
volcanic gases is one of the main tasks in volcano monitoring
programs. Highly mobile volcanic gases are released to the
atmosphere owing to progressive depressurization of magma
during ascent and can reach the surface well before their
parental magma (Hernandez et al. 2001; Granieri et al. 2006;
Aiuppa et al. 2009; Pérez et al. 2012; Padrón et al. 2013).
Among volcanic gases, CO2 is widely used in volcano stud-
ies and monitoring because it is one of the first gas species
released from ascending magma, and it is considered con-
servative (Gerlach 1986; Giggenbach 1996). Many studies
have shown that increase of fumarolic activity and diffuse
gas emissions correlate with magmatic activity (Gerlach
1986; Goff et al. 1998; Taran et al. 2000; Hernandez et al.
2001; Pérez et al. 2012). Measurement of diffuse CO2 emis-
sions in soil is effective in identifying structures within
volcanic areas that are most permeable to volcanic gases
(Chiodini et al. 1998; Rogie et al. 2001; Frondini et al.
2004). Therefore, it is important to investigate CO2 emission
at Taal Volcano because it is an active basaltic system and
volcanism in Taal is significantly affected by local faults and
structures (Alcaraz and Datuin 1974; Listanco 1994;
Pubellier et al. 2000).
 Author's personal copy
747, Page 2 of 13
Monitoring of the volcanic activity of Taal Volcano is a
priority task in the Philippines, because several million peo-
ple live within a 20-km radius of Taal’s caldera rim. Since 26
April 2010, some of the parameters monitored by
PHIVOLCS at Taal Volcano showed anomalous changes,
indicating the start of a volcanic unrest period. In particular,
an increasing daily number of volcanic earthquakes; increas-
ing trends in ground temperatures and total magnetic field
were observed inside the Main Crater; lastly, an inflation
trend has been revealed by precise leveling measurements
since 2004 (PHIVOLCS Volcano Bulletin 2010). These ob-
servations resulted in the raising of Taal Volcano’s status to
Alert Level 2 (in an Alert Level scheme ranging from 0
(lowest) to 5 (highest)) in June 2010 (PHIVOLCS Taal
Volcano Alert Signal).
To improve the early warning system at Taal Volcano,
diffuse CO2 degassing studies started in 2008 through two
collaborative projects between the Philippine Institute of
Volcanology and Seismology (PHIVOLCS) and the
Instituto Tecnologico y de Energias Renovables (ITER).
Since 2008, nine surveys of diffuse CO2 emission have
been performed at the Main Crater Lake as well as in the
fumarole fields and geothermal areas within the Main
Crater. Because volcanic gas composition is another key
parameter to evaluate magma degassing processes beneath
volcanoes, fumarole gas composition was analyzed for
CO2/H2O, CO2/SO2, and SO2/H2S ratios in 2009, in March
2010 (1 month prior to the start of the seismic unrest) and
in March 2011, during the unrest period. This paper reports
the results of (1) diffuse gas surveys carried out at the
Main Crater Lake of Taal and at the inner northeastern
part of the Main Crater, and (2) periodic measurement of
the CO2/H2O, CO2/SO2, and SO2/H2S molar ratios in the
fumarole gases. The results are interpreted in relation to
the volcano-seismic crisis that occurred at Taal Volcano
between 2010 and 2011.
Geological setting
Taal Volcano in southwest Luzon, Philippines, lies between a
volcanic arc front (facing the subduction zone along the
Manila Trench) and a volcanic field formed from extension
beyond the arc front (Defant et al. 1988; Forster et al. 1990)
(Fig. 1). Lavas from Taal Volcano show the typical geochem-
ical signatures of subduction zone magmas and range in
composition from basalt to andesite (Miklius et al. 1991;
Listanco 1994; Mukasa et al. 1994). Taal Volcano Island
consists of a main tuff cone surrounded by several smaller
tuff cones, tuff rings, and scoria cones (Listanco 1994)
(Fig. 2). This island is located in the center of the 30-km
wide Taal Caldera, now filled by Taal Lake. The largest
crater in Taal Volcano Island is referred to as the Main Crater.
Bull Volcanol (2013) 75:747
It was the site of an eruption in 1911, which caused 1,300
casualties (Worcester 1912). The Main Crater is now filled
by a 1.2-km wide, 84-m deep acidic (∼pH 2.8) lake (Main
Crater Lake). Taal has erupted more than 30 times since 1572
(PHIVOLCS Volcano Catalog 2009), and most of its erup-
tions have been hydromagmatic. Its last eruptive period was
from 1965 to 1977 and was characterized by hydromagmatic
to phreatic eruptions that occurred on the southwest flank of
the island (Moore et al. 1966). Between 1992 and 1994, a
period of seismic unrest was manifested as seismic swarms,
opening of new ground cracks on the northern rim of the
Main Crater and on the southeast of the island, and increased
hydrothermal activity (PHIVOLCS Annual Reports 1992,
1993, 1994), but was not accompanied by an eruption. Vol-
canic hazard assessment for Taal Volcano is important be-
cause of the large population at risk. The population of the
island is around 3,700 (Batangas provincial government
2010) and the area around Taal Lake includes 14 cities and
municipalities.
Previous studies have shown the existence of two main
geothermal areas on the surface, one inside and another
outside the Main Crater, which may be produced by the
degassing of a huge hydrothermal system (Fikos et al.
2012). The deep hydrothermal reservoir beneath Taal Volca-
no is a mixture of volcanic water, meteoric water, and sea-
water (Delmelle et al. 1998). The largest geothermal area is
located on the inner northern part of Main Crater (Figs. 3a
and 4), between the crater rim and the north to northeastern
part of Main Crater Lake. Surface geothermal manifestations
such as gas bubbling, solfatara, fumaroles, outlets, hot
springs, and steaming grounds are present in this area, in-
cluding low temperature fumaroles (≤100 °C), and wide-
spread sulfur and Fe-oxide precipitates at the surface, typical
of argillic mineralization. Studies of the composition of these
low temperature fumaroles showed equilibration of magmat-
ic gases with the hydrothermal system under highly oxidiz-
ing conditions (Delmelle et al. 1998). The second area stands
outside the crater, below the east–west-trending fissures that
opened during the 1991–1994 seismo-volcanic crises.
Nishigami et al. (1994) carried out a seismic explosion
survey at Taal Volcano employing refraction, fan-shooting,
and reflection methods. They were able to locate (al-
though with large ambiguity) a low-velocity and low-Q
(Q = rock quality factor, for example: weathered, high
porosity rocks have low Q value) region around the main
crater at a depth of about 1.5 km. They detected a
reflector eastward of the main crater at a depth of about
6 km, which may suggest the top surface of a magma
reservoir.
Between 2005 and 2006, a multidisciplinary study fo-
cused on Taal’s hydrothermal system was launched based
on combined electromagnetic, geochemical, and thermal
surveys (Zlotnicki et al. 2009). This study concluded that
 Author's personal copy
Bull Volcanol (2013) 75:747 Page 3 of 13, 747

Fig. 1 Location of Taal Volcano, Philippines. The Taal caldera rim is indicated with a red line

the northern part of the volcano is undergoing strong Methods

thermal transfers and degassing, with activity taking place
mainly along east–west-trending fissures. These were also
observed by Fikos et al. (2012) by means of resistivity
measurements carried out in March 2012. The results show
also that the source of hydrothermal activity is mainly
located beneath the northern part of the crater and far
below the water level of the Main Crater Lake. Based on
results of magnetotelluric resistivity surveys, Yamaya et al.
(2013) identified a magma reservoir at around 4–6 km
depth and a hydrothermal reservoir at 1–4 km depth beneath
Taal Volcano Island.
From 2008–2011, the ITER-PHIVOLCS collaborative pro-
ject, supported by the Minister of Science and Education of
Spain and the Spanish Aid International Agency (AECID),
performed regular CO2 efflux surveys at the surface of Taal
Main Crater Lake. Diffuse CO2 emission has been measured
in the Main Crater Lake and in the geothermal areas within
the Main Crater by the accumulation chamber method
(Parkinson 1981), using a West Systems (Pontedera, Italy)
portable diffuse flux meter equipped with a LI820 CO2 gas
analyzer. A 2,000-ppm cell was used during the earlier

Fig. 2 a Shaded relief map and aerial view of Taal Volcano. MCL is the Main Crater Lake of the central island of the volcano; b aerial picture of the
volcano taken from the southeast
 Author's personal copy
747, Page 4 of 13
Fig. 3 a Picture of the Main Crater Lake of Taal Volcano (MCL); b measurement of diffuse CO2 degassing at the MCL water surface by means of a
floating accumulation chamber; c picture of the largest hydrothermal discharge area on the northern inner part of the Taal main crater
surveys when the flux values were relatively low and it was
replaced with a 20,000-ppm cell during subsequent surveys.
The accumulation chamber was set on a floating device for
the Main Crater Lake survey following the method reported
by Pérez et al. (2011) (Fig. 3b). Diffuse CO2, together with
Fig. 4 a Spatial distribution of diffuse CO2 emission measurement
sites in the main crater (black squares). The location of the main
geothermal area is highlighted in red color. b Infrared camera images
reveal temperature anomalies at the surface of this area
Bull Volcanol (2013) 75:747
water, soil, and air temperatures were measured at each
survey point, depending on whether it was a lake or a soil
survey. Temperatures were measured using a K-type thermo-
couple probe and dual datalogger thermometer at 0.5 m to
1 m depths (water) and 0.4 m depth (soils). Several measure-
ments (110 to 164 measurement points) were selected for the
Main Crater Lake at intervals of 80 to 100 m in order to cover
the entire area of 1.2 km2. Measurements on land were done
at closer intervals (around 20 m). Figure 4a shows the spatial
distribution of measurement sites on the lake and the location
of the main geothermal area. An infrared camera model FLIR
ThermaCAM P65 was used to obtain the IR pictures. Air
temperature and humidity were measured in situ with a hand-
held digital thermometer–hygrometer before the thermal im-
age collection. Spatial distribution of diffuse CO2 emission
values were constructed using sequential Gaussian simula-
tion algorithms provided by GSLIB software (Deutsch and
Journel 1998; Cardellini et al. 2003).
In order to distinguish the possible different sources con-
tributing to the diffuse CO2 efflux data, a statistical–graph-
ical analysis (Sinclair 1974) was applied to the total data
from each survey in order to check whether each dataset was
composed of one or more statistical populations. The statis-
tical–graphical analysis method is based on the recognition
of inflection points along a curve defined by plotting data
cumulatively on a Log-normal probability scale. The diffuse
CO2 efflux data from each of the surveys plotted along
curves, which can be modeled as a combination of two
 Author's personal copy
Bull Volcanol (2013) 75:747 Page 5 of 13, 747

CO2/SO2
distinct Log-normal populations. These two populations are
interpreted as the background population and the peak pop-

689
99

93
–

–
–

–
–
–
–
ulation, with different mean values at each survey. The
results of this statistical analysis are summarized in Table 1.
SO2/H2S
Table 1 Summary of the diffuse CO2 emission and water temperature data in the Main Crater Lake and the CO2/H2O, SO2/H2S, and CO2/SO2 molar ratios during the study period

Concentrations of CO2, H2O, SO2, and H2S in air near the

0.45
4.50

5.14
– fumaroles (Fig. 3c) were measured using a multigas

–
–

–
–
–
–
sensor—a system already used in several studies with more
CO2/H2O

recent applications in Stromboli Volcano (Aiuppa et al.

2009) and Soufriere Hills (Edmonds et al. 2010). The instru-
0.012

0.058
0.34

ment pumped gas at a flow rate of 1 L/min from the ambient

–

–
–

–
–
–
–
air close to the fumaroles trying to repeat measurements in
water temp.

fresh air and in relatively concentrated plume for 5–50 min.

Average

The instrument was equipped with the following sensors: (1)

32.0
28.9
30.2
33.7
29.7
30.3
32.8
32.4
34.4
33.8
(°C)

LICOR-840 (LI-COR Biotechnology, USA), with a mea-

surement range between 0 and 3,000 ppm for CO2 and 0 to
80 ppt (80 ppt=80,000 ppm) for H2O, and an error lower
Mean peak
population
(g−2day−1)

than 1 ppm on 370 ppm of CO2 and lower than 0.01 ppt on
13,855
1,531
1,360

4,493
3,368

3,396
4,169
3,857
1,149
1,311

10 ppt of water vapor; (2) H2S-BH hydrogen sulfide sensor

(Alphasense, United Kingdom), with a detection range of 0–
50 ppm; (3) SO2-B4 sulfur dioxide sensor, (Alphasense,
background
population
(g−2day−1)

United Kingdom), with a measurement range between 0

and 20 ppm. To estimate the CO2/H2O, CO2/SO2, and
Mean

1,363

2,784
1,006
319
169
389

926

656
210
181

SO2/H2S molar ratios, we used the slope of the line obtained

by least squares regression of CO2 and SO2 peak areas
(t/day)

plotted versus H2O, SO2, and H2S peak areas, respectively

159

114
SD

(Shinohara 2005).
15
22
18
54
55

59

27
22
CO2 output

Results
(t/day)

2,716
1,875
4,670
2,057
1,821
948a
763a
506

482
627

Taal Main Crater Lake

Max. CO2 efflux

Table 1 shows some basic statistics for the measurements

(diffuse CO2 efflux and water temperature) carried out in
(g−2day−1)

18,792.5
1,830.6
1,423.0
2,207.7
5,579.4
4,436.5

6,009.9
9,544.2
5,759.4
1,678.5

each survey on the Main Crater Lake from 2008 to 2012. The
CO2 emission values measured in 2009 and 2010 were
previously reported by Pérez et al. (2011). Temperatures
measured at the surface of Taal Main Crater Lake during this
efflux (g−2day−1)

study (average of all points for each survey) ranged between

29 and 34 °C (Table 1), and are similar to or slightly lower
Min. CO2

than the average ambient air temperatures. The highest water

164.0
670.1
418.0
426.9
327.4

106.9
16.4
n.d.

n.d.
n.d.

temperatures were found near the northern shore of the lake

where strong bubbling was observed (Fig. 5). Because boat
access to this area is dangerous, it was decided not to perform
No. sampling
sites in MCL

water temperature measurements very close to the northern

Data from Pérez et al. (2011)

shore. High water temperatures were measured both near the

129
164
164
163
162

148
121
162
134
110

northern and southern shores, areas that coincide with fuma-

rolic fields and hydrothermally altered grounds within the
Aug.–Sept. 2010

Main Crater (Fig. 4b). Analysis of thermal images was

performed using FLIR R&D software, which allowed us to
March 2010

March 2011
April 2008

May 2011
June 2011
Feb. 2009

Feb. 2011

July 2012
Oct. 2011

correct the IR images for distance, humidity, and air temper-

ature recorded during the survey, and to estimate apparent
Date

water temperatures. After corrections, the average soil

a
 Author's personal copy
747, Page 6 of 13
temperature was 31 °C for the part of Taal Island outside the
geothermal area (Fig. 4b). Maximum soil temperature on the
geothermal area was ∼100 °C, based on field measurements.
The first three surveys conducted from April 2008 to March
2010 established a CO2 baseline value for the Main Crater
Lake. During this time, seismicity was considered low for
Taal and the volcano alert status was set at Alert Level 1
(based on a 0–5 Alert Level Scheme, PHIVOLCS Volcano
Bulletin 2008, 2009, 2010). Total diffuse CO2 emission from
the Main Crater Lake during this period ranged between
506±15 and 947±22 t day−1. Emissions were slightly higher
in February 2009 (947±22 t day−1) concurrent with slightly
higher seismicity; nonetheless seismicity was still consid-
ered to be at a low level (Alert level 1, PHIVOLCS Volcano
Bulletin 2009). Measured CO2 emissions from the lake from
August 2010 to July 2011 were at least three times higher
than the previous measurements, with the highest emissions
in March 2011 (4,670±159 t day−1; Table 1). Diffuse CO2
emissions on the lake have decreased since then, and were in
the range of baseline values in the last survey of July 2012.
Distribution maps showing the secular variations of total
diffuse CO2 emissions in the Main Crater Lake are shown
in Fig. 6.
Northeast fumarolic area
As stated before, the most prominent geothermal area in the
Main Crater—where fumaroles, solfataras, mudpools, and
extremely altered ground occur—is located in its northeast
sector (Fig. 4a). Measurements of soil temperature and diffuse
CO2 and H2S emissions were done for several surveys from
2008 to 2011 in this area. Gas emissions in this area are very
much affected by changing ground permeability because of
mineral precipitation near and at the surface, making the
interpretation of variations in anomalies more complex. How-
ever, temporal change in the overall CO2 output in the soils
Fig. 5 Picture of hot gas bubbling area on the northeast side of Main
Crater Lake
Bull Volcanol (2013) 75:747
reflects the general temporal trend observed for the CO2
emissions from the lake (Figs. 6 and 7). In agreement with
the temporal pattern of lake CO2 emissions, also diffuse CO2
emission in soil increased from 8±1 t day−1 in February 2009
and 10±1 t day−1 in March 2010 to 36±4 t day−1 in September
2010 and remained high in February 2011 (36±6 t day−1). A
visual inspection of the spatial distribution maps for the soil
temperature values measured in 2008, 2009, and March and
September 2010 indicates that relatively high values (>55 °C)
measured in March 2010 were more homogeneously distrib-
uted over the surveyed area than those measured in 2009 and
in September 2010 (Fig. 8), suggesting that the hydrothermal
discharges increased and affected almost the whole geother-
mal area some weeks before the onset of the volcano-seismic
unrest in April.
The obtained correlation for each chemical pair (CO2 vs.
H2O, CO2 vs. SO2, and SO2 vs. H2S) is shown in Table 1 and
depicted in Fig. 9 for 2009, 2010, and 2011 surveys. The
most remarkable characteristic in the evolution of the CO2/-
H2O and SO2/H2S ratios from 2009 to 2011 (Fig. 10) is the
important increase observed in both ratios around 1 month
prior to the onset of the volcano-seismic unrest, while at the
same time CO2/SO2 ratio was observed to decrease. During
the unrest period, the SO2 was the predominant sulfur spe-
cies, and SO2/H2S ratio remained high relative to the year
2009. However, the CO2/H2O ratio decreased again in 2011
to recuperate the values measured in 2009.
Discussion
Main Crater Lake CO2 emission
Considering the Main Crater Lake surface area (1.2 km2), the
normalized diffuse CO2 emission (CO2 output/area) range in
the study period is 402–3,892 t day−1 km−2. In a global
context, and based on the data reported by Pérez et al.
(2011), the maximum emission rate observed in this work
is the highest value reported to date for a volcanic lake in the
world. The CO2 background emission of the Main Crater
Lake was set at ∼351 t day−1 by multiplying the mean
average of the background population for the first three
surveys (292.5 g m−2 day−1; Table 1) by the total area
(1.2×106 m2). The background CO2 efflux population for
the Main Crater Lake cannot be interpreted as influenced by
biological activity of the lake since: (1) the acidity of the
waters is pH<3 (Delmelle et al. 1998), confirmed by repeat-
ed measurements during this work, and (2) Taal Lake, the
large alkaline lake surrounding Taal Volcano Island (Fig. 2),
which is widely used for fisheries, has shown a much lesser
maximum diffuse CO2 emission of ∼15.1 g m−2 day−1
(Melián et al. 2008). In comparison to other volcanoes, a
background mean population of 464 g m−2 day−1 and a mean
 Author's personal copy
Bull Volcanol (2013) 75:747 Page 7 of 13, 747

Fig. 6 Average spatial

distribution map of CO2 efflux
values measured at the water
surface of the MCL of Taal
Volcano from 100 sequential
Gaussian simulations. Owing to
the saturation of red-color values
using a scale up to
3,000 g m−2 day−1, the map
regarding the March 2011
survey, is shown also with a scale
up to 6,000 g m−2 day−1

peak population of 6,702 g m−2 day−1 were measured for the
crater lake of El Chichon Volcano (Mazot and Taran 2009).
Latest magmatic intrusion episode
Figure 11 depicts the high-frequency earthquake counts
recorded from a seismic station located in the Main Crater
and the diffuse CO2 degassing rate in the Main Crater Lake
and the fumarolic area shown in Figs. 6 and 7, respectively. A
good correlation between diffuse CO2 emissions from the
Main Crater and local seismicity is observed. In the period
August 2010 to June 2011, the CO2 emissions measured in the
Main Crater Lake were five to 13 times higher than the
background emission value of 351 t day−1. The seismic unrest
started increasing significantly in April 2010 (PHIVOLCS
Volcano Bulletin 2010) and lasted approximately for the same
period of anomalously high CO2 emission. The highest total
CO2 emission from the Main Crater Lake was recorded in
March 2011 (4,670±159 t day−1) 2 months before the highest
earthquakes (high-frequency volcanic quakes) count (115)
recorded (PHIVOLCS Volcano Bulletin 2011) in the unrest
period. The relationship between CO2 emissions and high
seismicity supports their common cause, likely due to the
occurrence of a magmatic intrusion event, which increased
the pressure of the Taal Volcano magma reservoir and local
tectonic system. For example, dike injection beneath Augus-
tine Volcano was shown to affect nearby faults resulting in
increased seismicity before its eruption in 2006 (Fisher et al.
2010). The pressure-dependent release of CO2 from an
upward-migrating magmatic intrusion at depth can in turn
increase gas emissions at the surface by advection/diffusion
of the gas through the sublayers (Gerlach 1986; Hernandez
 Author's personal copy
747, Page 8 of 13 Bull Volcanol (2013) 75:747

Fig. 7 Average spatial

distribution map of CO2 efflux
values measured at geothermal
areas inside the Main Crater of
Taal Volcano from 100
sequential Gaussian simulations.
The yellow dashed line shows
the crater rim

Fig. 8 Average spatial

distribution map of soil
temperature values measured in
2008, 2009, and March and
September 2010 at the north–
northeast fumarole area from 100
sequential Gaussian simulations.
The yellow dashed line shows
the crater rim
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Bull Volcanol (2013) 75:747 Page 9 of 13, 747

Fig. 9 Correlation plots of CO2 versus H2O and SO2, and SO2 versus H2S concentrations (peak area units) measured during the 2009, 2010, and
2011 surveys in the gases from the fumarole area. The solid black lines indicate the concentration ratio estimated from the best fit of data

et al. 2001). Another possible explanation for the observed
increase in seismicity is fracturing of country rock due to the
cooling magma intrusion. As the magma body cools, residual
release of heat and magmatic gases during crystallization
heats country rock pore waters producing overpressures and
resulting in hydraulic fracturing in the country rock (Titley
1990). Additional evidence for a magmatic intrusion event is
given by PHIVOLCS-JICA GPS data, which show significant
inflation from the start of 2011 (when data became continu-
ous) to mid 2011, comparable to the 1999 (Lowry et al. 2001)
and 2000 (Bartel et al. 2003) magnitude of displacements in
Taal. Below Taal Volcano, a low velocity zone has been
interpreted as a deep magma reservoir placed at 18 km depth,
based on shear wave velocity modeling (Besana et al. 1995)
while a shallow magma source for Taal was modeled at
5.2 km depth (95 % confidence range of 3.2–9.1 km depth),
based on GPS data from an inflation event that occurred in
2000 (Bartel et al. 2003). A similar depth for a shallow magma
reservoir (∼6 km) was interpreted from seismic surveys
(Nishigami et al. 1994) and resistivity surveys (Yamaya
et al. 2013). Melt inclusions in olivines with modeled pressure
of crystallization of 2.5 kbar (∼8 km depth), from a 5 ka
basaltic deposit of Taal, contained no CO2 (or less than the
minimum detection limit of the instrument used) (Martinez
and Williams 1999), implying that at this pressure depth most
of the CO2 in the magma has degassed already. Given these

Fig. 10 Temporal evolution of

the CO2/H2O (solid blue circles)
and SO2/H2S (solid red circles)
and CO2/SO2 (solid green
circles) ratios in the gases
emitted from the fumarole area.
The daily number of high-
frequency seismic events is also
displayed with gray bars
(PHIVOLCS Volcano Bulletin
2008–2012).
 Author's personal copy
747, Page 10 of 13 Bull Volcanol (2013) 75:747

Fig. 11 Temporal evolution of

the diffuse CO2 emission rate
through the water surface of the
MCL (red circles, in Log scale)
and through the soils of the
northern inner part of the Taal
main crater (blue squares) during
the study period. The daily
number of high-frequency
seismic events is also displayed
with gray bars

premises on the possible depths of magma reservoirs, the
increase in CO2 emissions recorded in the Main Crater Lake
could represent degassing of a magma body that moved from
a deep source to a shallower emplacement level in 2010–2011,
but did not result in an eruption. Based on previous studies
and reports since the last eruption period in 1965–1977, there
have been at least two other magma intrusion events in the
past—namely (1) in 1992–1994, magma intrusion produced
seismic swarms, ground fissuring, and increased hydrother-
mal activity (PHIVOLCS Annual Reports 1992, 1993, 1994)
and (2) in 2000, when magma intrusion produced an inflation
event recoded by GPS network (Bartel et al. 2003). Ground
deformation studies done on Santorini imply that the shallow
magma chamber is recharged episodically by discrete batches
of magma (Parks et al. 2012). A similar process may apply to
Taal, which is also a large magmatic system. In fact, this was
suggested from petrological and geochemical evidences,
which show that compositional trends in the Taal lavas can
be produced by fractionation of discrete magma batches and
mixing of these batches (Miklius et al. 1991).
high temperature, stressing that hydrothermal discharges in-
fluence ground temperature (Figs. 7 and 8) (Stevenson 1993).
Our data show a good correlation between CO2 efflux and soil
temperature, with temperature being increased by steam con-
densation (Frondini et al. 2004).
Aiuppa et al. (2009) showed that volcanic gases emitted
immediately prior to and during the eruptions at Stromboli
Volcano were remarkably different in composition (richer in
CO2) from those typical of ordinary Strombolian activity.
They interpreted the observed anomalously high CO2/SO2
plume ratios as evidence of enhanced supply of deeply
derived CO2-rich gas bubbles to the shallow plumbing sys-
tem of the volcano. Calculated CO2/SO2 ratio for Stromboli
gas emissions, using a thermodynamic saturation model,
show CO2/SO2 ratio of ∼150 at 240 Mpa (∼8 km depth)
and a decreasing curve for plotted CO2/SO2 ratios as pres-
sure decreases (Aiuppa et al. 2009). Our results show a
decrease in CO2/SO2 ratio from 689 (in 2009) to 99 (in

Soil gas emissions and fumarole gas chemistry

When increased CO2 emissions in the soil and lake were first
observed in August 2010, soil temperature in the fumarolic
area remained below 100 °C, consistent with the buffering
effect due to boiling of the shallow hydrothermal system. It
also suggests that the magma source of the gases was relatively
deep (Stevenson 1993). Unfortunately, soil temperature was
not measured during the February 2011 survey because the
thermometer logger was damaged, and soil efflux measure-
ments were not done on the fumarolic area in subsequent
surveys when the CO2 emissions were high. Despite maxi-
mum temperatures being lower than 100 °C during the time of Fig. 12 Evolution in CO2/SO2 and SO2/H2S ratios of gases emitted
the surveys, areas with high gas flux correlated with areas of from the fumarole area
 Author's personal copy
Bull Volcanol (2013) 75:747
2010) and 93 (in 2011; Fig. 9). Although the model for
Stromboli was developed with a set of parameters for
Stromboli's volcanism (basaltic magma), if we assume sim-
ilar conditions for Taal, we can consider that in 2009, with a
CO2/SO2 ratio of 689, the magma was at depths greater than
8 km. The decrease in CO2/SO2 ratio to 93 in 2011 can be
interpreted as an ascent of magma to depths close to the
shallow magma reservoir (∼6 km) identified for Taal from
geophysical methods (Nishigami et al. 1994; Bartel et al.
2003; Yamaya et al. 2013).
The relative proportions of H2S and SO2 in volcanic gases
are conditioned by temperature, pressure, and redox condi-
tions according to the reaction (Giggenbach 1987):
H2 S þ 2H2 O↔SO2 þ3H2 ð1Þ
This chemical equilibrium favors the exsolution of gases
with high SO2/H2S ratios from high-temperature, low-
pressure magmatic melts, while low SO2/H2S ratios in vol-
canic gases are favored by re-equilibration of magmatic
gases within colder and reducing hydrothermal envelope
(Giggenbach 1987; Aiuppa et al. 2006). At the low fumarole
temperature measured in Taal (boiling water temperature),
the predominant sulfur species should be H2S. The SO2/H2S
ratio measured in February 2009 (∼0.45) agrees with this
statement, but with a non-negligible amount of SO2. The
presence of SO2 in the low temperature fumarole gases in
Taal indicates the lack of fluid–rock equilibrium due to high
rise velocities of volcanic gases, as proposed by Giggenbach
(1987). The magmatic intrusion that occurred between 2010
and 2011 resulted in the injection of SO2-rich hot magmatic
gases in the H2S-rich cold hydrothermal system of Taal. This
injection increased the velocities of the rising gases, thus
exhibiting high SO2/H2S in the fumarole gases. The rise of
the magma probably started aseismically before March 2010,
because SO2/H2S increased two orders of magnitude in
March 1, 2010.
Edmonds et al. (2010) proposed a model for volcanic gas
composition during magma degassing and decompression,
based on a multicomponent equilibrium saturation model.
Based on a CO2/SO2 vs. SO2/H2S diagram, if magma is
decompressed and erupts, gases would evolve along a curve
defined by a decreasing trend of CO2/SO2 and an increasing
trend of SO2/H2S ratios. Assuming this model for Taal data,
the plot of CO2/SO2 and SO2/H2S ratios from Taal fumarole
discharges between 2009 and 2011 (Fig. 12), indicates that a
decompression of magma occurred sometime between 2009
and 2010. Unfortunately, the absence of a more detailed time
series of these valuable chemical ratios does not allow for
setting more accurately the start of this magmatic injection.
However, we can conclude that this magma intrusion oc-
curred before the onset of the anomalous seismicity. This
observation is the most important precursory signal of the
Page 11 of 13, 747
volcanic unrest that was observed at Taal volcano. The
observed drop of CO2/H2O ratio during the unrest period
was probably caused by interaction of the magmatic fluids
with meteoric waters.
Conclusions
In the period of August 2010 to June 2011, the Main Crater
Lake of Taal Volcano released the highest diffuse CO2 emis-
sion rates reported to date by volcanic lakes worldwide. This
significant increase in CO2 emission from the lake coincided
with the occurrence of a volcano-seismic unrest character-
ized mainly by a significant increase in the frequency of
volcanic earthquakes. The maximum CO2 emission rate
measured in the study period occurred 2 months before the
strongest seismic activity recorded during the unrest period.
Significant increases both in the CO2/H2O and in the
SO2/H2S molar ratios prior and during the seismic crisis
are clear geochemical precursory signals of the volcanic
unrest that was observed at Taal Volcano. The observed
changes both in gas emission and in its composition can be
interpreted as being caused by intrusion of fresh magma,
which degassed at depth but did not lead to an eruption.
The campaign-type CO2 emission surveys in the Main Crater
Lake and measurements of the fumaroles are done at least
once or twice a year with increased frequency of surveys
when signs of unrest are detected. These measurements
make an important contribution to the understanding of
volcanic activity and estimating volcanic gas hazards. The
observed patterns of CO2 emission and chemical ratios in the
fumarole gases with seismic activity provide significant in-
sight on the build up and release of volcanic gas pressure,
modalities of gas migration, and of fracture-controlled gas
release, and precursory potential of volcanic gases.
Acknowledgments This research was supported by the projects fi-
nanced by The Spanish Agency for International Development Coop-
eration (AECID) (08-CAP2-1202) and by the Spanish Ministry of
Science and Technology (CGL2005-07509), as well as by the Cabildo
Insular de Tenerife (Spain). We are also grateful to the staff of Taal
Volcano Observatory. Special thanks are given for logistical support by
residents of Taal Volcano Island, particularly our boat men Jerry and Jo-
em who skillfully paddled the canoe to each measurement sites for all
the many surveys. Inputs and comments from reviewers improved the
manuscript.
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