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Ferreira1999 Chemistry and Isotopic Composition of Fumarole
Ferreira1999 Chemistry and Isotopic Composition of Fumarole
Ferreira1999 Chemistry and Isotopic Composition of Fumarole
169–179
www.elsevier.comrlocaterjvolgeores
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.
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 hydrothermal water and surface water are loaded
Furnas village. The Lagoa das Furnas field ŽLG. with pyrite mud Ža heavy suspension of marcasite
issues at the ground water surface from a small and clays.. The hydrothermal water discharge is low
coastal platform on the north coast of Lagoa das and surface waters flood the fumarole ground from
Furnas. Surface alteration is characterised by kaolin- time to time. The coastal plain adjacent to the fuma-
ite, which indicates acid leaching of the surface role ground is impregnated by steam and carbon
layer. Steam heated pools of an acid mixture of dioxide saturated condensate resulting in low grade
T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179 171
alteration of the sandy surface layer. No signs of examine the fumarole discharges within the Furnas
previous or more extensive high temperature surface caldera by detailed analysis of chemical components
alteration are found in this locality. that take part in reactions within the hydrothermal
Caldeiras, in Furnas village, is the largest fuma- pressure–temperature regime. This will allow inter-
role ground within the Furnas caldera where several pretation of high temperature equilibria that might be
moderately large fumaroles of different character are used as a basis for chemical monitoring of the
active within an area of several hundred square discharge. The basic premise of the study is to
metres. The discharge issues through volcanic rocks attribute chemical components of the discharge to
which are a few metres above the ground water deep processes ŽOskarsson, 1984. that may give
surface. Surface alteration in Caldeiras is variable; at indications on the state of activity of the magmatic
the highest steaming elevations the rocks are broken system. The fumarole discharges of the Furnas
down to a kaolinite mass with abundant deposits of caldera are dominated by carbon dioxide ŽFerreira,
monoclinic sulphur and subsequently formed or- 1994; Martini, 1994; Ferreira et al., 1995. which
thorhombic sulphur and gypsum. Where condensate may, to a first approximation, be considered as an
pools have formed, the surface is covered with pyrite indication of deep-seated degassing. Carbon dioxide,
mud. Of special importance is Caldeira Grande ŽCG. however, is not appropriate for monitoring, since its
where pristine hydrothermal fluid is discharged Žthe high abundance in the discharge Ž95–99 mol% of
only occurrence within the Furnas caldera. with a gases. masks all fine-scale changes that might occur
steady steam separation in a water-filled bowl. in the carbon dioxide concentration. The present
Caldeira do Asmodeu is a vigorously boiling fuma- study, therefore, is focused upon reactive and inert
role where steam explosions have occasionally oc- trace components of the discharge.
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. 2. Sampling, analysis and analytical results
Fumarole CG issues the only fluid in Furnas that can
be used for chemical thermometry based on alkali Fumarole discharges were sampled in 100–200
and silica temperatures. ml borosilicate glass tubes with a septum and a
On the steep west bank of Ribeira dos Tambores, Teflon stopcock. Silicon rubber tubing was used to
SE of Caldeiras, the fumarole marked RT issues connect the tube stopcock to a polyethylene funnel,
from a fissure in the Marconas trachyte dome ŽFig. which was placed over the steam vent of the fuma-
1.. There are virtually no surface manifestations role. The first stage of sampling was to flush the
around this fumarole. A slight alteration across cracks entire sampling train with the fumarole discharge
in the trachytic rock is the only visible sign in through the septum assembly until it was considered
addition to some pyrite mud downslope from the to contain clean discharge. After flushing, the sep-
fumarole vent. tum outlet of the tube was closed and 10–15 ml 12
All the Furnas fumarole grounds are surrounded M KOH were injected through the septum and the
by intensive soil degassing of carbon dioxide. This tube was placed in cooling water. The acid gases are
indicates that the hydrothermal aquifers, as well as adsorbed during sampling so only the fixed gases
the cold springs in Furnas are close to saturation comprise the gas volume of the tube while the
with carbon dioxide. hydroxide becomes diluted by condensate. Sampling
Origins of the carbon dioxide dominated dis- is continued until the tube is almost at the atmo-
charge of fumaroles on Sao ˜ Miguel were attributed spheric pressure. This sampling method is essentially
to deep mantle degassing, based on carbon the so called Giggenbach method ŽGiggenbach and
dioxiderhelium ratios ŽTolstikhin et al., 1991.. He- Goguel, 1989. with only a minor modification.
lium isotope ratios at about six times atmospheric Samples of the fumarole discharge for deuterium
ratio were related to a mantle source of anomalous and oxygen isotopic analysis were condensed Žtotal
isotopic composition, matching the continental man- condensation of steam. in a glass bulb and kept in
tle. The aim of the present contribution was to glass bottles. Carbon isotope analysis was made on
172 T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179
The atmospheric gases, nitrogen and argon are, as boiling. Chemical effects of traces of atmospheric
pointed out by Tolstikhin et al. Ž1991. derived mostly oxygen on a weakly basic hydrothermal aquifer are
by their dissolution in cold down-flowing waters. In inevitably the oxidation of bisulphide into sulphate
Fig. 4, the nitrogen argon relations for fumarole and lowering of the partial pressure of hydrogen
˜ Miguel ŽFerreira, 1994. are shown
discharges in Sao sulphide gas. The scatter in Fig. 5 is suggested to
to be confined between the atmospheric ratios and a arise from such air contamination of the discharge
solubility controlled ratio of about 37. We point out and the lack of time to restore equilibrium among the
that atmospheric ratios for these gases do not exclu- sulphur species.
sively imply contamination during sampling. The Hydrogen and methane are trace constituents of
most common reason for atmospheric ratios of nitro- the discharge but show the most regular abundances
gen and argon in these samples is minor mixing of of all analysed components. In Fig. 6 the samples
the fumarole discharge and the cold surface waters plotted in Fig. 5 show a clear trend with only slightly
which inevitably are degassed by heating in the different hydrogen methane ratios. The average ratio
vicinity of fumarole vents. The most visible effect for each fumarole is significantly different from the
this has on the discharge composition is the oxida- ratio for the others. It is assumed, therefore, that
tion of hydrogen sulphide in the fumarole conduit. there may be different conditions in terms of temper-
In Fig. 5, the hydrogen sulphide carbon dioxide ature of fluid compositions beneath the hydrothermal
relations in the fumarole discharges of Furnas are aquifers as suggested by Ferreira Ž1994.. In theory,
shown as a scatter of points which seem to be these conditions may be related to plutonic rocks at
confined below a control line. Samples from fu- different degrees of cooling and degassing.
maroles below the north flank of the Fogo volcano Equilibrium of the Fisher–Tropsh reaction is not
ŽCV and RG in the figure. are shown for reference generally reached at low temperatures Žbelow some
ŽFerreira, 1994.. With reference to the deuterium 3008C. and is practically borne out in the Furnas
oxygen isotope relations of the hydrothermal fluid fluids based on the evidence from chemical ther-
we point out that this probably is a solubility control mometry and deuterium fractionation.
line which indicates slightly different degrees of We therefore seek a deeper and hotter source for
boiling in the aquifers. The higher solubility of the regular hydrogen methane chemistry of the dis-
hydrogen sulphide as compared with carbon dioxide charges. We apply a simple model describing the
results in a regular rise of the ratio with increased equilibrium relations of hydrogen and methane at
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 gen methane relations of the system may therefore
and carbon dioxide. A simulation of supercritical be described by the ratio:
conditions such as within a shallow plutonic rock
body is made by examining a binary mixture of 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 . . .
steam and carbon dioxide at different temperatures
as described by the Fisher–Tropsh reaction: Ž 3.
CO 2 q 4H 2 s CH 4 q 2H 2 O. Ž 1.
In Fig. 7, this ratio, based on data from Robie et
Assuming a constant pressure in a binary system al. Ž1978. is plotted for three compositions of the
the partial pressure of steam is pŽH 2 O. s Ž1 y modelled binary mixture; 0.1, 0.5 and 0.9 mole
pŽCO 2 .. and the thermodynamic equilibrium con- fraction of carbon dioxide. These ratios enclose the
stant K th may be expressed: range of water–carbon dioxide ratios in fluid inclu-
sions in minerals of volcanic rocks, but we point out
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 . . . 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 reaction is most sensitive to changes in the the different fumaroles. Within the modelled compo-
partial pressure of hydrogen, which accordingly sitional levels the hottest source condition conform-
would have the greatest influence on the hydrogen ing to the modelled system are found for the CG and
methane relations of the fluid in the system. Hydro- 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 but stable deep sources. The monitoring of these
significantly colder system. trace gases might therefore be considered for chemi-
We are aware that the present simple model only cal monitoring of source-related phenomena.
gives an indication of the reality. It is, however, We have neither explored nor tested all possible
likely that more sophisticated modelling of the hy- geochemical corollaries of the present model for the
drogen–methane relations would also conclude su- Furnas fumarole discharge. The hypothesis of deep-
percritical temperature ranges for the observed hy- seated carbon dioxide source from which emanations
drogen–methane ratios. act as a carrier for trace gases may also have pro-
The effect of source composition on the ratio is found effects upon water soluble components of the
large, almost 3008C for the modelled compositions. aquifer system. Some of these effects can be easily
The dominating carbon dioxide composition of the tested, such as leaching of radioactive elements. We
Furnas caldera favours high mole fractions of carbon point out that selective leaching of uranium is in-
dioxide. This corresponds to a maximum source evitable within the carbon dioxide saturated thermal
temperature of some 7508C which is close to the aquifers of Furnas. Long standing hydrothermal
solidus temperature for the local trachytic rocks. So, aquifers will become low in uranium with time,
in conclusion, the simple modelling of the hydrogen which in turn will have effects on their gas chem-
and methane systematic of the Furnas fumaroles istry, namely the level of degassed radon. The pre-
suggests hot but dry plutonic heat sources below the sent model for fumarole discharge of the Furnas
fumaroles. Circumstantial evidence for this is also caldera thus predicts low radon activity in the dis-
given by the geological setting of the fumaroles charge, much lower than normally expected for dis-
below and within eruptive craters and trachytic charge issuing from alkalic rocks.
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 4. Conclusions
hydrothermal system where degassing of deep
sources is visible at the surface. A remarkable case is The fumaroles within the Furnas caldera derive
the most recent 1630 eruption within the Furnas their discharge from shallow hydrothermal aquifers
caldera ŽCole et al., 1995. where no anomalous originating from the local groundwater. Based on
surface degassing is observed. chemical thermometry and the observed deuterium–
In terms of abundance, both hydrogen and oxygen isotope shift the aquifer temperatures are
methane in the Furnas discharge are, however, in- about 1808C at a depth of within 200 m and the
significant which strongly suggests that their sources steam fractionation amounts to some 10–20%.
are below the reach of the hydrosphere, some 3 km Dissolved solids of the groundwaters are primar-
below the ground. It is assumed that they are carried ily derived by low temperature leaching of rocks by
to the surface by the regionally outgassing carbon carbon dioxide rich water. Excess carbon dioxide of
dioxide. Another explanation might be that these deep origin impregnates the hydrothermal system
gases were a part of the carbon dioxide source and from below. Atmospheric gases derived from the
that they reached equilibrium at deep conditions groundwater are found as trace constituents of the
before chilling and transport to the surface. The fumarole discharge. Hydrogen and methane are in-
almost invariant hydrogen–methane ratios observed significant trace components of the discharge, which
in the fumarole discharge, however, speak against bear no obvious reaction relation to its temperature
such transport controlled origin. controlled composition. Based on modelling of a
Among the components analysed in this study the binary carbon dioxide–steam system, these gases are
hydrogen and methane are the most stable and their suggested to derive from shallow plutonic rocks at
ratio is virtually insensitive to surface conditions, supercritical temperatures below the fumarole
degree of boiling in an aquifer and contamination grounds. These gases might be considered for chemi-
during sampling or air entrapment in the fumarole cal monitoring of the magmatic contribution to the
conduit. These gases are most likely related to small fumarole discharge.
T. Ferreira, N. Oskarssonr Journal of Volcanology and Geothermal Research 92 (1999) 169–179 179