Journal of Volcanology and Geothermal Research 92 Ž1999.

169–179
www.elsevier.comrlocaterjvolgeores

Chemistry and isotopic composition of fumarole discharges of

Furnas caldera
a,) b
Teresa Ferreira , Niels Oskarsson
a
˜ de Deus, 9500 Ponta Delgada, Portugal
Geosciences Department, UniÕersity of the Azores, Rua da Mae
b
Nordic Volcanological Institute, GrensasÕegur 50, IS-108 ReykjaÕik, Iceland
Accepted 20 April 1999

Abstract

Two fumarole grounds at Lagoa das Furnas and Furnas village and a fumarole on the bank of Ribeira dos Tambores are
located on a west–east tectonic lineament across the topographic low of the Furnas caldera. The discharge of the fumaroles
derives from steam separation from shallow Ž100–200 m. aquifers at temperatures of about 1808C. As inferred from
nitrogenrargon relations and deuterium–oxygen isotope relations the hydrothermal fluid is derived from local precipitation
after some 10% steam fractionation in the fumarole conduits. Sulphur isotope ratios of the discharge, being close to those of
juvenile rock sulphur, indicate extensive rock-leaching within the aquifers. The carbon isotope composition of the fumarole
discharge and carbon dioxide saturated waters encountered across the caldera floor suggests that the source of carbon is
regional outgassing of mantle derived juvenile carbon dioxide. Chemistry of the acid gases, carbon dioxide and hydrogen
sulphide in the discharge indicates a slight fractionation induced by different boiling in the shallow hydrothermal aquifers.
Traces of hydrogen and methane contained in the discharge bear no relation to the low temperature water–steam equilibria
of the Furnas fumaroles. Assuming a deeper origin of these gases, a simple model for binary mixtures of methane and
hydrogen indicates that these gases are derived from supercritical conditions, presumably equilibrated within hot rocks below
the hydrothermal system. The remarkably stable ratios of hydrogen and methane, also considering their inferred deep origin,
suggest that these gases might be considered for future chemical monitoring of the fumarole discharge in Furnas. q 1999
Elsevier Science B.V. All rights reserved.

Keywords: hydrothermal aquifer; fumarole discharge; Furnas caldera

1. Introduction stantly around the boiling point of the fluids. There

The fumarole grounds ŽFig. 1. of Furnas caldera
ŽGaspar et al., 1996; Guest et al., 1999-this issue. are
small surface manifestations of boiling in shallow
hydrothermal aquifers. Surface temperatures are con-
)
Corresponding author. Tel.: q351-096653044r1345; fax:
q351-096-653640; E-mail: tf@alf.uac.pt
is a lineament of warm springs and carbon dioxide
saturated waters across the caldera floor from west to
east. These waters are of a remarkably stable compo-
sition and have remained so for at least the last 100
years ŽCruz et al., 1999-this issue. and the fumarole
discharge is assumed to have remained stable for a
long time. This is supported by the surface alteration
around the fumaroles which is confined to small

0377-0273r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 7 - 0 2 7 3 Ž 9 9 . 0 0 0 7 4 - 8
170 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179

Fig. 1. Morphostructural map of Furnas volcano ŽGaspar et al., 1996. showing the locations of the fumarole grounds. LG denotes the
fumarole ground at the north bay of Lagoa das Furnas, CG denotes the Caldeiras fumarole ground in Furnas Village and RT marks the
Ribeira dos Tambores fumarole at the western bank of the river. Note that the fumarole grounds are encountered along the regional fault
system.

areas around Lagoa das Furnas and Caldeiras in the
Furnas village. The Lagoa das Furnas field ŽLG.
issues at the ground water surface from a small
coastal platform on the north coast of Lagoa das
Furnas. Surface alteration is characterised by kaolin-
ite, which indicates acid leaching of the surface
layer. Steam heated pools of an acid mixture of
hydrothermal water and surface water are loaded
with pyrite mud Ža heavy suspension of marcasite
and clays.. The hydrothermal water discharge is low
and surface waters flood the fumarole ground from
time to time. The coastal plain adjacent to the fuma-
role ground is impregnated by steam and carbon
dioxide saturated condensate resulting in low grade
 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
alteration of the sandy surface layer. No signs of
previous or more extensive high temperature surface
alteration are found in this locality.
Caldeiras, in Furnas village, is the largest fuma-
role ground within the Furnas caldera where several
moderately large fumaroles of different character are
active within an area of several hundred square
metres. The discharge issues through volcanic rocks
which are a few metres above the ground water
surface. Surface alteration in Caldeiras is variable; at
the highest steaming elevations the rocks are broken
down to a kaolinite mass with abundant deposits of
monoclinic sulphur and subsequently formed or-
thorhombic sulphur and gypsum. Where condensate
pools have formed, the surface is covered with pyrite
mud. Of special importance is Caldeira Grande ŽCG.
where pristine hydrothermal fluid is discharged Žthe
only occurrence within the Furnas caldera. with a
steady steam separation in a water-filled bowl.
Caldeira do Asmodeu is a vigorously boiling fuma-
role where steam explosions have occasionally oc-
curred. Caldeira Grande and Caldeira do Asmodeu
are referred to as samples PF-09 and PF-10 in Cruz
et al. Ž1999. and in the subsequent text and figures.
Fumarole CG issues the only fluid in Furnas that can
be used for chemical thermometry based on alkali
and silica temperatures.
On the steep west bank of Ribeira dos Tambores,
SE of Caldeiras, the fumarole marked RT issues
from a fissure in the Marconas trachyte dome ŽFig.
1.. There are virtually no surface manifestations
around this fumarole. A slight alteration across cracks
in the trachytic rock is the only visible sign in
addition to some pyrite mud downslope from the
fumarole vent.
All the Furnas fumarole grounds are surrounded
by intensive soil degassing of carbon dioxide. This
indicates that the hydrothermal aquifers, as well as
the cold springs in Furnas are close to saturation
with carbon dioxide.
Origins of the carbon dioxide dominated dis-
charge of fumaroles on Sao ˜ Miguel were attributed
to deep mantle degassing, based on carbon
dioxiderhelium ratios ŽTolstikhin et al., 1991.. He-
lium isotope ratios at about six times atmospheric
ratio were related to a mantle source of anomalous
isotopic composition, matching the continental man-
tle. The aim of the present contribution was to
171
examine the fumarole discharges within the Furnas
caldera by detailed analysis of chemical components
that take part in reactions within the hydrothermal
pressure–temperature regime. This will allow inter-
pretation of high temperature equilibria that might be
used as a basis for chemical monitoring of the
discharge. The basic premise of the study is to
attribute chemical components of the discharge to
deep processes ŽOskarsson, 1984. that may give
indications on the state of activity of the magmatic
system. The fumarole discharges of the Furnas
caldera are dominated by carbon dioxide ŽFerreira,
1994; Martini, 1994; Ferreira et al., 1995. which
may, to a first approximation, be considered as an
indication of deep-seated degassing. Carbon dioxide,
however, is not appropriate for monitoring, since its
high abundance in the discharge Ž95–99 mol% of
gases. masks all fine-scale changes that might occur
in the carbon dioxide concentration. The present
study, therefore, is focused upon reactive and inert
trace components of the discharge.
2. Sampling, analysis and analytical results
Fumarole discharges were sampled in 100–200
ml borosilicate glass tubes with a septum and a
Teflon stopcock. Silicon rubber tubing was used to
connect the tube stopcock to a polyethylene funnel,
which was placed over the steam vent of the fuma-
role. The first stage of sampling was to flush the
entire sampling train with the fumarole discharge
through the septum assembly until it was considered
to contain clean discharge. After flushing, the sep-
tum outlet of the tube was closed and 10–15 ml 12
M KOH were injected through the septum and the
tube was placed in cooling water. The acid gases are
adsorbed during sampling so only the fixed gases
comprise the gas volume of the tube while the
hydroxide becomes diluted by condensate. Sampling
is continued until the tube is almost at the atmo-
spheric pressure. This sampling method is essentially
the so called Giggenbach method ŽGiggenbach and
Goguel, 1989. with only a minor modification.
Samples of the fumarole discharge for deuterium
and oxygen isotopic analysis were condensed Žtotal
condensation of steam. in a glass bulb and kept in
glass bottles. Carbon isotope analysis was made on
172 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179

bulk barium carbonate precipitates from the basic Table 2

condensate after oxidation of sulphide to sulphate by Chemical composition of fumarole discharge, in mol%, ŽFerreira,
1994. from Lagoa das Furnas ŽLG. and Ribeira dos Tambores
hydrogen peroxide. Sulphur isotopes were analysed ŽRT. ŽFig. 1.. Sample labels for the LG series denote collection
in barium sulphate derived by acid washing of the date Žyymmdd.. Samples from RT were collected in May–June
bulk precipitate. Water samples for deuterium and 1991
oxygen isotopic analysis were filtered through 0.45 Sample CO 2 H2S CH 4 H2 N2 O 2 qAr
micron cellulose membrane filters and kept in glass LG910510 92.50 0.034 0.0129 0.950 60164 0.335
bottles. Carbon and sulphur isotopes in water were LG910604 98.73 0.326 0.0018 0.103 0.658 0.177
analysed in combined barium carbonate–sulphate LG910604A 98.81 0.325 0.0024 0.138 0.603 0.122
precipitate from 2 l of water. The combined precipi- LG910618 98.88 0.443 0.0021 0.121 0.412 0.138
tate was filtered, dried and kept in glass bottles. LG910618A 98.45 0.477 0.0020 0.119 0.728 0.220
LG910704 98.84 0.434 0.0019 0.125 0.442 0.153
Mass balance of the sampling procedure is kept LG910704A 98.94 0.441 0.0019 0.117 0.380 0.125
by weighing of the gas tube before and after collec- LG910729 98.59 0.467 0.0019 0.123 0.623 0.196
tion and weighing the tube after internal pressure LG910729A 98.55 0.546 0.0021 0.124 0.567 0.209
adjustment by injection of degassed water. The vol- LG910812 99.01 0.436 0.0019 0.109 0.341 0.098
ume and density of the KOH absorbing solution is LG910812A 98.84 0.402 0.0019 0.125 0.464 0.165
LG910826 99.19 0.472 0.0019 0.100 208 0.031
measured and its mass is subtracted form the mass of LG910826A 99.18 0.458 0.0019 0.102 0.218 0.036
the tube contents. LG910909 99.22 0.493 0.0016 0.084 0.174 0.030
LG910909A 99.07 0.460 0.0019 0.106 0.308 0.058
LG910924 98.60 0.439 0.0017 0.109 0.687 0.166
Table 1 LG910924A 98.83 0.68 0.0018 0.104 0.484 0.108
Chemical composition of fumarole discharge, in mol%, ŽFerreira, LG911008 99.00 0.546 0.0022 0.118 0.238 0.035
1994. from Caldeira Grande in Furnas Village ŽFig. 1.. Sample LG911008A 99.11 0.528 0.0021 0.107 0.218 0.034
labels denote collection date Žyymmdd. LG911025 98.95 0.481 0.0021 0.114 0.391 0.065
a
LG920128 99.08 0.387 0.0026 0.133 0.358
Sample CO 2 H2S CH 4 H2 N2 O2 q b
LG920128A 99.02 0.377 0.0020 0.110 0.428
Ar
LG910510 92.63 0.500 0.0309 1.672 4.926 0.241 Ribeira dos Tambores
LG910510A 92.11 0.311 0.0214 1.298 5.595 0.666 FU91RT01 97.02 0.770 0.0290 0.504 1.567 0.331
LG910510B 99.00 0.637 0.0033 0.161 0.191 0.005 FU91RT02 97.41 0.400 0.0181 0.309 1.828 0.038
LG910510C 91.60 5.407 0.0291 1.286 1.628 0.052 FU91RT03 97.65 1.010 0.0229 0.343 0.940 0.038
LG910603 98.64 0.648 0.0051 0.272 0.403 0.031
a
LG910603A 98.28 1.115 0.0045 0.224 0.348 0.033 Ar s 0.0085 mol%, Oxygens 0.0350 mol%.
b
LG910618 98.38 0.873 0.0049 0.263 0.355 0.125 Ar s 0.0085 mol%, Oxygens 0.0545 mol%.
LG910618A 98.39 0.935 0.0043 0.241 0.322 0.111
LG910704 98.60 0.849 0.0042 0.225 0.257 0.066
LG910704A 97.95 0.835 0.0041 0.222 0.775 0.210
LG910729 97.92 1.380 0.0045 0.223 0.359 0.117 Carbon dioxide in the basic condensate was anal-
LG910729A 97.42 0.821 0.0065 0.350 1.182 0.220
ysed by automated titration with hydrochloric acid
LG910812 98.57 0.717 0.0041 0.209 0.380 0.121
LG910812A 98.39 0.881 0.0042 0.220 0.374 0.127 and hydrogen sulphide was titrated with mercury
LG910826 97.23 0.861 0.0043 0.219 1.362 0.321 acetate using dithizone for end point detection.
LG910826A 97.71 0.897 0.0039 0.201 0.983 0.205 The fixed gases were analysed on a chromato-
LG910909 98.49 0.971 0.0042 0.215 0.257 0.064 graph ŽFerreira, 1994. with automated fixed sample
LG910909A 98.58 0.821 0.0039 0.179 0.335 0.083
loop, molecular sieve column and thermal conductiv-
LG910924 98.45 0.971 0.0044 0.219 0.279 0.077
LG910924A 98.24 0.939 0.0040 0.191 0.492 0.130 ity detector. Flushing and filling of the sample loop
LG911008 97.72 0.985 0.0044 0.226 0.855 0.213 was made at atmospheric pressure. Argon and oxy-
LG911008A 97.77 0.886 0.0113 0.586 0.582 0.162 gen are eluted together from the molecular sieve
a
LG920128 98.54 0.787 0.0047 0.236 0.383 column so argon was analysed in a separate run after
b
LG920128A 98.46 0.811 0.0045 0.237 0.384
washing the sample with basic pyrogallol solution.
a
Ar s 0.0108 mol%, Oxygens 0.0418 mol%. Analytical results for the gas content of the fuma-
b
Ar s 0.0199 mol%, Oxygens 0.0841 mol%. role discharges are listed in Table 1 ŽCG-samples.
 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179 173

Table 3 hydrothermal and spring waters is considered by for

Isotopic composition of waters and fumarole discharge from the in Cruz et al. Ž1999-this issue..
Furnas caldera. Samples CG ŽCaldeira Grande., LG ŽLagoa das
Furnas. and RT ŽRibeira dos Tambores. are listed at the head of
the table. Sample labels for the water samples are given in Table
2, Cruz et al. Ž1999-this issue.. Water samples 09 and 10 represent 3. Discussion
Caldeira Grande and Caldera Asmodeu in Furnas Village. Sample
marked Ribeira Quente was collected in May 1991. This sample is The origin of the waters of Furnas caldera and the
assumed to represent the average composition of waters in the
Furnas caldera ŽSee Fig. 2.. Isotopic analyses were made by Dr.
relations between the local ground waters, hydrother-
Karel Zak at The Czech Geological Survey, Praha mal fluids and the fumarole discharges are outlined
Sample dD‰ d 18 O‰ d 13 C‰ d 34 S‰ in terms of deuterium and oxygen isotopes in Fig. 2.
The principal runoff from the Furnas caldera is
Fumarole samples
CG y26.0 y4.3 y6.1 y1.8 discharged by Ribeira Quente towards the south
LG 2.5 y0.4 y4.8 y0.7 coast ŽFig. 1.. The water sample marked Ribeira
RT y4.0 y1.9 y3.3 y2.1 Quente in Table 3 and Fig. 1 was collected close to
fumarole location RT. This sample is assumed to
Water samples
represent the average isotopic composition of the
PF01 y17.0 y4.2 0.6
PF02 2.4 Furnas waters and precipitation. In Fig. 2, this sam-
PF04 1.7 ple Žfilled diamond. falls within a cluster of water
PF05 4.0 samples which show a short fractionation range
PF07 y11.0 y3.2 y4.8 15.5 slightly above the global meteoric fractionation line.
PF09 y3.0 0.3 1.7 6.8
Fumarole CG represents the only uncontaminated
PF10 6.5 2.8 y3.7
PF13 y17.0 12.2
PF14 y19.9 9.0
PF15 y18.5 y4.3 y16.3 7.3
PF16 y15.0 y3.9
PF18 y10.5 y4.0 y3.3 8.8
PF19 y3.5
PF20 y18.5 y4.3
PF21 y5.5 y2.8
PF24 y16.0 y4.4 y5.7
PF27 y20.0 y1.9 y20.4 10.3
Ribeira Quente 14.5 y4.0

and in Table 2 ŽLG and RT-samples.. It is noted that

the uniformly high carbon dioxide of the discharge
makes the collection and analysis of these samples
difficult in terms of contamination. In effect, all
components but carbon dioxide and steam are trace
constituents of the gas as illustrated by methane
values as low as 20 ppm in the fixed gases which
corresponds to about 1 ppm in the fumarole dis-
charge. The quality of the present data set is, how-
ever, found to be adequate for interpretation of these
constituents.
Isotopic compositions of the fumarole discharge
samples, hydrothermal waters from Caldeira Grande
and Caldeira do Asmodeu and selected water sam-
ples are given in Table 3. The chemistry of the
Fig. 2. Deuterium–oxygen isotope relation of the Furnas fu-
maroles in relation to spring water form within Furnas caldera
ŽCruz et al., 1999-this issue.. Fumarole discharges are indicated
by filled squares, hydrothermal water is indicated by diamonds
and water samples are indicated by small open squares. Filled
diamond indicates the assumed average isotopic composition rep-
resented by sample from Ribeira Quente ŽTable 3.. The global
meteoric line ŽNuti, 1989. is drawn across the figure. The arrows
indicate isotope fractionation by steam separation. The upper
arrow connects the assumed initial water composition with the
Žresidual. hydrothermal fluid and the lower arrow connects the
water and the steam Ždischarge. of Caldeira Grande.
174 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
hydrothermal fluid in Furnas caldera. In Fig. 2, a
steam fractionation line connects the isotopic compo-
sition of the Ribeira Quente water and the water in
Caldeira Grande ŽSample 09. and in Caldeira do
Asmodeu ŽSample 10.. We are aware that the present
data set on isotopic composition of the Furnas fluid
is far from being complete enough for a quantitative
account for steam fractionation within the Caldeiras
fumarole ground. However, based on the data at
hand, it is suggested that samples 09 and 10 repre-
sent steam fractionation of the local water as indi-
cated by an arrow in the figure. The slope of the line
ŽNuti, 1989. indicates fractionation between 10 and
20% at about 1808C. The composition of fumarole
discharge condensate from the CG vent shows a light
isotope shift which is in accordance with the above
suggestion.
There is no doubt that the isotopic compositions
of fumarole condensates RT and LG indicate exten-
sive surface mixing of hydrothermal water and local
ground water. This conforms well with the surface
conditions for these fumaroles which may be de-
scribed as steam heated pools or gas bubbling through
a local ground water cover.
Deuterium and oxygen isotopes of the discharge
in Furnas suggest low aquifer temperatures. There
are no signs of boiling in underlying hotter aquifers
which would be displayed by deuterium fractionation
at or above the inversion temperature of 2208C.
The origins of the dissolved volatiles in the Fur-
nas fluids are outlined in Fig. 3 where the isotopic
compositions of sulphur and carbon show distinct
grouping related with their sources ŽAllard, 1983..
Sulphur isotopes of the water samples ŽCruz et al.,
1999-this issue. show that spring waters represent
mixtures of marine sulphur and juvenile sulphur
derived from leaching of volcanic rocks. The hy-
drothermal waters are rich in rock sulphur and the
sulphur in the fumarole discharge is dominantly of
juvenile origin.
Carbon isotopes of the Furnas fluids indicate a
biogenic source for the carbonate in cold spring
waters outside the central part of the caldera. All
fluids, regardless of temperature and chemistry, that
issue from the carbon dioxide rich lineament across
the caldera are fed by a carbon source of a deep
origin. The thermal waters are an exception to this
general pattern as expected due to degassing during
Fig. 3. Sulphur and carbon sources of the Furnas fluids outlined
by isotopic composition. Fumaroles and carbon dioxide saturated
waters ŽCruz et al., 1999-this issue. show a narrow isotopic range
in carbon, enclosed within dashed, vertical lines in the figure. This
carbon source is assumed to be mantle-derived regional out-
gassing of carbon dioxide. Cold waters with low carbonate Žopen
squares. in the middle left of the figure indicate a biogenic carbon
source. The hydrothermal waters Žopen diamonds. indicate carbon
dioxide loss and isotope fractionation by boiling. Isotopic compo-
sition of sulphur in the Furnas fluids confirms that the fumaroles
are dominated by juvenile leached rock sulphur and that the low
salinity waters fall on a mixing trend with meteoric sulphur
derived from seawater. Isotopic composition of sulphur in the
hydrothermal waters Žless than 5%. indicates the dominance of
juvenile sulphur.
boiling and steam loss. In general, the hydrothermal
fluid issuing from Caldeira Grande ŽCruz et al.,
1999-this issue. is in equilibrium with minerals of
the aquifer, as inferred from chemical analysis and
chemical thermometry ŽGiggenbach, 1980; Fournier
´
and Potter, 1982; Arnorsson, 1991.. However, the
comparison of results derived from chemical ther-
mometers based on fluids and gases points towards
disequilibrium among fluid and gases. Gas geother-
´
mometers ŽArnorsson, 1991. show high but inconsis-
tent values as compared with the internally consis-
tent results based on the silica and alkali relations of
the fluid. The actual reason for this is the high
carbon dioxide level of the discharge and
hydrogen–methane relations which seem to indicate
temperatures much higher than the hydrothermal re-
action regime.
 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
The atmospheric gases, nitrogen and argon are, as
pointed out by Tolstikhin et al. Ž1991. derived mostly
by their dissolution in cold down-flowing waters. In
Fig. 4, the nitrogen argon relations for fumarole
˜ Miguel ŽFerreira, 1994. are shown
discharges in Sao
to be confined between the atmospheric ratios and a
solubility controlled ratio of about 37. We point out
that atmospheric ratios for these gases do not exclu-
sively imply contamination during sampling. The
most common reason for atmospheric ratios of nitro-
gen and argon in these samples is minor mixing of
the fumarole discharge and the cold surface waters
which inevitably are degassed by heating in the
vicinity of fumarole vents. The most visible effect
this has on the discharge composition is the oxida-
tion of hydrogen sulphide in the fumarole conduit.
In Fig. 5, the hydrogen sulphide carbon dioxide
relations in the fumarole discharges of Furnas are
shown as a scatter of points which seem to be
confined below a control line. Samples from fu-
maroles below the north flank of the Fogo volcano
ŽCV and RG in the figure. are shown for reference
ŽFerreira, 1994.. With reference to the deuterium
oxygen isotope relations of the hydrothermal fluid
we point out that this probably is a solubility control
line which indicates slightly different degrees of
boiling in the aquifers. The higher solubility of
hydrogen sulphide as compared with carbon dioxide
results in a regular rise of the ratio with increased
˜ Miguel indicate that dissolution of atmospheric gases in cold down-flowing
Fig. 4. Nitrogen–argon relations of fumarole discharge from Sao
waters is the dominating source of nitrogen and argon. Note that atmospheric contamination indicated by the higher range of values in the
ppm range.
175
boiling. Chemical effects of traces of atmospheric
oxygen on a weakly basic hydrothermal aquifer are
inevitably the oxidation of bisulphide into sulphate
and lowering of the partial pressure of hydrogen
sulphide gas. The scatter in Fig. 5 is suggested to
arise from such air contamination of the discharge
and the lack of time to restore equilibrium among the
sulphur species.
Hydrogen and methane are trace constituents of
the discharge but show the most regular abundances
of all analysed components. In Fig. 6 the samples
plotted in Fig. 5 show a clear trend with only slightly
different hydrogen methane ratios. The average ratio
for each fumarole is significantly different from the
ratio for the others. It is assumed, therefore, that
there may be different conditions in terms of temper-
ature of fluid compositions beneath the hydrothermal
aquifers as suggested by Ferreira Ž1994.. In theory,
these conditions may be related to plutonic rocks at
different degrees of cooling and degassing.
Equilibrium of the Fisher–Tropsh reaction is not
generally reached at low temperatures Žbelow some
3008C. and is practically borne out in the Furnas
fluids based on the evidence from chemical ther-
mometry and deuterium fractionation.
We therefore seek a deeper and hotter source for
the regular hydrogen methane chemistry of the dis-
charges. We apply a simple model describing the
equilibrium relations of hydrogen and methane at
176 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179

Fig. 5. Hydrogen sulphide–carbon dioxide relations of fumarole discharge of the Furnas caldera. Filled triangles, squares and circles denote
the LG, RT and CG fumaroles respectively. Small diamonds and crosses indicate fumaroles CV and RT below the North flank of Fogo
Volcano ŽFerreira, 1994.. The solid line suggests a steam separation for the soluble acid gases, based on the higher solubility of hydrogen
sulphide. Samples plotting to the left of the line indicate different degree of air-oxidation of hydrogen sulphide.

Fig. 6. Hydrogen–methane relations of fumarole discharge from Sao ˜ Miguel. The figure shows the low range of the covariation. Samples
from the fumarole CV in Fogo plot out of the range shown in the figure, at much lower hydrogenrmethane ratio Žsee Fig. 7.. Symbols as in
Fig. 5.
 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179 177

different temperatures and at different ratios of steam
and carbon dioxide. A simulation of supercritical
conditions such as within a shallow plutonic rock
body is made by examining a binary mixture of
steam and carbon dioxide at different temperatures
as described by the Fisher–Tropsh reaction:
CO 2 q 4H 2 s CH 4 q 2H 2 O.
Assuming a constant pressure in a binary system
the partial pressure of steam is pŽH 2 O. s Ž1 y
pŽCO 2 .. and the thermodynamic equilibrium con-
stant K th may be expressed:
2 4
K th s p Ž CH 4 . Ž 1 y p Ž CO 2 . r Ž p Ž CO 2 . p Ž H 2 . . .
The reaction is most sensitive to changes in the
partial pressure of hydrogen, which accordingly
would have the greatest influence on the hydrogen
methane relations of the fluid in the system. Hydro-
gen methane relations of the system may therefore
be described by the ratio:
4 2
p Ž CH 4 . rp Ž H 2 . s K th p Ž CO 2 . r Ž 1 y p Ž CO 2 . . .
Ž 3.
Ž 1.
In Fig. 7, this ratio, based on data from Robie et
al. Ž1978. is plotted for three compositions of the
modelled binary mixture; 0.1, 0.5 and 0.9 mole
fraction of carbon dioxide. These ratios enclose the
range of water–carbon dioxide ratios in fluid inclu-
sions in minerals of volcanic rocks, but we point out
that fluid inclusions in shallow plutonic minerals
Ž 2. generally belong to the carbon dioxide-rich range.
Horizontal lines in the figure indicate the range for
the different fumaroles. Within the modelled compo-
sitional levels the hottest source condition conform-
ing to the modelled system are found for the CG and
RT fumaroles. According to the model, the LG

Fig. 7. Hydrogen–methane relations of the Fisher–Tropsh reaction illustrated as the ratio pŽCH 4 .rŽ pŽH 2 .. 4 plotted against temperature in
degree centigrade. The figure illustrates a binary system of carbon dioxide and water. Three different mole fractions of carbon dioxide Ž0.1,
0.5 and 0.9. are indicated by curved lines in the diagram. The labelled horizontal lines indicate the averaged ratio for the different
fumaroles. Note that the intersections between the observed ratios and the calculated lines all fall above the supercritical temperatures of
water, indicated in the lower left of the figure.
178 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
fumarole derives its hydrogen and methane from a
significantly colder system.
We are aware that the present simple model only
gives an indication of the reality. It is, however,
likely that more sophisticated modelling of the hy-
drogen–methane relations would also conclude su-
percritical temperature ranges for the observed hy-
drogen–methane ratios.
The effect of source composition on the ratio is
large, almost 3008C for the modelled compositions.
The dominating carbon dioxide composition of the
Furnas caldera favours high mole fractions of carbon
dioxide. This corresponds to a maximum source
temperature of some 7508C which is close to the
solidus temperature for the local trachytic rocks. So,
in conclusion, the simple modelling of the hydrogen
and methane systematic of the Furnas fumaroles
suggests hot but dry plutonic heat sources below the
fumaroles. Circumstantial evidence for this is also
given by the geological setting of the fumaroles
below and within eruptive craters and trachytic
domes. Recent volcanism alone is not a source of
volatiles at the surface. The combination of hot rocks
at depth and down-flow of water gives rise to a
hydrothermal system where degassing of deep
sources is visible at the surface. A remarkable case is
the most recent 1630 eruption within the Furnas
caldera ŽCole et al., 1995. where no anomalous
surface degassing is observed.
In terms of abundance, both hydrogen and
methane in the Furnas discharge are, however, in-
significant which strongly suggests that their sources
are below the reach of the hydrosphere, some 3 km
below the ground. It is assumed that they are carried
to the surface by the regionally outgassing carbon
dioxide. Another explanation might be that these
gases were a part of the carbon dioxide source and
that they reached equilibrium at deep conditions
before chilling and transport to the surface. The
almost invariant hydrogen–methane ratios observed
in the fumarole discharge, however, speak against
such transport controlled origin.
Among the components analysed in this study the
hydrogen and methane are the most stable and their
ratio is virtually insensitive to surface conditions,
degree of boiling in an aquifer and contamination
during sampling or air entrapment in the fumarole
conduit. These gases are most likely related to small
but stable deep sources. The monitoring of these
trace gases might therefore be considered for chemi-
cal monitoring of source-related phenomena.
We have neither explored nor tested all possible
geochemical corollaries of the present model for the
Furnas fumarole discharge. The hypothesis of deep-
seated carbon dioxide source from which emanations
act as a carrier for trace gases may also have pro-
found effects upon water soluble components of the
aquifer system. Some of these effects can be easily
tested, such as leaching of radioactive elements. We
point out that selective leaching of uranium is in-
evitable within the carbon dioxide saturated thermal
aquifers of Furnas. Long standing hydrothermal
aquifers will become low in uranium with time,
which in turn will have effects on their gas chem-
istry, namely the level of degassed radon. The pre-
sent model for fumarole discharge of the Furnas
caldera thus predicts low radon activity in the dis-
charge, much lower than normally expected for dis-
charge issuing from alkalic rocks.
4. Conclusions
The fumaroles within the Furnas caldera derive
their discharge from shallow hydrothermal aquifers
originating from the local groundwater. Based on
chemical thermometry and the observed deuterium–
oxygen isotope shift the aquifer temperatures are
about 1808C at a depth of within 200 m and the
steam fractionation amounts to some 10–20%.
Dissolved solids of the groundwaters are primar-
ily derived by low temperature leaching of rocks by
carbon dioxide rich water. Excess carbon dioxide of
deep origin impregnates the hydrothermal system
from below. Atmospheric gases derived from the
groundwater are found as trace constituents of the
fumarole discharge. Hydrogen and methane are in-
significant trace components of the discharge, which
bear no obvious reaction relation to its temperature
controlled composition. Based on modelling of a
binary carbon dioxide–steam system, these gases are
suggested to derive from shallow plutonic rocks at
supercritical temperatures below the fumarole
grounds. These gases might be considered for chemi-
cal monitoring of the magmatic contribution to the
fumarole discharge.
 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
Acknowledgements
This project was supported by the European Sci-
ence Foundation ŽCONTRACT CEC: ERB EV5V-
CT92-0173. and the Icelandic Ministry of Education.
We thank the staff of the Geoscience Department of
the University of Azores for their kind assistance.
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