Paper 1

PII S0016-7037(01)00583-X
Geochemical evidence for the existence of high-temperature hydrothermal brines at

Vesuvio volcano, Italy
GIOVANNI CHIODINI,
1,
* LUIGI MARINI,
2
and MASSIMO RUSSO
1
1
Osservatorio Vesuviano, via Manzoni 249, 80122 Napoli, Italy
2
DIPTERIS, Universita` di Genova, Corso Europa 26, 16132 Genova, Italy
(Received December 20, 1999; accepted in revised form January 29, 2001)
AbstractA high-temperature hydrothermal system is present underneath the crater area of Vesuvio volcano.
It is suggested that NaCl brines reside in the high-temperature reservoir and inuence the chemical compo-
sition of the gases discharged by the fumaroles of the crater bottom (vents FC1, FC2, and FC5). These have
typical hydrothermal compositions, with H
2
O and CO
2
as major components, followed by H
2
, H
2
S, N
2
, CH
4
,
and CO (in order of decreasing contents) and undetectable SO
2
, HCl, and HF. Fumarolic H
2
O is either
meteoric water enriched in
18
O through high-temperature water-rock oxygen isotope exchange or a mixture
of meteoric and arc-type magmatic water. Fumarolic CO
2
is mainly generated by decarbonation reactions of
marine carbonates, but the addition of small amounts of magmatic CO
2
is also possible. All investigated gas
species (H
2
O, CO
2
, CO, CH
4
, H
2
, H
2
S, N
2
, and NH
3
) equilibrate, probably in a saturated vapor phase, at
temperatures of 360 to 370C for vent FC1 and 430 to 445C for vents FC2 and FC5. These temperatures are
conrmed by the H
2
-Ar geoindicator. The minimum salt content of the liquid phase coexisting with the vapor
phase is 14.9 wt.% NaCl, whereas its maximum salinity corresponds to halite saturation (49.252.5 wt.%
NaCl). These poorly constrained salinities of NaCl brines reect in large uncertainties in total uid pressures,
which are estimated to be 260 to 480 bar for vents FC2 and FC5 and 130 to 220 bar for vent FC1.
Pressurization in some parts of the hydrothermal system, and its subsequent discharge through hydrofractur-
ing, could explain the relatively frequent seismic crises recorded in the Vesuvio area after the last eruption.
An important heat source responsible for hydrothermal circulation is represented by the hot rocks of the
eruptive conduits, which have been active from 1631 to 1944. Geochemical evidence suggests that no input
of fresh magma at shallow depths took place after the end of the last eruptive period. Copyright 2001
Elsevier Science Ltd
1. INTRODUCTION
At present, Vesuvio volcano is in a quiescent period char-
acterized by widespread fumarolic activity in the inner slopes
and the bottom of the crater (Fig. 1). The chronogram of the
maximum temperatures measured in the crater area after the
last eruption, which took place in 1944 (Fig. 2), clearly shows
a hot period from 1944 to 1960 when temperatures of 600 to
800C were recorded, and a cold period afterward. Tempera-
tures close to the boiling point of water at the crater altitude
(95C) were attained during the 1990s.
This temperature decline was accompanied by remarkable
changes in the mineralogy of sublimates and alteration products
deposited at the fumarolic vents (Parascandola, 1951; Russo
and Langella, 1996, in prep.; Russo, 1997b). Chloride of Na
(halite) and Pb (cotunnite) and oxide of Cu (tenorite) were the
most important minerals at temperatures of 500 to 800C,
whereas the present mineral assemblage includes sulfur, gyp-
sum, and compound sulfates, such as alunite, potassium alum,
metavoltine, pickeringite, and halotrichite.
Despite the absence of chemical data on fumarolic uids,
both outlet temperatures and minerals collected at the fumarolic
vents suggest that magmatic gases were probably discharged
during the hot period. The fumaroles of the crater rim were
sampled in 1979 and 1982, when maximum temperatures
ranged between 220 and 230C, and showed chemical compo-
sitions dominated by air components with 2 vol.% of CO
2
(Roberto Cioni, pers. comm.). The fumaroles of the crater
bottom were sampled in 1987 (T 210C) and in 1988 (T
101C) by Patrick Allard (pers. comm.). Discharged uids
resulting were made up mainly of H
2
O (93.995.4 vol.%) and
CO
2
(4.45.8 vol.%).
Since 1996, we started to sample and analyze, both chemi-
cally and isotopically, crater fumarolic efuents in the frame-
work of the volcanic surveillance programme. These data are
presented and discussed in this communication with the aim to
elaborate a conceptual geochemical model of the Vesuvio
magmatic-hydrothermal system.
These initial results will be of help to interpret future vari-
ations in the chemical and isotopic characteristics of fumarolic
gases and, in particular, to detect the evolution of the Vesuvio
magmatic system toward the next eruption. Therefore, this
initial geochemical information is of great importance for the
evaluation and mitigation of volcanic risk in this densely in-
habited area.
2. GEOVOLCANOLOGIC BACKGROUND
Somma-Vesuvio is a volcanic complex consisting of a rela-
tively old strato volcano, Monte Somma, which underwent a
series of caldera collapses (Cioni et al., 1999), and a younger
intracaldera cone, Vesuvio. The deep geothermal borehole
Trecase-1 (Fig. 1) drilled on the southern anks of the volcanic
complex, met 373 22 ka old lavas at a depth of 1125 m
*Author to whom correspondence should be addressed (chiod@ischia.
osve.unina.it).
Pergamon
Geochimica et Cosmochimica Acta, Vol. 65, No. 13, pp. 21292147, 2001
Copyright 2001 Elsevier Science Ltd
Printed in the USA. All rights reserved
0016-7037/01 $20.00 .00
2129
(Brocchini et al., 1997). These lavas are representative of the
rst volcanic activity in the study area. Somma-Vesuvio activ-
ity started between 18 and 37 ka B.P. (Principe et al., 1999) and
alternated with (1) relatively frequent open-conduit activity,
consisting of effusive eruptions sometimes accompanied by
Strombolian events, and (2) less frequent Plinian eruptions, that
typically followed long periods of quiescence (Arno` et al.,
1987). Effusive Strombolian events discharged small batches
(0.001 km
3
or less) of primitive magmas, whereas Plinian
eruptions involved larger batches (from 0.1 to 1 km
3
) of more
evolved magmas. These had been stored and had differentiated
in magma chambers located at depths of 3 to 5 km within a
thick sedimentary sequence of chiey carbonate rocks (Barberi
et al., 1981; Santacroce, 1983), which is sited at depths 2.5
km underneath the volcano (Principe et al., 1987). After the last
Plinian eruption, which took place in 1631 (Rosi et al., 1993),
Vesuvio has been marked by open-conduct activity, which
ended with the eruption of 1944.
Somma-Vesuvio volcanics generally show a high potassic
character and large differences in silica saturation, which per-
mits to discriminate (1) nearly saturated rocks, i.e., leucite-
basalts, leucite-trachybasalts, latites, and trachytes, (2) mildly
undersaturated rocks, i.e., phonolitic tephrites, tephritic phono-
lites, and phonolites, and (3) highly undersaturated rocks, i.e.,
leucititic tephrites, leucititic tephrit-phonolites, and leucititic
phonolites (Joron et al., 1987).
3. SAMPLING AND CHEMICAL AND ISOTOPIC
ANALYSES
Fumarolic uids were sampled in evacuated 250 mL cylin-
drical asks equipped with two Teon stopcocks and contain-
ing 50 mL of a 4 N NaOH solution (Giggenbach, 1975a;
Giggenbach and Goguel, 1989). Fumarolic uids were also
passed through a condenser cooled with boiling diethyl ether,
which maintains a constant condensation temperature of 38C,
to collect samples of steam condensates (for the determination
of NH
3
and of the D/
1
H and
18
O/
16
O ratios of H
2
O) and of the
separated incondensable gases (for the analyses of CO and of
the
13
C/
12
C and
18
O/
16
O ratios of CO
2
).
CO
2
absorbed in the alkaline solution was analyzed by
acid-base titration, whereas H
2
S was oxidized to sulfate
through reaction with H
2
O
2
and determined by ion chromatog-
raphy. The nonabsorbed gases (He, Ar, O
2
, N
2
, H
2
, and CH
4
),
mainly present in the headspace over the NaOH solution, were
measured by gas chromatography through a unique injection.
Ammonia was determined by the colorimetric Nessler method,
CO was analyzed by means of a gaschromatograph tted with
a reduced gas detector (HgO), and the isotopic ratios were
measured by mass spectrometry.
Some fumarolic samples were also collected in asks con-
taining an AgNO
3
-NH
4
OH solution to precipitate H
2
S as Ag
2
S.
Hydrogen sulde concentrations are comparable, within ana-
lytical uncertainties, with those obtained from the analysis of
the NaOH solution, which excludes the presence of detectable
SO
2
.
Some steam condensates were also analysed for Na and Cl,
obtaining concentrations of 0.6 to 1.5 ppm Na and 1.2 to 3.3
ppm Cl. The absence of excess chloride (i.e., Cl-equivalent
concentrations higher than the sum of the equivalent concen-
trations of cations other than proton) exclude the presence of
measurable HCl in the fumarolic discharge. Ion chromato-
graphic analyses also revealed the absence of detectable F and
its compounds (e.g., HF). Analytical results are reported in
Tables 1 and 2.
4. COMPOSITION OF VESUVIO FUMAROLES FROM 1996
TO 1998
Two different compositions characterize the fumaroles of
Vesuvio. The fumaroles of the crater rim and of the inner crater
Fig. 1. Location of the sampled fumaroles of Vesuvio crater.
Fig. 2. Chronogram of the maximum temperatures measured in the
Vesuvio crater area from 1944 to 1999 (data from Imbo`, 1947, 1950;
Imbo` et al., 1964; Parascandola, 1959, 1960; Russo, 1995, 1997a;
Nazzaro, 1997; Allard, pers. comm.; Cioni, pers. comm.; Avino, pers.
comm.).
2130 G. Chiodini, L. Marini, and M. Russo
slopes (vents V1, B1, B2, and B3) discharge uids whose
incondensable fraction is mainly composed of an atmospheric
component (made up of N
2
, O
2
, and Ar in relative proportions
equal to those of atmospheric air) with 3000 to 120,000 mol/
mol of CO
2
(Table 2). Apart from vent V1, which has outlet
temperatures close to 90C, the other fumaroles of this group
have discharge temperatures of 60 to 75C. Water content in
total uid is estimated to be 215,000 to 420,000 mol/mol,
assuming that P
H
2
O
is xed by the presence of liquid water and
considering a total pressure of 930 mbar (average atmospheric
pressure at 1000 m). As these fumarolic efuents are dominated
by atmospheric gases, they will not be considered in the fol-
lowing discussion.
In the fumaroles of the crater bottom (vents FC1, FC2, and
FC5), H
2
O is the major component followed by CO
2
, H
2
, H
2
S,
N
2
, CH
4
, CO, and NH
3
in order of decreasing importance. Acid
gases, SO
2
, HCl, and HF, are virtually absent. Since these
compositions are typical of deeply originated, hydrothermal
uids, it is unlikely that these gases are degassed from a magma
body and directly reach the surface as such. Although acid gas
constituents could be eliminated through steam condensation
(due to their high solubility in the liquid phase) upstream of the
discharge points, the relatively high CH
4
and NH
3
contents
testify to the provenance of these uids from a hydrothermal
system (Giggenbach, 1987; Chiodini et al., 1993a), which is
evidently located underneath the crater area. Of course, it is
possible that this hydrothermal system is recharged, at least in
part, by magmatic uids entering from below, similar to what
was observed in many active volcanoes such as Nevado del
Ruiz, Colombia (Giggenbach et al., 1990), Guagua Pichincha,
Ecuador (Marini et al., 1991), Montserrat Island, West Indies
(Chiodini et al., 1996a), Galeras, Colombia (Fischer et al.,
1997; Sano et al., 1997), and Guadeloupe, West Indies (Brom-
bach, 2000; Brombach et al., 2000).
5. HIGH-SALINITY NACL AQUEOUS SOLUTIONS OR
LOW-SALINITY SUPERCRITICAL FLUIDS?
Hydrothermal gas equilibria in the H
2
-CO
2
-CO-CH
4
-H
2
O
system have been recently reviewed by Chiodini and Marini
(1998), who presented several plots comparing analytical data
Table 1. Chemical and isotopic composition of the fumaroles located in the bottom of the Vesuvio crater. Gas concentrations are expressed in
mol/mol.
Date TC H
2
O CO
2
N
2
Ar O
2
H
2
S CH
4
H
2
CO He NH
3
18
O
(H
2
O)
D
(H
2
O)
18
O
(CO
2
)
18
C
(CO
2
)
FC1 230498 98.0 863800 134500 217 0.31 0.16 170 76.8 1106 11.2 0.64 0.52 13.97 91.9 na na
FC1 240698 96.3 919200 79700 138 0.30 0.03 91 48.0 791 10.8 0.38 0.55 13.28 83 23.61 0.24
FC1 141198 94.0 922100 76800 172 0.49 6.10 102 52.1 797 9.5 0.45 0.50 na na 23.06 0.06
FC1 141099 96.2 911400 87400 169 0.49 nd 111 61.6 912 5.5 0.44 na na na na na
FC2 160596 96.0 885200 103800 9100 na na 482 74.6 1297 39.0 0.46 na na na na na
FC2 310796 99.0 892500 105700 214 na na 472 59.2 1051 35.9 0.22 na na na na na
FC2 190497 95.4 909200 89230 236 na na 422 42.7 875 45.2 na na na na na na
FC2 230498 95.6 840300 156800 268 0.29 0.17 776 86.1 1635 66.2 0.57 0.61 7.3 34.6 na na
FC2 240698 93.7 895800 102200 183 0.31 0.02 490 58.0 1195 43.7 0.52 7.50 7.5 32.7 29.41 0.24
FC2 141198 94.0 892700 105300 214 0.37 0.82 416 68.1 1250 47.4 0.61 1.50 na na 28.77 0.12
FC2 50299 94.5 899100 99100 176 0.46 nd 513 53.2 1020 39.3 0.50 na na na na na
FC2 280799 94.1 893500 104700 199 0.31 0.05 458 63.2 1084 40.4 0.44 na na na na na
FC2 280899 93.0 909000 89300 205 0.82 nd 432 53.4 957 34.7 0.42 na na na na na
FC2 250999 97.3 908500 89800 175 0.19 nd 451 57.8 979 31.4 0.41 na na na na na
FC2 141099 96.5 905300 93000 167 0.21 nd 449 55.8 992 29.1 0.27 na na na na na
FC5 230498 98.0 781200 215200 389 0.70 0.22 873 146.2 2035 75.3 0.47 0.67 8.33 52.5 na na
FC5 240698 97.8 922800 75900 136 0.27 0.08 330 36.5 843 28.8 0.37 1.26 7.28 36.5 28.9 0.29
FC5 141198 94.5 884700 113300 237 0.69 0.71 479 61.2 1240 37.2 0.61 0.80 na na 30.44 0.34
FC5 280799 93.3 893200 105000 196 0.17 nd 463 55.6 1036 35.7 0.46 na na na na na
na: not analysed
nd: not detected
Table 2. Chemical composition of the fumaroles located in the inner
slopes and in the rim of the Vesuvio crater. Analytical data are
expressed as mol/mol in a water-free basis.
Date TC CO
2
N
2
O
2
Ar CH
4
V1 120794 90.0 121000 696000 189000 95.0
V1 170496 91.1 120000 668700 178300 na
B1 240395 72.7 3150 760000 198000 na
B1 110795 69.1 15700 755000 211000 na
B1 110795 69.1 15000 780000 216000 na
B1 120995 74.5 15200 778000 215000 na
B1 030196 74.0 20100 747700 205100 na
B1 200196 73.6 14200 757900 204500 na
B1 160396 68.7 14000 774000 202000 na
B1 060596 71.1 16600 762800 199800 na
B1 300998 na 28700 760000 210300 9.5
B2 110795 70.3 15600 778000 214000 na
B2 110795 70.3 17100 765000 212000 na
B2 120995 70.3 17000 777000 215000 na
B2 120995 70.3 19200 772000 214000 na
B2 030196 76.0 20200 723100 198000 na
B2 200196 73.0 16800 772100 211800 na
B2 160396 73.1 14700 728000 195500 na
B2 060596 74.0 18300 754900 199100 na
B2 300998 na 26400 744800 205800 7.4
B3 080395 63.9 3130 761000 201000 na
B3 110795 75.1 7300 785000 217000 na
B3 030196 64.7 3100 773900 210400 na
B3 200196 67.3 2900 779000 216300 na
B3 060596 72.5 7200 771500 202100 na
na: not analysed
2131 Hydrothermal brines at Vesuvio volcano
with the compositions of equilibrium vapor and equilibrium
liquid phases and the compositions of the vapor phases sepa-
rated in a single-step from equilibrium liquids at varying tem-
peratures. Theoretical compositions were calculated consider-
ing gas solubilities and thermodynamic data for pure water. The
four samples of fumaroles FC1 and FC2 of Vesuvio, which
were included in the database of Chiodini and Marini (1998),
indicated equilibrium temperatures and pressures above the
critical point of pure water (374C and 221 bar). These fu-
marolic uids are unlikely to be produced by the boiling of pure
liquid water or by a low-salinity aqueous solution.
For a correct appraisal of the origin of the Vesuvio crater
fumaroles, it must be taken into account that high-salinity NaCl
aqueous solutions do readily form in active volcanic environ-
ments through (1) the absorption of SO
2
- and HCl-rich mag-
matic gases in deeply circulating groundwaters and (2) neutral-
ization of these initially acidic groundwaters by reaction with
wall rock containing minerals capable of neutralizing acids,
such as feldspars, micas, and other silicates (Giggenbach, 1988,
1997a; Reed, 1997). These processes have been recognized in
most (if not all) geothermal systems located in active volcanic
areas. The interaction of deeply circulating groundwaters with
sublimates deposited during previous hot cycles of the volcano
(Giggenbach, 1975b) represents another readily available
source of dissolved salts. Another potential source of NaCl
brines is a second boiling of magmas (Fournier, 1987; Burn-
ham, 1997). The extreme situation is represented by the hyper-
saline brines that have been found in some deep geothermal
wells drilled in active volcanic areas, such as Nisyros (Chiodini
et al., 1993b), Mofete (Guglielminetti, 1986), and Kakkonda
(Kasai et al., 1998), whose origins and evolution have been
discussed by Fournier (1987).
Depending on the salt content of the NaCl-H
2
O system, the
critical point is shifted to pressures and temperatures signi-
cantly higher than those of pure water (e.g., Bischoff and
Pitzer, 1989; Knight and Bodnar, 1989). Consequently, the
behavior of high-temperature natural uids in active volcanic
environments is unlikely to be controlled by conditions above
the critical point of pure water, but may more correctly be
outlined in terms of the coexistence of gas-rich vapors with
high-salinity liquids (Reyes et al., 1993).
The next step to be considered is the chemical composition
of the hydrothermal liquid phase, which is present underneath
Vesuvio crater and boils off the fumarolic uids discharged by
crater bottom vents. The main four water types encountered in
the geothermal systems sited in active volcanic areas are (e.g.,
Ellis and Mahon, 1977; Henley et al., 1984; Giggenbach,
1988): (1) neutral NaCl waters, typically circulating in high-
enthalpy geothermal reservoirs (see above), (2) acid SO
4
wa-
ters, formed by the absorption of geothermal gases in near-
surface, O
2
-bearing groundwaters or surface waters and
subsequent oxidation (driven by atmospheric O
2
) of H
2
S to
H
2
SO
4
, (3) Na-HCO
3
waters, originated through absorption of
geothermal gases into relatively deep, O
2
-free groundwaters,
and (4) acid Cl-SO
4
to SO
4
-Cl waters.
The latter type of water is commonly found in crater lakes
such as El Chichon (Casadevall et al., 1984), Kawah Ijen
(Delmelle and Bernard, 1994), Poas (Brantley et al., 1987;
Rowe et al., 1992), Ruapehu (Giggenbach, 1975c; Christenson
and Wood, 1993), Sirung (Poorter et al., 1989), Soufrie`re of St.
Vincent (Sigurdsson, 1977), and Yugama and Yakeyama (Ta-
kano and Watanuki, 1990). The chemistry of crater lake waters,
especially during periods of intense volcanic activity, is obvi-
ously dominated by inow and absorption of magmatic gases
rich in HCl and S species, mainly SO
2
and H
2
S (e.g., Aguilera
et al., 2000 and references therein), leading to the production of
strongly reactive aqueous solutions. In fact, through dissolution
in liquid water, SO
2
disproportionates as specied by the fol-
lowing reaction (Murray and Cubicciotti, 1983):
4 SO
2
4 H
2
O fH
2
S 3 H
2
SO
4
. (1)
In crater lakes these highly acid oxidized solutions are very
reactive with respect to cation leaching or rock dissolution
leading to deposition of alunite, anhydrite, pyrite, and kaolinite.
Nevertheless, the low availability of rocks in lacustrine envi-
ronments often prevents the neutralization of the acid aqueous
solutions. At greater depths, magmatic gases interact with
water and masses of rocks much larger than in crater lakes and
at higher temperatures and for longer periods of time, with
respect to crater lakes, thus leading to higher extents of neu-
tralization and ultimately to the formation of neutral NaCl
waters (Giggenbach, 1997a).
Consistently, acid Cl-SO
4
to SO
4
-Cl waters are rare in geo-
thermal reservoirs associated with recent volcanism, as pointed
out by Truesdell (1991), who reports the best documented
examples of deep geothermal wells producing acid waters and
discusses their origin. For instance, at Tatun, acid Cl-SO
4
waters come from a geothermal reservoir which is mostly
developed within a 900 m-thick sequence of orthoquartzitic
sandstones (containing only quartz, kaolinite, minor alunite,
and elemental sulfur) and subordinately within highly altered
andesites. The HCl introduced in the Tatun reservoir water,
most probably from a volcanic source, is not neutralized
through water-rock interaction, because no minerals capable of
neutralizing acids are present in the reservoir rocks.
In the geologic setting of Vesuvio, the minerals capable of
neutralizing acids are abundant and are represented not only by
the silicates and reduced Fe oxides of the volcanic rocks but
also by calcite and dolomite of the sedimentary carbonate
sequence. In this framework, acid immature waters, chemically
dominated by the absorption of magmatic uids, are readily
neutralized and are possibly present only in the proximity of the
magma chamber. Therefore, it can be concluded that neutral
NaCl aqueous solutions of still unknown concentration proba-
bly circulate in the hydrothermal reservoir underneath Vesuvio
crater, as is generally found in hydrothermal systems with close
volcanic-magmatic association (Giggenbach, 1988, 1997a).
Where is this reservoir located? In principle, the thick sedi-
mentary sequence of chiey carbonate rocks, which is sited at
depths 2.5 km underneath the volcano (Principe et al., 1987),
could host the main hydrothermal aquifer, particularly where its
permeability is enhanced by fracturing and dissolution phe-
nomena. This possibility is conrmed by studies of explosive
eruptions, such as those of AD 79, 1631, and 1906 (e.g.,
Sigurdsson et al., 1985; Barberi et al., 1989; Rosi et al., 1993).
All these eruptions consist of an early magmatic phase and a
late phreatomagmatic phase, which are clearly documented by
both historic chronicles and deposit characteristics. Phreato-
magmatic deposits, which are produced by explosive interac-
tion of magma with groundwater, contain abundant lithic
ejecta, some of which come from the carbonate aquifer. The
local abundance of these peculiar lithic ejecta has been ascribed
to explosive vaporization of groundwater, which brings about
fragmentation of the rocks hosting the aquifer and entrainment
of lithic ejecta in the erupting magma. These carbonate ejecta
contain quartz, albite, illite, and pyrite (Joron et al., 1987),
evidently formed through water-rock interaction under the
high-temperature, low-f
O
2
conditions which are typical of ma-
ture hydrothermal environments. Accepting the use of the past
as a key to the present (by reversing the approach generally
taken to solve geological riddles), it is likely that at present, the
main hydrothermal aquifer is hosted chiey in the carbonate
basement of the volcanic edice and again, neutral NaCl solu-
tions circulate in this aquifer.
On the basis of the previous discussion, we have decided to
reconsider gas equilibria for systems involving an NaCl aque-
ous solution of specied concentration instead of pure water.
We refer here to the NaCl H
2
O system, which is the obvious,
simplest analog of complex, natural geothermal liquids. The
data needed to calculate equilibrium vapor and liquid gas
compositions for NaCl aqueous solutions of specied concen-
trations are water fugacities and solubilities of gas species at
varying temperatures.
Linear equations linking log f
H
2
O
and 1/T (Table 3) have
been obtained for 1, 2, and 3 m NaCl solutions from Dittman
(1977). Under the extreme condition of vapor liquid halite
equilibrium, water fugacities (Tanger and Pitzer, 1989) obey
the following linear equation for temperatures up to 460C (T
is in K):
log f
H2O
4.85 1767/T, (2)
which is similar to that given by Giggenbach (1987) for saline
brines:
log f
H2O
4.9 1820/T. (3)
5.1. Gas solubilities in NaCl solutions
Gas solubilities of CO
2
in pure water and in 0.5, 1, and 2 m
NaCl solutions were measured at temperatures of 172 to 334C
by Ellis and Golding (1963), whereas the solubility of H
2
S in
pure water and in NaCl solutions up to 2.5 m were determined
at temperatures up to 320C by Suleimenov and Krupp (1994).
These are the most complete datasets on the solubility of these
two gases in high-temperature NaCl solutions. Unfortunately,
no experimental data are available on the solubilities of other
geothermal-volcanic gases in high-temperature NaCl solutions.
Solubility of H
2
S in pure water at high temperatures was also
investigated by Drummond (1981) and Kozintseva (1964).
Gas solubilities in salt solutions are usually expressed
through the salting out coefcient of Sechenov (i.e., Setchenov
or Setschenow). This is a useful generalization for gas species
of known solubilities both in pure water and salt solutions, but
they cannot be used to predict the behavior of other gases.
To this purpose, we found a tight linear relation between the
logarithm of the vapor-liquid distribution coefcient:
B
i
(n
i
/n
H2O
)
V
/(n
i
/n
H2O
)
L
(4)
of CO
2
and H
2
S both in pure water and in NaCl aqueous
solutions (which have been calculated from available experi-
mental data) and the following parameter:
L
log (
V
/
L
) log
C
, (5)
where
L
is the density of the salt solution (Ellis and Golding,
1963),
V
is the density of the vapor phase and
C
is the critical
density (Knight and Bodnar, 1989). The density of the vapor
phase in equilibrium with NaCl solutions has been assumed
equal to the that of pure steam at the same P and T conditions
(data from Keenan et al., 1969). As suggested by Tanger and
Pitzer (1989), this is an acceptable approximation because the
fraction of NaCl present in the vapor phase is very small.
Inspection of Figure 3 shows that all the log B
CO
2
values for
pure water and salt solutions dene a unique alignment, which
is described by the following linear regression equation (R
0.997):
log B
CO2
0.66566 (0.00701) 1.1807 (0.0132) L
. (6)
A similar linear regression equation is obtained for H
2
S, at least
for L
0.9, corresponding to T 275C (R 0.997):

log B
H2S
0.6058 (0.0110) 0.9503 (0.0108) L
. (7)
For L 0.9 (T 275C) experimental solubility data, both
in pure water and NaCl solutions, deviate from the linear trend
depicted by Eqn. 7. Besides, at L
0.9, the B
H
2
S
in NaCl
solutions are signicantly lower than in pure water for the same
Table 3. Temperature dependence of the vapor-liquid distribution coefcients of different gases and of water fugacity for 1, 2, and 3 m NaCl
solutions. The a and b coefcients refer to the log B
i
a bT (C) and log f
H
2
O
a b/T(K) equations, respectively.
1 m 2 m 3 m
a b a b a b
CO
2
4.9448 0.01063 5.0036 0.01044 5.0786 0.01038
H
2
6.4663 0.01366 6.5419 0.01341 6.6382 0.01334
CH
4
6.3129 0.01346 6.3874 0.01322 6.4824 0.01315
CO 6.8702 0.01471 6.9517 0.01444 7.0554 0.01436
Ar 6.7537 0.01557 6.8400 0.01529 6.9499 0.01521
NH
3
1.4605 0.00284 1.4762 0.00279 1.4963 0.00278
H
2
S 4.2215 0.00955 4.2744 0.00938 4.3417 0.00933
N
2
6.6828 0.01378 6.7591 0.01353 6.8563 0.01346
He 6.1709 0.01235 6.2393 0.01213 6.3264 0.01206
f
H2O
5.4954 2046.69 5.4791 2046.69 5.4620 2046.69
L
values. These discrepancies might be due to experimental

problems (perhaps due to the strongly corrosive nature of the
mixed sulde-chloride solutions) (Kozintseva, 1965), which
are probably more severe at higher temperatures. Therefore, we
prefer to rely on the measurements carried out at T 275C.
Coupling Eqn. 6 and 7 with the linear equation linking L
and T(C) for a specied NaCl concentration, log B

CO
2
-T and
log B
H
2
S
-T relationships are easily obtained for this NaCl
concentration. Equations linking log B
i
and L
have been
derived for other geothermal-volcanic gases from solubilities in
pure water (Giggenbach, 1980; Naumov et al., 1974) and
corresponding L
values. Assuming that these equations also

hold true for NaCl solutions, as documented above for CO
2
and
H
2
S, log B
i
-T relationships for 1, 2, and 3 m NaCl solutions
have been readily obtained through substitution of L
-T equa-
tions in log B
i
-L
equations (Table 3).

With these new estimation techniques (there is, of course, no
substitute for experimental solubility data which are much
needed), we are now ready to reconsider gas equilibria for
systems where concentrated NaCl solutions are present instead
of pure water. However, it must be stressed that Eqn. 6 and 7,
and consequently all the relationships reported in Table 3, are
expected to give erratic results close to the critical point of any
NaCl-H
2
O solution. In fact, approaching this condition, log B
i
3 0 and L
3 log
C
. Since the critical density of NaCl-H
2
O
solutions varies with the NaCl concentration, these equations
lose their validity approaching critical conditions.
6. GAS EQUILIBRIA IN THE H
2
-CO
2
-CO-CH
4
-H
2
O
SYSTEM
Gas equilibria governing the concentrations of H
2
, CO
2
, CO,
CH
4
, and H
2
O in the fumarolic efuents of Vesuvio crater
bottom have been investigated by means of (1) the two sums of
log ratios log (X
H
2
O
/X
H
2
) log (X
CO
/X
CO
2
) and 3 log (X
CO
/
X
CO
2
) log (X
CO
/X
CH
4
), that are controlled by two indepen-
dent variables (e.g., temperature and either water fugacity or
the fraction of separated vapor) and are independent of the
redox potential, and (2) the CO/CO
2
, H
2
/H
2
O and CH
4
/CO
2
ratios that are controlled by three independent variables, such
as temperature, redox potential, and either water fugacity or the
fraction of separated vapor (Chiodini and Marini 1998).
6.1. The sums of log-ratios log (X
H
2
O
/X
H
2
) log (X
CO
/
X
CO
2
) and 3 log (X
CO
/X
CO
2
) log (X
CO
/X
CH
4
)
These two sums of log-ratios are plotted in Figure 4, where
the theoretical values for a single saturated vapor phase and
single saturated liquid phases are shown as vapor line and
liquid lines, respectively. Equilibrium vapor compositions are
obviously independent on the NaCl concentration of the liquid
Fig. 3. Correlation plots between the logarithm of the vapor-liquid
distribution coefcient B
i
for (a) CO
2
and (b) H
2
S, and the L
param-
eter, which is equal to log (
V
/
L
)-log (
C
).
Fig. 4. Gas ratio diagram of log (X
H
2
O
/X
H
2
) log (X
CO
/X
CO
2
) vs. 3
log (X
CO
/X
CO
2
) log (X
CO
/X
CH
4
). The theoretical values of both
variables in a single saturated vapor phase and in a single saturated
liquid phase, for NaCl concentrations of 0, 1, 2, and 3 m, are shown,
together with the analytical gas ratios for the fumaroles of Vesuvio
crater bottom.
phase, but this variable has a strong effect on equilibrium liquid
compositions as expected. The compositions of vapors sepa-
rated in a single step at temperature Ts, from boiling liquids of
original temperature To, are also reported as single-step vapor
separation (SSVS) lines for the pure water grid. In addition, the
composition of superheated vapors equilibrated at different
temperature and f
H
2
O
values is also shown (Chiodini and
Marini, 1998).
Despite some spread, most fumarolic efuents of the Vesu-
vio crater bottom plot close to the equilibrium saturated vapor
line. Samples from vents FC2 and FC5 are between the grids
for the 1 m and the 3 m NaCl solutions, whereas samples from
vent FC1 plot close to the critical point of pure water and below
it. Focussing on the fumarolic efuents of vents FC2 and FC5,
it is evident that they can be separated from boiling of an NaCl
solution whose minimum salinity is approximately 2 to 3 m.
However, the involvement of a more concentrated NaCl solu-
tion cannot be excluded, whose liquid curve is expected to lie
to the right of the 3 m NaCl liquid curve in Figure 4 simply
because the critical point increases with the NaCl content of the
system. For practical purposes, the minimum salinity of the
hydrothermal liquid phase has been assumed as 3 m, whereas
its maximum salinity is obviously represented by a brine sat-
urated with respect to halite.
Under the alternative hypothesis, i.e., attainment of chemical
equilibrium in a supercritical phase, samples are not expected
to be aligned along the saturated vapor line contrary to what is
observed in Figure 4. Again, this supports the presence of
saline liquids rather than supercritical uids.
Equilibrium temperatures and water pressures have been
calculated for the two limiting salinities (Table 4) and obtained
(1) equilibrium temperature values of 372 13C (FC1) and
445 9C (FC2 and FC5) for the 3 m NaCl solution and 361
12C (FC1) and 429 8C (FC2 and FC5) for the halite-
saturated brine and (2) f
H
2
O
values of 195 28 bar (FC1) and
410 35 bar (FC2 and FC5) for the 3 m NaCl solution and
117 14 bar (FC1) and 216 15 bar (FC2 and FC5) for the
halite-saturated brine. Water fugacities in the zones of the
hydrothermal system, where gases presumably equilibrate, are
poorly constrained, mainly due to uncertainties in the NaCl
content of the liquid phase circulating in the hydrothermal
environment.
The fugacity of the second gas constituent, CO
2
, has been
computed referring to the water-gas shift reaction:
H
2
O CO CO
2
H
2
(8)
whose equilibrium constant is rearranged as follows (modied
after Chiodini and Cioni, 1989):
log f
CO2
2.485 2248/T log(X
H2
/X
CO
) log f
H2O
. (9)
This equation is derived for vapor phases and, therefore, does
not include any term accounting for the partition of CO and H
2
between the vapor and liquid phases. Computed f
CO
2
are 23
3 bar (FC1) and 66 9 bar (FC2 and FC5) for the 3 m NaCl
solution and 16 2 bar (FC1) and 41 5 bar (FC2 and FC5)
for the halite-saturated brine.
In the log f
CO
2
vs. 1000/T(K) diagram (Fig. 5), equilibrium
temperatures and f
CO
2
values of Vesuvio fumarolic uids plot
to the left of the full equilibrium function of Giggenbach (1984,
1988) and fall in the eld of metamorphic-(metasomatic?)
reactions involving carbonate minerals. The fumarolic uids of
the other two Campanian systems (see Fig. 1 for location),
Ischia Island (I) and Solfatara di Pozzuoli, Campi Flegrei (S),
are also plotted in Figure 5 for comparison. The uids of
Solfatara di Pozzuoli are close to the full equilibrium line at
temperatures of 200 to 250C and f
CO
2
of 0.5 to 5 bar, whereas
efuents of Ischia plot in the metamorphic reaction eld, but at
temperatures and f
CO
2
values lower than Vesuvio fumaroles.
Under the hypothesis of ideal gas behavior, total uid pres-
sures, which are closely approximated by P
H
2
O
P
CO
2
, are
218 31 bar (FC1) and 477 44 bar (FC2 and FC5) for the
Table 4. Equilibration temperatures and pressures for the H
2
O-H
2
-CO
2
-CH
4
-CO system.
Date TC
a
TC
b
f
H
2
O
a
(bar)
f
H
2
O
b
(bar)
f
CO
2
a
(bar)
f
CO
2
b
(bar)
P
tot
a
(bar)
P
tot
b
(bar)
FC1 230498 348 358 102 165 14 20 115 185
FC1 240698 371 382 128 218 18 26 146 244
FC1 141198 365 376 121 203 16 23 136 226
FC1 141099 333 342 86 136 9 12 95 148
FC2 160596 425 440 208 391 34 55 242 446
FC2 310796 422 438 204 382 39 62 243 444
FC2 190497 449 467 254 497 55 92 309 588
FC2 230498 436 452 228 436 45 73 273 509
FC2 240698 436 452 228 438 40 66 269 503
FC2 141198 437 454 230 443 42 68 272 511
FC2 50299 432 448 221 422 43 69 264 491
FC2 280799 429 445 215 408 42 67 257 475
FC2 280899 429 445 216 410 41 66 257 476
FC2 250999 422 437 203 381 37 58 240 439
FC2 141099 417 431 194 360 34 54 228 414
FC5 230498 421 436 202 378 42 67 244 445
FC5 240698 431 447 220 418 38 62 258 479
FC5 141198 421 436 201 376 34 55 236 431
FC5 280799 423 439 206 386 39 63 245 448
a
Saturated NaCl brine
b
3 m NaCl brine
3 m NaCl solution and 132 16 bar (FC1) and 257 20 bar
(FC2 and FC5) for the halite-saturated brine. In a simple
hydrostatic model, the uids delivered by vents FC2 and FC5
come from depths of 2.6 to 4.8 km, whereas the uids dis-
charged by vent FC1 proceed from 1.3 to 2.2 km (Fig. 5).
Accepting this hypothesis, the hydrothermal system would be
hosted within the carbonate sequence and in the overlying
volcanic rocks.
In Figure 6, the compositions of coexisting vapors and liq-
uids in the NaCl-H
2
O system (Tanger and Pitzer, 1989) are
reported as a function of pressure along the isotherms of 425
and 450C, which closely approximate the average equilibrium
temperature of vents FC2 and FC5. Figure 6 shows that the
expected NaCl contents in the vapor phase range between
maximum values of 8400 to 23,800 mg/kg, for the minimum
salinity of the hydrothermal liquid phase 14.9 wt.% NaCl (3
m), and minimum values of 160 to 310 ppm for the maximum
salinity of the hydrothermal liquid phase, 49.2 to 52.5 wt.%
NaCl at saturation with halite. These gures are signicantly
higher than the measured NaCl content of sampled fumarolic
uids, a few ppm (see section 3) probably due to the occurrence
of steam condensation. In fact, even if a negligible amount of
steam is condensed, NaCl is almost completely removed from
the vapor phase, since it shows a strong preferential distribution
toward the liquid phase with B
NaCl
(
V
/
L
)
4.4
(Ellis, 1979).
This behavior of volatile constituents with high solubility in
water is well known to people working in geothermoelectric
power plants, since the so-called rst drop of condensate
from superheated geothermal steam typically has low pH and
high salinity and induces corrosion and scaling of turbine
blades (Andreussi et al., 1994).
Equilibrium temperatures inferred on the basis of Figure 4
are used below to investigate other gas equilibria by means of
suitable graphic techniques. Since fumarolic uids discharged
at the Vesuvio crater bottom are representative of equilibrium
vapor phases, the equilibrium liquid lines are not reported in the
diagrams presented below.
6.2. The X
CO
/X
CO
2
, X
H
2
/X
H
2
O
and X
CH
4
/X
CO
2
ratios
The behavior of the individual ratios X
CO
/X
CO
2
, X
H
2
/X
H
2
O
,
and X
CH
4
/X
CO
2
in the hydrothermal system present underneath
Vesuvio crater deserves further consideration as, in general,
CH
4
reacts more slowly than H
2
and CO to changes in tem-
perature, pressure, or redox potential. Consequently, the com-
bination of these species in a unique system (e.g., Fig. 4) leaves
some doubt as to its reliability (Giggenbach, 1987, 1991a).
As stated previously, the X
CO
/X
CO
2
, X
H
2
/X
H
2
O
and X
CH
4
/
X
CO
2
ratios depend not only on the temperature and water
fugacity (or the fraction of separated vapor), but also on the
redox conditions in the gas equilibration zone. The distribution
of redox conditions in different hydrothermal systems located
in active volcanic areas cannot be adequately explained by
means of a unique f
O
2
buffer (Chiodini and Marini, 1998). Even
single hydrothermal systems include mature environments
where adularia and muscovite (or illite) coexist as typical
product minerals, and immature environments where kaolinite,
alunite, and anhydrite develop due to the presence of acidic and
oxidizing uids (Giggenbach, 1993, 1997a). Nevertheless, to
keep the subsequent discussion to a reasonably simple level,
possible redox conditions in hydrothermal environments are
assumed to be approximated satisfactorily by either the (FeO)-
(FeO
1.5
) buffer of Giggenbach (1987):
log f
O2
10.736 25414/T (10)
or by the empirical relationship of DAmore and Panichi
(1980):
log f
O2
8.20 23643/T. (11)
Fig. 5. Plot of log f
CO
2
vs. 1000/T(K), showing the full equilibrium
function of Giggenbach (1984, 1988), the f
CO
2
-T conditions of meta-
morphic reactions involving carbonate minerals and the f
CO
2
values
computed from the analytical data for the fumarolic uids discharged
from Vesuvio crater bottom. Other Campanian fumarolic uids from
Ischia Island (I) and Solfatara di Pozzuoli (S) are shown for comparison
(data from Tedesco, 1996; Chiodini et al., 1992; Chiodini and Marini,
1998).
Fig. 6. NaCl concentrations of vapor and liquid along the 425 and
450C isothermal, vapor liquid coexistence curves as a function of
pressure (from Tanger and Pitzer, 1989). The expected NaCl concen-
trations for vents FC2 and FC5 of Vesuvio are obtained starting from
the minimum and maximum NaCl content of the liquid phase, i.e., 14.9
and 49.2 to 52.5 wt.%, respectively.
Based on this assumption, theoretical X
CO
/X
CO
2
, X
H
2
/X
H
2
O
and
X
CH
4
/X
CO
2
ratios in a single saturated vapor phase have been
computed (Chiodini and Marini 1998) and reported in Figure 7,
where the corresponding analytical ratios for the fumaroles of
Vesuvio crater bottom are also plotted at the equilibrium tem-
peratures evaluated by means of Figure 4. In Figure 7, the
theoretical X
CO
/X
CO
2
, X
H
2
/X
H
2
O
, and X
CH
4
/X
CO
2
ratios ex-
pected for redox conditions governed by the magmatic SO
2
-
H
2
S buffer (Giggenbach, 1987) are also shown for reference. It
must be noted that (1) in the temperature range of interest, the
two hydrothermal f
O
2
buffers give similar results and (2) more
important, analytical ratios agree satisfactorily with theoretical
hydrothermal values, suggesting that CO, H
2
, as well as CH
4
evidently attain chemical equilibrium within the hydrothermal
system under redox conditions closely approximated by any of
the two hydrothermal f
O
2
buffers. Although this conclusion is
not totally independent on that reached by means of Figure 4,
such an overall chemical equilibrium is not always observed,
especially for what concerns CH
4
, which is known to be a very
unreactive molecule. Attainment of chemical equilibrium be-
tween CH
4
and CO
2
in natural systems probably requires the
involvement of suitable catalysts, such as the oxides or Fe or
other metals. Further research is needed to fully understand the
kinetics of the CO
2
-CH
4
conversion in the presence of these
natural catalysts. However, investigating the production of hy-
drocarbons accompanying olivine serpentinization at 300C,
Berndt et al. (1996) found that 1% of the CO
2
was converted
to CH
4
in 2 months. Based on these results and assuming that
this CO
2
-CH
4
conversion is a pseudo rst-order reaction,
Giggenbach (1997b) derived a reaction half-time of 11.7 yr at
300C. Assuming that this natural process has the same acti-
vation energy of the Fischer-Tropsch technical process (85
kJ/mol), Giggenbach (1997b) obtained the following tempera-
ture dependence for the reaction half-time, t
1/2
(T in K):
log t
1/2
6.69 4440/T. (12)
At the equilibrium temperatures estimated for the fumaroles of
Vesuvio crater bottom, the time for 90% conversion of CO
2
to
CH
4
is estimated to be 1.1 to 1.5 yr for vents FC2 and FC5 and
5.5 to 7.2 yr for vent FC1 by using Eqn. 12. It turns out that
CH
4
is quite reactive in these high-temperature hydrothermal
environments and attainment of chemical equilibrium with CO
2
is therefore plausible.
2
-H
2
S-H
2
O SYSTEM
The total sulfur content of Vesuvio fumaroles is unusually
low with respect to fumarolic uids from other active volca-
noes. Besides, the absence of SO
2
suggests that sulfur species
are xed by redox reactions in the same hydrothermal environ-
ments where C-H-O species equilibrate.
Previous investigations (Giggenbach, 1980) have shown that
the H
2
S fugacity in hydrothermal environments is controlled by
coexisting pyrite, an unspecied Fe-Al-silicate (here indicated
as [FeO], probably chlorite or epidote in natural systems) and
the corresponding Al-silicate in its protonated, Fe-free form,
[H
2
O], as expressed by the following reaction (after Giggen-
bach, 1980, modied):
FeS
2
H
2
O [H
2
O] [FeO] 1/2 O
2
2 H
2
S, (13)
whose equilibrium constant is conveniently written as:
log (X
H2S
/X
H2O
)
1
2 log K
S
1
4 log f
O2
1
2 log f
H2O
. (14)
Fig. 7. Diagram of (a) log X
CO
/X
CO
2
, (b) log X
H
2
/X
H
2
O
, and (c) log
X
CH
4
/X
CO
2
vs. 1000/T(K). Theoretical ratios in a single saturated vapor
phase, under redox conditions controlled by the hydrothermal f
O
2
buffers of Giggenbach (1987) and DAmore and Panichi (1980) are
shown for reference. Theoretical ratios expected for varying water
fugacities and redox conditions xed by the magmatic SO
2
-H
2
S buffer
(Giggenbach, 1987) are also plotted. Analytical ratios for the fumaroles
of Vesuvio crater bottom are plotted against the equilibrium tempera-
tures calculated through H
2
-CO
2
-CO-CH
4
-H
2
O equilibria.
As indicated by Eqn. 14, equilibrium X
H
2
S
/X
H
2
O
ratios depend
upon temperature, redox potential, and water fugacity in the gas
equilibration zone. The temperature dependence of the thermo-
dynamic constant K
S
is given by the following equation:
log K
S
2.388 13211.8/T(K), (15)
which is based on an empirical correlation by Giggenbach
(1980) and on the thermodynamic constant of water formation
from elements (Stull et al., 1969). Assuming that redox condi-
tions in the gas equilibration zone are xed by either Eqn. 10 or
11 and water fugacity is constrained by Eqn. 3, the temperature
dependence of the theoretical X
H
2
S
/X
H
2
O
ratio in a single sat-
urated vapor phase has been computed and reported in Figure
8. In the same gure the analytical X
H
2
S
/X
H
2
O
ratios for the
fumaroles of Vesuvio crater bottom are plotted against the
equilibrium temperatures computed through gas equilibria in
the H
2
-CO
2
-CO-CH
4
-H
2
O system. Since the analytical data of
most fumaroles are close to the theoretical values, it can be
concluded that H
2
S approaches chemical equilibrium within
the hydrothermal system at temperatures similar to those esti-
mated by C-H-O gas equilibria. The few samples that plot
below the theoretical vapor lines could be affected by minor
steam condensation, which determines a remarkable loss of
H
2
S due to its high solubility in the liquid phase.
2
-N
2
-NH
3
-H
2
O SYSTEM
Ammonia and N
2
are involved in the following redox reac-
tion (Giggenbach, 1980, modied):
N
2
3 H
2
O 2 NH
3
3/2 O
2
(16)
whose equilibrium constant can be written as
L
N
log (X
NH3
/X
N2
) log (X
NH3
/X
H2O
)
log K
N
3/2 log f
O2
2 log f
H2O
. (17)
Eqn. 17 indicates that theoretical L
N
values are controlled by
temperature, redox conditions, and water fugacity in the gas
equilibration zone. On the basis of the thermodynamic data of
Stull et al. (1969), the temperature dependence of the thermo-
dynamic constant K
N
is described by:
log K
N
3.996 32863/T(K). (18)
Again, the temperature dependence of theoretical L
N
values in
a single-saturated vapor phase has been calculated for redox
conditions described by the f
O2
buffers of Giggenbach (1987)
and DAmore and Panichi (1980) and for water fugacities
constrained by Eqn. 3. Results are reported in Figure 9, also
showing the theoretical L
N
values expected for redox condi-
tions controlled by the magmatic SO
2
-H
2
S buffer (Giggenbach,
1987), which probably becomes active underneath the hydro-
thermal environment that is approaching the deeper magmatic
environment. Most analytical L
N
values for the fumaroles of
Vesuvio crater bottom are close to the equilibrium values under
typical hydrothermal redox conditions at the temperatures es-
timated through gas equilibria in the H
2
-CO
2
-CO-CH
4
-H
2
O
system. Hence, ammonia and N
2
also appear to equilibrate
within the hydrothermal system at temperatures similar to those
estimated by C-H-O gas equilibria.
Fig. 8. Plot of log X
H
2
S
/X
H
2
O
vs. 1000/T(K). The theoretical values
of the X
H
2
S
/X
H
2
O
ratio in a single saturated vapor phase, under redox
conditions controlled by both the (FeO)-(FeO
1.5
) buffer of Giggenbach
(1987) and the f
O2
buffer of DAmore and Panichi (1980), are shown
for reference. Analytical X
H
2
S
/X
H
2
O
ratios for the fumaroles of Vesuvio
crater bottom are plotted against the equilibrium temperatures esti-
mated through gas equilibria in the H
2
-CO
2
-CO-CH
4
-H
2
O system.
Fig. 9. Diagram of L
N
log (X
NH
3
/X
N
2
) log (X
NH
3
/X
H
2
O
) vs.
1000/T(K). The theoretical L
N
values in a single saturated vapor phase,
under redox conditions controlled by the two hydrothermal redox
buffers of Giggenbach (1987) and DAmore and Panichi (1980), are
shown for reference. Also shown are the theoretical values of L
N
in a
single saturated vapor phase and at varying water fugacities for redox
conditions controlled by the magmatic SO
2
-H
2
S buffer (Giggenbach
1987). Analytical L
N
values for the fumaroles of Vesuvio crater bottom
are plotted against the equilibrium temperatures estimated through the
gas-ratio diagram of Figure 4.
9. THE H
2
-AR GEOINDICATOR
Giggenbach (1991a) derived an H
2
-Ar geoindicator, which is
based on the strong dependence of f
H
2
on temperature and on
the assumption that the Ar content of hydrothermal uids is
equal to that of air-saturated groundwater. A derivation slightly
different from that of Giggenbach (1991a), which includes (at
least in part) the salting-out effect on Ar solubility, is presented
below.
First a test of the Giggenbachs hypothesis is needed, i.e., let
us determine if the Ar content of Vesuvio fumarolic uids is
equal to that of air-saturated groundwater. This exercise is
conveniently carried out by means of the H
2
O-N
2
-Ar triangular
plot (Fig. 10), where the fumarolic samples from vents FC1,
FC2, and FC5 have been plotted together with the points
representative of atmospheric air and air-saturated groundwa-
ters at 5, 10, 15, and 20C. The composition of air-saturated
groundwaters was computed referring to the solubility data of
Wilhelm et al. (1977), and considering that the average atmo-
spheric partial pressures of Ar and N
2
are 0.00934 bar and
0.7808 bar, respectively. Most FC1, FC2, and FC5 samples
have Ar/H
2
O ratios within the range of air-saturated ground-
waters at 5 to 20C (i.e., 3.5 10
7
to 2.5 10
7
). Only the
sample collected on April 23, 1998 from vent FC5 has some-
what higher Ar/H
2
O and N
2
/H
2
O ratios, likely due to steam
condensation. Besides, two other samples are slightly shifted
toward the air point due to either trivial air contamination
during or after sampling, or entrainment of air in the fumarolic
channels upstream of the surface discharge, probably at very
shallow depths. Addition of radiogenic Ar (which would shift
the samples toward the Ar vertex) either does not occur or plays
a very subordinate role, in line with the low
40
Ar/
36
Ar ratios
obtained on phenocrysts separated from historical lavas (Te-
desco et al., 1998).
Figure 10 also shows that the N
2
/Ar ratios of Vesuvio
fumarolic uids are, at 250 to 1150, signicantly greater than
those of air-saturated groundwaters (38). Based on data com-
ing from several areas, Giggenbach (1992b) showed that the
N
2
/Ar ratios of vapor discharges from geothermal and volcanic
systems sited along convergent plate boundaries are generally
higher than those of vapors from midocean ridges and hotspots,
which have N
2
/Ar ratios similar to those of air-saturated
groundwaters. The relatively high N
2
/Ar ratios of gases asso-
ciated with convergent-plate magmatism were ascribed to the
addition of N
2
, chiey coming from the thermal decomposition
of the organic matter contained in subducted sediments (Mat-
suo et al., 1978; Giggenbach, 1992b). Similar processes might
be active underneath Vesuvio as well. Vesuvio fumarolic uids
also exhibit high He/Ar ratios (0.52.7), which might be due to
the addition of either magmatic uids with mantle signature or
4
He from radioactive decay of crustal U and Th (Giggenbach,
1996). The fumarolic uids of Vesuvio crater have compara-
tively low
3
He/
4
He ratios of 2.32 0.10 as R/Ra (Tedesco,
1997), suggesting that both sources might be involved in local
He production. Despite some analytical problems, low
3
He/
4
He
ratios were also measured in pyroxene and olivine phenocrysts
separated from Vesuvio lavas erupted after 1631 (Tedesco and
Scarsi, 1999 and references therein). Since the present under-
standing of the processes governing the
3
He/
4
He ratios in
volcanic and hydrothermal uids is still at a very qualitative-
descriptive stage, further inferences from these data are highly
speculative in our opinion.
Summing up, the Ar content of most Vesuvio fumarolic
uids appear to be very close to that of air-saturated ground-
water. According to Giggenbach (1987), the log (f
H
2
/f
H
2
O
)
log (X
H
2
/X
H
2
O
)
V
of hydrothermal uids is buffered by the
(FeO)-(FeO
1.5
) redox buffer of the rock system at 2.82, at any
temperature of interest. Assuming that the X
Ar
/X
H
2
O
ratio in the
liquid phase is equal to that of average air saturated ground-
water, i.e., log (X
Ar
/X
H
2
O
)
L
6.52 (again, based on the
solubility data of Wilhelm et al. (1977) at 12.5C, and consid-
ering that the average atmospheric partial pressure of Ar is
0.00934 bar), and assuming that X
H
2
O
is close to unity, both in
the liquid and vapor phases, the X
Ar
/X
H
2
O
ratio in the vapor
phase is given by:
log (X
Ar
/X
H2O
)
V
log B
Ar
log (X
Ar
/X
H2O
)
L
log B
Ar
6.52.
(19)
The theoretical X
H
2
/X
Ar
ratio in the vapor phase is readily
obtained as follows:
log (X
H2
/X
Ar
)
V
log (X
H2
/X
H2O
)
V
log (X
Ar
/X
H2O
)
V
3.7 log B
Ar
. (20)
When log B
Ar
3 0, that is, when temperature approaches the
critical point, Eqn. 20 reduces to log (X
H
2
/X
Ar
)
V
3.7, which
holds true for any aqueous solution, independent of its salinity
(of course, assuming that redox conditions are xed by the
(FeO)-(FeO
1.5
) buffer). The measured log (X
H
2
/X
Ar
) of Vesu-
vio fumaroles span a narrow range, from 3.1 to 3.8, with a
mean of 3.5 0.2, suggesting temperatures close to the critical
temperatures of the boiling solutions.
Inserting in Eqn. 20 the expression describing the tempera-
ture dependence of the vapor-liquid distribution coefcient of
Ar for solutions of different NaCl contents (Table 3), H
2
-Ar
Fig. 10. Triangular plot H
2
O-N
2
-Ar, showing the analytical data of
fumaroles FC1, FC2, and FC5 and the compositions of atmospheric air
and of air-saturated groundwater at 5 to 20C.
geothermometers specic for each salinity are easily obtained.
For example, for 3 m NaCl solutions, the following equation
holds true (where T is in C):
log (X
H2
/X
Ar
)
V
3.25 0.01521 T. (21)
Of course, in the derivation of these H
2
-Ar geothermometers,
the possible salinity effects on the H
2
/H
2
O ratio have been
ignored, assuming that the (FeO)-(FeO
1.5
) redox buffer is sa-
linity independent. H
2
-Ar geothermometers cannot be derived
for halite-saturated brines as gas solubilities cannot be extrap-
olated for these highly saline environments.
The H
2
-Ar geothermometers have been applied to the fuma-
roles of Vesuvio crater bottom by using two different log
(X
H
2
/X
Ar
) vs. log (X
CO
/X
CO
2
) diagrams (Fig. 11). In Figure
11a, redox conditions are considered to be xed by the (FeO)-
(FeO
1.5
) buffer, while in Figure 11b, the redox potential is
assumed to be constrained by the DAmore and Panichi (1980)
buffer. Four distinct curves represent the theoretical log ratio
values in a single saturated vapor phase in equilibrium with
pure water and 1 m, 2 m, and 3 m NaCl solutions. In addition,
relevant isotherms and the curve of the critical temperatures are
also shown in Figure 11. Despite a certain scatter of analytical
data, they generally overlap theoretical compositions. Again,
samples from vents FC2 and FC5 show equilibration temper-
atures (430450C or higher) and salinities (generally 13 m)
greater than FC1 samples, which plot close to the curve of pure
water at temperatures of 310 to 360C. These indications are in
substantial agreement with those given by the H
2
-CO
2
-CO-
CH
4
-H
2
O system. It must be underscored that since H
2
O is not
involved in the H
2
-Ar geothermometers, these are totally un-
affected by steam condensation.
10. ISOTOPIC COMPOSITION OF CO
2
AND H
2
O
10.1. The
13
C values of CO
2
The
13
C values of CO
2
in all the samples of Vesuvio
fumaroles span a narrow range, from 0.06 to 0.34 vs.
PDB. These relatively high
13
C values agree with previous
measurements (Allard et al., 1997; Tedesco, 1997) and suggest
that most CO
2
derives from decarbonation of marine carbon-
ates. We will show that this hypothesis is consistent with the
equilibrium f
CO
2
and temperatures of Vesuvio fumarolic uids
(see section 6.1 and Fig. 5). Taking the full equilibrium reac-
tions of Giggenbach (1988), i.e.,
Ca-Al
2
-silicate K-feldspar CO
2
K-mica calcite,
(22)
as thermodynamic proxies for water-rock reactions in the hy-
drothermal reservoir, and considering the correspondent log
P
CO
2
-T (C) relation:
log P
CO2
0.0168 T 3.78, (23)
full equilibrium P
CO2
values of approximately 2 to 6 kbar are
expected for the highest equilibrium temperatures of the Vesu-
vio hydrothermal system, i.e., 425 to 450C (see above). These
P
CO2
values are much higher than those estimated for this
system, 0.02 to 0.07 kbar, based on the chemistry of fumarolic
uids, and are unlikely to be reached in a relatively shallow
system such as that of Vesuvio (depth of few km). Conse-
quently, these reactions are expected to run in the opposite
sense of Eqn. 22, that is, they will consume calcite, producing
Fig. 11. Correlation plots of log (X
H
2
/X
Ar
) vs. log(X
CO
/X
CO
2
) for the fumarolic uids from vents FC1, FC2, and FC5.
Theoretical values for a single saturated vapor phase in equilibrium with pure water and 1, 2, and 3 m NaCl solutions are
shown both for redox conditions controlled by (a) the (FeO)-(FeO
1.5
) buffer of Giggenbach (1987) and (b) the f
O
2
buffer
of DAmore and Panichi (1980).
CO
2
, which will tend to escape from the system. The same
considerations apply also to the metamorphic reaction:
dolomite 2 quartz diopside 2 CO
2
, (24)
whose equilibrium T, f
CO
2
values plot to the right of the
analytical data in Figure 5. However, the T, f
CO
2
evaluated from
vents FC2 and FC5 are very close to the equilibrium T, f
CO2
values of the other metamorphic reactions plotted in Figure 5,
i.e.,
diopside 3 dolomite 2 forsterite 4 calcite 2 CO
2
(25)
and
calcite quartz wollastonite CO
2
, (26)
suggesting that CO
2
can be either produced or consumed by
these reactions in response to small changes in either T, or f
CO
2
,
or both. Although the reactions listed above are only some of
the innumerable possible reactions, the T, f
CO
2
conditions of the
Vesuvio hydrothermal system favor CO
2
production through
decarbonation of marine carbonates, which are abundant in the
Vesuvian geological framework. A thick carbonate sequence is
in fact located at depths 2.5 km underneath the volcano
(Principe et al., 1987, Fig. 13). In addition, the past occurrence
of decarbonation reactions is documented by the skarns and
impure marbles, which were ejected in several explosive erup-
tions (e.g., Thompson, 1798; Barberi and Leoni, 1980; Joron et
al., 1987; Crocetti, 1996).
The isotopic composition of the CO
2
produced by decarbon-
ation reactions depends on several factors, including the mode
of CO
2
separation (either batch or Rayleigh, or intermediate
between these two endmember processes), reaction progress,
temperature, etc., but produced CO
2
has
13
C values more
positive than the reacting rock, as the CO
2
-calcite fractionation
factor at relevant temperatures (400600C) ranges from 2.6
to 2.7 (Ohmoto and Goldhaber, 1997; Valley, 1986).
Based on these fractionation factor values and considering that
the average
13
C values of carbonate rocks of marine origin of
Cambrian to Tertiary age is 0.56 1.55 vs. PDB (Keith
and Weber, 1964), the isotopic composition of the CO
2
at the
beginning of the decarbonation process is expected to be close
to 3.21 1.55, that is signicantly more positive than
measured in Vesuvio fumaroles.
The reason for this discrepancy could be either a signicant
progress of the decarbonation reaction or the presence of a
relatively small fraction of magmatic CO
2
, which generally has
lighter isotopic composition, 4 to 8 (Deines and Gold,
1973; Kyser, 1986). However, the
13
C value of magmatic CO
2
is poorly constrained, depending on the extent of degassing as
well as on melt composition, mode of gas separation, and
temperature. The experimentally determined equilibrium iso-
tope fractionation factors for CO
2
degassing from basaltic
melts (where the prevailing C-species is carbonate) range be-
tween 2 and 4.3, depending on temperature, whereas
CO
2
degassing from rhyolitic melts does not induce any isotope
fractionation, since the prevailing C-species is molecular CO
2
(Holloway and Blank, 1994; Blank and Brooker, 1994). It is
generally accepted that the CO
2
/CO
3
2
ratio increases, moving
from mac to silicic compositions, implying a concurrent de-
crease of the isotope fractionation factor. Moreover, an equi-
librium isotope fractionation factor of 2.4 was obtained at
1200 to 1400C for a sodamelilite (NaCaAlSi
2
O
7
) liquid,
where dissolved C occurs as carbonate ions (Mattey et al.
1990). Therefore, apart from the extreme case of rhyolitic melts
(that have no relevance for Vesuvio), the heavy isotope is
partitioned preferentially into the gas phase during magma
degassing and the
13
C value of the melt is expected to exhibit
a progressive decrease, as shown by Holloway and Blank
(1994). Because of the low solubility of CO
2
in silicate melts
(Blank and Brooker, 1994), degassing of CO
2
can begin at
depths approaching the zone of magma generation (Giggen-
bach, 1996), thus inducing strong variations in the isotopic
signature of magmatic CO
2
.
A further complication in constraining the isotopic compo-
sition of the local magmatic source is due to possible source
contamination brought about by subduction of carbonate-rich
sediments (Tedesco, 1997).
Summing up, the isotopic composition of the CO
2
produced
by decarbonation reactions as well as that of magmatic CO
2
may exhibit substantial variations for the reasons discussed
above. The presence of a relevant fraction of CO
2
derived from
decarbonation reactions in the fumarolic uids of Vesuvio is
very likely (but cannot be computed) and agrees with the
indications provided by gas chemistry (see above), with the
local geological setting, and with the presence of skarn and
impure marble ejecta in the products of explosive eruptions.
10.2. The effect of oxygen isotope fractionation between
CO
2(g)
and H
2
O
(g)
The D and
18
O values of H
2
O and the
18
O value of CO
2
of fumaroles FC2 and FC5 (33 to 53, 7.3 to 8.3,
and 28.8 to 30.4, respectively) are signicantly different
from those of vent FC1, which shows lighter isotope compo-
sitions of both water (D 83 to 92 and
18
O 13.3 to
14.0) and CO
2
(
18
O 23.1 to 23.6).
In the classic D vs.
18
O diagram (Fig. 12), local ground-
waters from 40 shallow wells (Caliro et al., 1998), showing D
values of 35 to 41 and
18
O values of 5.9 to 7.4,
plot close to the worldwide meteoric water line. All the samples
from fumaroles FC1, FC2, and FC5 plot, instead, slightly to the
left of the worldwide meteoric water line, far from the eld of
arc-type (andesitic) magmatic waters identied by Giggenbach
(1992a).
The correct interpretation of these data demands consider-
ation of the difference between the
18
O values of CO
2
and
H
2
O. The
18
O
CO
2
-H
2
O
is available for only three samples (one
from of each vent) and spans a very small range, 36.2 to
36.9. These values coincide with the theoretical oxygen
isotope fractionation factor between CO
2(g)
and H
2
O
(g)
(Richet
et al., 1977) at temperatures of 93 to 96C, suggesting that these
two species are in isotopic equilibrium at outlet conditions.
This in turn implies occurrence of rapid oxygen isotope ex-
change between CO
2(g)
and H
2
O
(g)
along the uprising channels
of the Vesuvio crater fumarolic system, as already observed for
many natural systems (Chiodini et al., 2000). Following these
authors, the initial
18
O value of water,
18
O
H
2
O,i
(i.e., in the
hydrothermal reservoir), can be calculated from the nal
18
O
value of water,
18
O
H
2
O,f
(i.e., at the surface discharge), com-
bining a simple oxygen isotope mass balance with the oxygen
isotope fractionation factors under both initial and nal condi-
tions, thus obtaining the following relationship:
18
O
H2O,i

18
O
H2O,f
[2 X
CO2
/(1 X
co2
)] [1000 ln
i
1000 ln
f
], (27)
Here identies the oxygen isotope fractionation factor be-
tween CO
2(g)
and H
2
O
(g)
, whose temperature dependence is
satisfactorily explained by this third order polynomial equation
(Chiodini et al., 2000):
1000 ln 5.7232 20.303 (10
3
/T) 11.977(10
6
/T
2
)
3.7432 (10
9
/T
3
) (28)
that closely ts the theoretical fractionation of Richet et al.
(1977) below 400C and those of Friedman and ONeil (1977)
at higher temperatures of up to 1000C. The
18
O
H
2
O,i
values
were calculated taking the outlet temperatures and the equilib-
rium temperatures based on gas equilibria in the H
2
-CO
2
-CO-
CH
4
-H
2
O system (Fig. 4) to be representative of nal and
initial conditions, respectively. Since the temperature depen-
dence of is not very pronounced above 350 to 400C, the
uncertainties in the gas equilibrium temperatures (see above)
have small effects on the calculation of
18
O
H
2
O,i
. Occurrence
of steam condensation increases X
CO
2
, possibly inducing an
overcorrection of the
18
O of H
2
O. This is the case in the
sample collected on April 23, 1998 from vent FC5, whose
position in Figure 12 suggests that it originated from a uid of
initial isotopic composition similar to that of the other FC2 and
FC5 samples through a signicant extent of steam condensation
at temperature close to 100C. Line D1 depicts the theoretical
effects of steam condensation induced by conductive heat
losses at a constant temperature of 100C (Brombach et al.,
2000, 2001) and reports the fraction of condensed steam, which
is close to 0.5 for the sample collected on April 23, 1998 from
vent FC5. The occurrence of steam condensation for this sam-
ple is not surprising, since it was already hypothesized on the
basis of its relative H
2
O, N
2
, and Ar contents (see above).
However, apart from this sample, which is excluded from the
following discussion, such large effects of steam condensation
are unlikely for the other fumarolic samples.
10.3. The D and
18
O values of H
2
O
To help the interpretation of available D and
18
O data of
fumarolic uids, they are reported in Figure 12 together with
the theoretical D and
18
O values of the vapors produced
through single-step separation (Giggenbach and Stewart, 1982;
Giggenbach, 1991b) from:
1. A parent hydrothermal liquid (PHL) from 450 to 100C
(curve A). For the purpose of this discussion, we assume
that the PHL has D of 37.5 and
18
O of 0.33, i.e.,
the isotopic composition of the liquid phase in equilibrium
Fig. 12. Plot of D vs.
18
O values showing the analytical data of fumaroles FC1, FC2, and FC5 and their equilibrium
compositions at depth, computed taking into account the oxygen isotope exchange between CO
2(g)
and steam (Chiodini et
al., 2000). The worldwide meteoric water line, the eld of magmatic arc-type (andesitic) waters (Giggenbach 1992a), and
local groundwaters from shallow wells (Caliro et al. 1998, closed squares) are shown for reference. Also plotted are the
theoretical D and
18
O values of the vapors separated through single-step separation (from 450100C, each 25C) from
(1) a possible parent hydrothermal liquid (PHL), curve A, (2) the PHL mixed with average shallow groundwater, curve B,
and (3) the PHL mixed with a liquid produced through total condensation of the steam separated at 100C from the pure
PHL, curve C. The effects of steam condensation brought about by conductive heat loss at 100C are shown as lines D1
and D2 (numbers represent the fraction of condensed steam).
with the fumarolic sample collected from vent FC2 in April
1998. The isotope composition of this PHL was computed
after correcting the analytical
18
O
H
2
O
for the oxygen iso-
tope exchange between CO
2(g)
and H
2
O
(g)
and assuming a
3 m NaCl concentration.
2. The PHL mixed with the mean shallow groundwater (curve
B). The local groundwater has on average D of 38,
18
O of 6.4, and temperature of 15C (Caliro et al.
1998).
3. The PHL mixed with a liquid phase produced through total
condensation of the steam separated at 100C from the pure
PHL (curve C). This steam condensate has D of 47.0,
18
O of 1.66, and temperature of 100C.
The specic enthalpies of saturated vapors and liquids were
taken from Tanger and Pitzer (1989) above 300C and Dittman
(1977) below 300C. Liquid-vapor fractionation factors of O
and H isotopes, valid for NaCl solutions from 0 to at least 5 m
NaCl, were taken from Horita et al. (1995) below 350C. At
higher temperatures, the fractionation factors were calculated
interpolating between the value at 350C and 0, i.e., the
theoretical value at the critical temperature (which is a function
of the NaCl concentration) (Knight and Bodnar, 1989). Since at
these high temperatures the fractionation factors are relatively
small (10 to 0 for H isotopes and 1 to 0 for O
isotopes), uncertainties in this interpolation have negligible
effects in the overall theoretical boiling trend.
In addition, the theoretical effects of steam condensation
determined by heat loss through conduction at a constant tem-
perature of 100C are also shown for two different steam
compositions as lines D1 (see above) and D2.
Comparison of the analytical data, suitably corrected for
oxygen isotope fractionation between CO
2(g)
and H
2
O
(g)
, with
the theoretical trends suggests that (1) fumarolic uids dis-
charged from vents FC2 and FC5 can be separated at high
temperatures from the PHL, either pure or slightly diluted, with
either shallow groundwaters or steam condensates and (2)
fumarolic uids of vent FC1 are much lighter than local me-
teoric waters and plot below curve C, indicating that they
cannot be simply separated from the PHL mixed with a liquid
phase produced through total condensation of the steam sepa-
rated at 100C from the pure PHL. However, their position
along the condensation path D2 does not necessarily imply that
they have experienced some condensation, which would be at
variance with gas chemistry (Fig. 10 and related discussion). A
possible way to reconcile isotopic and chemical evidence is by
admitting that the PHL mixes with a condensate lighter than
that assumed in the calculation of curve C, which could be
produced, for instance, by splitting different fractions of steam
condensates. Suppose we condense 50% of the steam separated
at 100C from the pure PHL and eliminate it. The remaining
steam will have D of 60.9 and
18
O of 4.28. If this
steam condenses separately and mixes with the PHL, the mix-
ture will boil off (at low temperatures) steams of isotopic
compositions very similar to those of fumarolic uids from
vent FC1.
The occurrence of recycling steam condensate is not surpris-
ing and, similar to what was observed at Vulcano crater and
Solfatara di Pozzuoli, Italy (Chiodini et al., 1996b; Chiodini et
al., 2001), and at Nisyros, Greece (Brombach 2000; Brombach
et al., 2001), an important ux of hydrothermal uids ascends
towards the surface below the Vesuvio crater as well. Most
steam condenses close to the surface and the heat given off is
transferred conductively to the atmosphere through the soil,
which is crossed by a large ux of CO
2
(130 t d
1
, Osser-
vatorio Vesuviano, unpubl. data). The condensation process is
particularly important at the margins of the fumarolic eld,
where the downward-owing steam condensate is partly en-
trained in the uprising uids, as observed especially for vent
FC1.
In view of the uncertainties associated with temperature,
isotopic composition, and chemical composition of both the
hypothetical parent hydrothermal liquid and the recycled steam
condensate, the theoretical trends reported in Figure 12 and the
mechanisms proposed to explain the origin of Vesuvio fu-
marolic uids have to be considered qualitative attempts. It is
also difcult to constrain the origin of the hypothetical parent
hydrothermal liquid. It might be either a meteoric water en-
riched in
18
O due to water-rock oxygen isotope exchange or a
mixture of meteoric waters and arc-type magmatic waters.
Although the equilibrium fractionation factors between miner-
als and water (Matsuhisa et al., 1979) are small at the high
temperatures present in the hydrothermal reservoir of Vesuvio
crater, this does not exclude the possible role of water-rock
oxygen isotope exchange, but an essentially stagnant, rock-
dominated system (according to Giggenbach, 1991b) should be
invoked to explain the high, apparent oxygen shift (8) of
the hypothetical parent hydrothermal liquid of Vesuvio.
11. CONCEPTUAL GEOCHEMICAL MODEL AND
CONCLUSIVE REMARKS
At present, fumarolic activity is widespread in the crater area
of Vesuvio volcano. Fumaroles of the crater rim and of the
inner crater slopes discharge uids rich in atmospheric gases
and their outlet temperatures are generally in the range 60 to
75C. The chemistry of these uids is not very informative, but
they transport a signicant ux of heat toward the surface.
The fumarolic uids of the crater bottom (vents FC1, FC2,
and FC5) have, instead, typical hydrothermal compositions,
with H
2
O as a major constituent, followed by CO
2
, H
2
, H
2
S,
N
2
, CH
4
, and CO in order of decreasing concentrations, and
undetectable SO
2
, HCl, and HF. These fumaroles, whose outlet
temperatures have been close to the local boiling point of water
since 1988, are fed by a hydrothermal system located under-
neath the crater.
Fumarolic water is either meteoric water enriched in
18
O
through water-rock oxygen isotope exchange in the hydrother-
mal environment or a mixture of meteoric and arc-type mag-
matic water, as indicated by the
18
O
H
2
O
values, suitably cor-
rected for oxygen isotope exchange between H
2
O and CO
2
, and
the D
H
2
O
values. It is equally possible that both water-rock
oxygen isotope exchange and addition of magmatic water take
place in the hydrothermal system of Vesuvio crater.
Fumarolic CO
2
is produced chiey through metamorphic
reactions involving marine carbonates (although the addition of
a small fraction of magmatic CO
2
cannot be ruled out), as
suggested by both the
13
C
CO
2
values and gas equilibria. These
decarbonation reactions take place in response to a thermal
anomaly locally present in the thick carbonate sequence, which
is known to be located at depths 2.5 km underneath the
volcano (Fig. 13).
Because of the large availability of salts in deep volcanic-
hydrothermal environments, mainly due to absorption of acid,
magmatic gases in deeply circulating groundwaters and the
subsequent neutralization of these acidic aqueous solutions
through water-rock interaction, it seems likely that NaCl liquids
of unknown (probably high) salt content rather than pure water
circulate in the Vesuvio hydrothermal system. Accepting this
hypothesis, gas equilibria were investigated taking into account
the solubility of relevant gas constituents in NaCl aqueous
solutions of specied concentrations. It turns out that C-H-O
gas species equilibrate, probably in a saturated vapor phase, at
very high temperatures: 360 to 370C for vent FC1 and 430 to
445C for vents FC2 and FC5. The minimum salinity of the
liquid phase coexisting with the vapor phase is close to 14.9
wt.% NaCl (3 m), whereas its maximum salinity is 49.2 to 52.5
wt.% NaCl, corresponding to saturation with halite. These
equilibrium temperature values have been obtained applying
two different geothermometric approaches. The rst is based on
the two sums of log-ratios log (X
H
2
O
/X
H
2
) log (X
CO
/X
CO
2
),
and 3 log (X
CO
/X
CO
2
) log (X
CO
/X
CH
4
), the second considers
the individual CO/CO
2
, H
2
/H
2
O, and CH
4
/CO
2
ratios. It turns
out that not only H
2
and CO but also CH
4
(which is generally
considered very unreactive) attain chemical equilibrium in the
hydrothermal environments of Vesuvio. Available kinetic data
suggest that the time required for 90% conversion of CO
2
to
CH
4
is only 1 to 7 yr. Therefore, the unreactive CH
4
is
actually quite reactive in very high temperature hydrothermal
environments.
The equilibrium temperatures evaluated by gas equilibria
between H
2
, CO
2
, CO, CH
4
, and H
2
O are conrmed by H
2
-
H
2
S-H
2
O and H
2
-N
2
-NH
3
-H
2
O gas equilibria, and by the
H
2
-Ar geoindicator, leaving little doubt on the thermal state of
the Vesuvio hydrothermal system.
Unfortunately, the salt content of the aqueous solutions cir-
culating in this system cannot be constrained satisfactorily, and,
consequently, total uid pressures (which are closely approxi-
mated by P
H
2
O
P
CO
2
) in the zones of the hydrothermal system
where gases equilibrate are poorly constrained too. They are
260 to 480 bar for vents FC2 and FC5 and 130 to 220 bar for
vent FC1. Based on a simple hydrostatic model, the hydrother-
mal reservoirs connected with these fumarolic vents are located
at depths of 2.6 to 4.8 km and 1.3 to 2.2 km, respectively.
Consequently, the deepest hydrothermal reservoir appears to be
hosted within the carbonate sequence, which is located at
depths 2.5 km underneath the volcano, whereas the shallow-
est reservoir is sited in the overlying volcanic rocks. However,
Fig. 13. Conceptual geochemical model of the volcanic-hydrothermal system of Vesuvio crater.
it is also possible that uid pressure distribution does not
always follow a hydrostatic regime throughout the hydrother-
mal system, but at least some parts of the system become
overpressurized from time to time. The high uid pore pres-
sure, and the possible discharge of these overpressures through
fracturing, could explain the relatively frequent seismic crises
that affected the Vesuvio apparatus after the last 1944 eruption,
as is already suggested based on seismic analyses (Ventura and
Vilardo, 1999).
At present, the nature of the heat source responsible for
hydrothermal circulation and decarbonation reactions is not
known. However, there is no need to invoke the input of fresh
magma at shallow crustal levels. An important heat source is, in
fact, represented by the magma batches not expulsed during the
last eruptive period (16311944) and the rocks heated in those
years when volcanic eruptions took place with a very high
frequency, averaging 1 event every 7 yr.
The same eruptive conduits of the volcanic system and
nearby rocks now host the high-temperature hydrothermal sys-
tem described above, which acts as the main cooling tool of the
entire system through the expulsion of fumarolic uids (Fig.
13). The progressive temperature decline of crater fumaroles
from 600 to 800C in the 1950s to 95C in the 1990s is likely
one of the clearest effects of this cooling process. Seismic
crises can be considered as another way to dissipate the thermal
energy of the volcano.
Again, the conceptual geochemical model of the Vesuvio
hydrothermal-volcanic system and its present state suggest that
no input of fresh magma at shallow depths took place after the
end of the last eruptive period. On the other hand, the high-
temperature hydrothermal system of Vesuvio could either bring
about hydrothermal eruptions or be involved in magma-water
explosive interaction or both phenomena upon reactivation of
the volcanic (magmatic) system.
AcknowledgmentsThis work was nanced by the Italian National
Group for Volcanology GNV. The authors are grateful to Bruce Chris-
tenson and Jacob Lowenstern for their useful comments and sugges-
tions on the early version of the manuscript.
Associate editor: M. A. McKibben
REFERENCES
Aguilera E., Chiodini G., Cioni R., Guidi M., Marini L., and Raco B.,
(2000) Water chemistry of Lake Quilotoa (Ecuador) and assessment
of natural hazards. J. Volcanol. Geotherm. Res. 97, 271285.
Allard P., Jean-Baptiste P., DAlessandro W., Parello F., Parisi B., and
Flehoc C. (1997) Mantle-derived helium and carbon in groundwaters
and gases of Mount Etna, Italy. Earth Planet. Sci. Lett. 148, 501
516.
Andreussi P., Corsi R., Guidi M., and Marini L. (1994) Theoretical
prediction of physical and chemical characteristics of the rst drop
of condensate from superheated geothermal steam. Implications for
corrosion and scaling in turbines. Geothermics. 23, 233255.
Arno` V., Principe C., Rosi M., Santacroce R., Sbrana A., and Sheridan
M.F. (1987) Eruptive history. In Somma-Vesuvius (ed. R. San-
tacroce), CNR Quaderni de La Ricerca Scientica, CNR, Roma,
114-8, 53103.
Barberi F. and Leoni L. (1980) Metamorphic carbonate ejecta from
Vesuvius Plinian eruptions: Evidence of the occurrence of shallow
magma chambers. Bull. Volcanol. 43, 107120.
Barberi F., Bizouard H., Clocchiatti R., Metrich N., Santacroce R., and
Sbrana A. (1981) The Somma-Vesuvius magma chamber: A petro-
logical and volcanological approach. Bull. Volcanol. 44, 295315.
Barberi F., Cioni R., Rosi M., Santacroce R., Sbrana A., and Vecci R.
(1989) Magmatic and phreatomagmatic phases in explosive erup-
tions of Vesuvius as deduced by grain-size and component analysis
of the pyroclastic deposits. J. Volcanol. Geotherm. Res. 38, 287307.
Berndt M. E., Allen D. E., Seyfried W. E. (1996) Reduction of CO
2
during serpentinization of olivine at 300C and 500 bars. Geology
24, 351354.
Bischoff J. L. and Pitzer K. S. (1989) Liquid-vapor relations for the
system NaCl-H
2
O: Summary of the P-T-X surface from 300C to
500C. Am. J. Sci. 289, 12171248.
Blank J. G. and Brooker R. A. (1994) Experimental studies of carbon
dioxide in silicate melts: Solubility, speciation, and stable carbon
isotope behavior. In Volatiles in Magmas (ed. M. R. Carroll and J. R.
Holloway), Rev. Mineral. 30, 157186.
Brantley S. L., Borgia A., Rowe G., Fernandez J. F., Reynolds J. R.
(1987) Poas volcano acts as a condenser for acid metal-rich brine.
Nature 330, 470472.
Brocchini D., Laurenzi M. A., and Principe C. (1997) Nuove datazioni
delle lave del pozzo Trecase 1 (Campania). Atti del Convegno
Annuale GNV 1996 (abstract), 35 Marzo 1997, 110111.
Brombach T. (2000) Fluid geochemistry of hydrothermal systems in
volcanic island arcs: Guadeloupe (Lesser Antilles) and Nisyros
(Greece). Ph.D. Thesis. Universite de Lausanne.
Brombach T., Marini L., and Hunziker J. C. (2000) Geochemistry of
the thermal springs and fumaroles of Basse-Terre Island, Guada-
loupe, Lesser Antilles. Bull. Volcanol. 61, 477490.
Brombach T., Hunziker J. C., Chiodini G., Cardellini C., and Marini L.
(2001) Soil diffuse degassing and thermal energy uxes from the
southern Lakki plain, Nisyros (Greece). Geophys. Res. Lett. 28,
6972.
Burnham W. C. (1997) Magmas and hydrothermal uids. In Geochem-
istry of Hydrothermal Ore Deposits, 3rd Edition (ed. H. L. Barnes),
pp. 63123, John Wiley & Sons, New York.
Caliro S., Panichi C., and Stanzione D. (1998) Baseline study of the
isotopic and chemical composition of waters associated with the
Somma-Vesuvio volcanic system. Acta Vulcanologica 10, 1925.
Casadevall T. J., De La Cruz-Reyna S., Rose W. I., Bagley S.,
Finnegan D. L., and Zoller W. H. (1984) Crater lake and post-
eruption hydrothermal activity, El Chichon volcano, Mexico. J.
Volcanol. Geotherm. Res. 23, 169191.
Chiodini G. and Cioni R. (1989) Gas geobarometry for hydrothermal
systems and its application to some Italian geothermal areas. Appl.
Geochem. 4, 465472.
Chiodini G. and Marini L. (1998) Hydrothermal gas equilibria: The
H
2
O-H
2
-CO
2
-CO-CH
4
system. Geochim. Cosmochim. Acta 62,
26732687.
Chiodini G., Cioni R., Guidi M., Marini L., Raco B., and Taddeucci G.
(1992) Gas geobarometry in boiling hydrothermal systems: A pos-
sible tool to evaluate the hazard of hydrothermal explosions. Acta
Vulcanologica, Marinelli Volume 2, 99107.
Chiodini G., Cioni R., and Marini L. (1993a) Reactions governing the
chemistry of crater fumaroles from Vulcano Island, Italy, and im-
plications for volcanic surveillance. Appl. Geochem. 8, 357371.
Chiodini G., Cioni R., Leonis C., Marini L., and Raco B. (1993b) Fluid
geochemistry of Nisyros island, Dodecanese, Greece. J. Volcanol.
Geotherm. Res. 56, 95112.
Chiodini G., Cioni R., Frullani A., Guidi M., Marini L., Prati F., and
Raco B. (1996a) Fluid geochemistry of Montserrat Island, West
Indies. Bull. Volcanol. 58, 380392.
Chiodini G., Frondini F., and Raco B. (1996b) Diffuse emission of CO
2
from the Fossa crater, Vulcano Island. Bull. Volcanol. 58, 4150.
Chiodini G., Allard P., Caliro S., and Parello F. (2000)
18
O exchange
between steam and carbon dioxide in volcanic and hydrothermal
gases: Isotopic and genetic implications. Geochim. Cosmochim. Acta
64, 24792488.
Chiodini G., Cardellini C., Frondini F., Granieri D., Marini L., and
Ventura G. (2001) CO
2
degassing and energy release at Solfatara
Volcano, Campi Flegrei, Italy. J. Geophys. Res. (in press)
Christenson B. W. and Wood C. P. (1993) Evolution of a vent-hosted
hydrothermal system beneath Ruapehu Crater Lake, New Zealand.
Bull. Volcanol. 55, 547565.
Cioni R., Santacroce R., and Sbrana A. (1999) Pyroclastic deposits as
a guide for reconstructing the multi-stage evolution of the Somma-
Vesuvius caldera. Bull. Volcanol. 60, 207222.
Crocetti S. (1996) Levoluzione vesuviana del 1631: Studio dei litici e
reazioni termometasomatiche ai margini della camera magmatica.
Thesis, Pisa University.
DAmore F. and Panichi C. (1980) Evaluation of deep temperature of
hydrothermal systems by a new gas-geothermometer. Geochim. Cos-
mochim. Acta 44, 549556.
Deines P. and Gold D. P. (1973) The isotopic composition of carbona-
tite and kimberlite carbonates and their bearing on the isotopic
composition of deep-seated carbon. Geochim. Cosmochim. Acta 37,
17091733.
Delmelle P. and Bernard A. (1994) Geochemistry, mineralogy, and
chemical modeling of the acid crater lake of Kawah Ijen Volcano,
Indonesia. Geochim. Cosmochim. Acta 58, 24452460.
Dittman G. L. (1977) Calculation of brine properties. Lawrence Liv-
ermore Laboratory. Report UCID-17406.
Drummond S. E. (1981) Boiling and mixing of hydrothermal uids:
Chemical effects on mineral precipitation. Ph.D. thesis, Pennsylva-
nia State University.
Ellis A. J. (1979) Explored geothermal systems. In Geochemistry of
Hydrothermal Ore Deposits, 2nd Edition (ed. H. L. Barnes), pp.
632683, John Wiley & Sons, New York.
Ellis A. J. and Golding R. M. (1963) The solubility of carbon dioxide
above 100C in water and in sodium chloride solutions. Am. J. Sci.
261, 4760.
Ellis A. J. and Mahon W. A. J. (1977) Chemistry and Geothermal
Systems, Academic Press, New York.
Fischer T. P., Sturchio N. C., Stix J., Arehart G. B., Counce D., and
Williams S. N. (1997) The chemical and isotopic composition of
fumarolic gases and spring discharges from Galeras Volcano, Co-
lombia. J. Volcanol. Geoth. Res. 77, 229253.
Fournier R. O. (1987) Conceptual models of brine evolution in mag-
matic-hydrothermal systems. U.S. Geological Survey Professional
Paper 1350, 14871506.
Friedman I. and ONeil J. R. (1977) Compilation of stable isotope
fractionation factors of geochemical interest. U. S. Geological Sur-
vey Professional Paper 440, 44.
Giggenbach W. F. (1975a) A simple method for the collection and
analysis of volcanic gas samples. Bull. Volcanol. 39, 132145.
Giggenbach W. F. (1975b) Variations in the carbon, sulfur and chlorine
contents of volcanic gas discharges from White Islands, New Zea-
land. Bull. Volcanol. 39, 1527.
Giggenbach W. F. (1975c) The chemistry of Crater Lake, Mt. Ruapehu
(New Zealand) during and after the 1971 active period. New Zeal. J.
Sci. 17, 3345.
Giggenbach W. F. (1980) Geothermal gas equilibria. Geochim. Cos-
mochim. Acta 44, 20212032.
Giggenbach W. F. (1984) Mass transfer in hydrothermal alterations
systems. Geochim. Cosmochim. Acta 48, 26932711.
Giggenbach W. F. (1987) Redox processes governing the chemistry of
fumarolic gas discharges from White Island, New Zeland. Appl.
Geochem. 2, 143161.
Giggenbach W. F. (1988) Geothermal solute equilibria. Derivation of
Na-K-Mg-Ca geoindicators. Geochim. Cosmochim. Acta 52, 2749
2765.
Giggenbach W. F. (1991a) Chemical techniques in geothermal explo-
ration. In Application of Geochemistry in Geothermal Reservoir
Development. (coordinator F. DAmore), pp. 119144. UNITAR,
New York.
Giggenbach W. F. (1991b) Isotopic composition of geothermal water
and steam discharges. In Application of Geochemistry in Geothermal
Reservoir Development. (coordinator F. DAmore), pp. 253273.
UNITAR, New York.
Giggenbach W. F. (1992a) Isotopic shifts in waters from geothermal
and volcanic systems along convergent plate boundaries and their
origin. Earth Planet. Sci. Lett. 113, 495510.
Giggenbach W. F. (1992b) The composition of gases in geothermal and
volcanic systems as a function of tectonic setting. In Proceedings of
the Seventh International Symposium on Water-Rock Interaction, pp.
873878. Park City, Utah.
Giggenbach W. F. (1993) Redox control of gas compositions in Phil-
ippine volcanic-hydrothermal systems. Geothermics 22, 575587.
Giggenbach W. F. (1996) Chemical composition of volcanic gases. In
Monitoring and Mitigation of Volcano Hazards (ed. R. Scarpa and
R. I. Tilling), pp. 221256, Springer, Berlin.
Giggenbach W. F. (1997a) The origin and evolution of uids in
magmatic-hydrothermal systems. In Geochemistry of Hydrothermal
Ore Deposits, 3rd Edition (ed. H. L. Barnes), pp. 737796, John
Wiley & Sons, New York.
Giggenbach W. F. (1997b) Relative importance of thermodynamic and
kinetic processes in governing the chemical and isotopic composi-
tion of carbon gases in high-heatow sedimentary basins. Geochim.
Cosmochim. Acta 61, 37633785.
Giggenbach W. F. and Goguel R. L. (1989) Collection and analysis of
geothermal and volcanic water and gas discharges. Report No. CD.
2401, Department of Scientic and Industrial Research, Chemistry
Division, Petone, New Zealand.
Giggenbach W. F. and Stewart M. K. (1982) Processes controlling the
isotopic composition of steam and water discharges from steam
vents and steam-heated pools in geothermal areas. Geothermics 11,
7180.
Giggenbach W. F., Garcia N. P., Londono A. C., Rodriguez L. V.,
Rojas N. G., and Calvache M. L. V. (1990) The chemistry of
fumarolic vapor and thermal spring discharges from the Nevado del
Ruiz volcanic-magmatic-hydrothermal system, Colombia. J. Volca-
nol. Geoth. Res. 42, 1339.
Guglielminetti M. (1986) Mofete geothermal eld. Geothermics 15,
781790.
Henley R. W., Truesdell A. H., Barton Jr. P. B., and Whitney J. A.
(1984) Fluid-mineral equilibria in hydrothermal systems. Reviews in
Economic Geology 1, 267.
Holloway J. R. and Blank J. G. (1994) Application of experimental
results to C-O-H species in natural melts. In Volatiles in Magmas
(ed. M. R. Carroll and J. R. Holloway), Rev. Mineral. 30, 187230.
Horita J., Cole D. R., and Wesolowski D. J. (1995) The activity-
composition relationship of oxygen and hydrogen isotopes in aque-
ous salt solutions: III. Vapor-liquid water equilibration of NaCl
solutions to 350C. Geochim. Cosmochim. Acta 59, 11391151.
Imbo` G. (1947) Considerazioni ed osservazioni comprovanti che
leruzione del 1944 fu terminale. Boll. Soc. Natural. 56, 113,
Napoli.
Imbo` G. (1950) Manifestazioni effusive subterminali della primavera
del 1942 e fenomeni termici attuali interessanti la medesima zona del
versante meridionale vesuviano. Rend. Acc. Sc. Fis. Mat., s. 4, 17,
112, Napoli.
Imbo` G., Casertano L., and Bonasia V. (1964) Attivita` vesuviana negli
ultimi anni dellattuale periodo di riposo. Annali Oss. Ves., s. 6, 6,
189204, Napoli.
Joron J. L., Metrich N., Rosi M., Santacroce R., and Sbrana A. (1987)
Chemistry and petrography. In Somma-Vesuvius (ed. R. Santacroce),
CNR Quaderni de La Ricerca Scientica, CNR, Roma 114-8, 105
174.
Kasai K., Sakagawa Y., Komatsu R., Sasaki M., Akaku K., and Uchida
T. (1998) The origin of hypersaline liquid in the Quaternary Kak-
konda granite, sampled from well WD-1a, Kakkonda geothermal
system, Japan. Geothermics 27, 631645.
Keenan J. H., Keyes F. G., Hill P. G., and Moore J. G. (1969) Steam
tables. Thermodynamic Properties of Water Including Vapor, Liq-
uid, and Solid Phases, pp. 162, John Wiley & Sons, New York.
Keith M. L. and Weber J. N. (1964) Isotopic composition and envi-
ronmental classication of selected limestones and fossils. Geochim.
Cosmochim. Acta 28, 17871816.
Knight C. L. and Bodnar R. J. (1989) Synthetic uid inclusions: IX.
Critical properties of NaCl-H
2
O solutions. Geochim. Cosmochim.
Acta 53, 38.
Kozintseva T. N. (1964) Solubility of hydrogen sulphide in water at
elevated temperatures. Geochem. Intl. 750756.
Kozintseva T. N. (1965) Solubility of hydrogen sulphide in water and
in salt solutions at elevated temperatures. In Geochemical Investi-
gation in the Field of Higher Temperatures and Pressures (ed. N. I.
Khitarov), pp. 121134, Nauka, Moscow.
Kyser T. K. (1986) Stable isotope variations in the mantle. In Stable
Isotopes in High Temperature Geological Processes (ed. J. W.
Valley, H. P. Taylor, Jr., and J. R. ONeil) Rev. Mineral. 16,
141164.
Marini L., Agostini A., Cioni R., Guidi M., and Leon O. (1991) Guagua
Pichincha volcano, Ecuador: Fluid geochemistry in volcanic surveil-
lance. J. Volcanol. Geotherm. Res. 46, 2135.
Matsuhisa Y., Goldsmith J. R., and Clayton R. N. (1979) Oxygen
isotope fractionation in the systen quartz-albite-anorthite-water.
Geochim. Cosmochim. Acta 43, 11311140.
Matsuo S., Suzuki M., and Mizutani Y. (1978) Nitrogen to agron ratio
in volcanic gases. Adv. Earth Planet. Sci. 3, 1725.
Mattey D. P., Taylor W. R., Green D. H., and Pillinger C. T. (1990)
Carbon isotopic fractionation between CO2 vapor, silicate and car-
bonate melts: An experimental study to 30 kbar. Contrib. Mineral.
Petrol. 104, 492505.
Murray C. and Cubicciotti D. (1983) Thermodynamics of aqueous
sulfur species to 300C and potential-pH diagrams. J. Electrochem.
Soc. 38, 863869.
Naumov G. B., Ryzhenko B. N., and Khodakovsky I. L. (1974)
Handbook of Thermodynamic Data, Report No. USGS-WRD-74-
001. U.S. Geological Survey. Water Resources Division, Menlo
Park, California.
Nazzaro A. (1997) Il Vesuvio (storia eruttiva e teorie vulcanologiche).
1374, Liguori Editore, Napoli.
Ohmoto H. and Goldhaber M. B. (1997) Sulfur and carbon isotopes. In
Geochemistry of Hydrothermal Ore Deposits, 3rd Edition (ed. H. L.
Barnes), pp. 517612, John Wiley & Sons, New York.
Parascandola A. (1951) I minerali del Vesuvio nella eruzione del marzo
1944 e quelli formati durante lattuale periodo di riposo. Boll. Soc.
Geol. It. 70(1), 523526.
Parascandola A. (1959) Notizie vesuviane. il Vesuvio dal marzo 1948
al dicembre 1958. Boll. Soc. Natural. 68, 1184, 4 gg., 20 tavv.,
Napoli.
Parascandola A. (1960) Notizie vesuviane. il Vesuvio dal gennaio 1959
al dicembre 1960. Boll. Soc. Natural. 69, 263298, 10 tavv., Napoli.
Poorter R. P. E., Varekamp J. C., van Bergen M. J., Kreulen B.,
Siriwana T., Vrool P. Z., and Wirakusumah A. D. (1989) The Sirung
volcanic boiling spring: An extreme chloride-rich, acid brine on
Pantar (Lesser Sunda Islands, Indonesia). Chem. Geol. 76, 215228.
Principe C., Brocchini D., and Perillo M. (1999) The Cognoli di
Trocchia volcano and Monte Somma growth. Plinius 22, 316317.
Principe C., Rosi M., Santacroce R., and Sbrana A. (1987) Explanatory
notes to the geological map. In Somma-Vesuvius (ed. R. Santacroce),
CNR Quaderni de La Ricerca Scientica, CNR, Roma, 114-8, 11
51.
Reed M. H. (1997) Hydrothermal alteration and its relationship to ore
uid composition. In Geochemistry of Hydrothermal Ore Deposits,
3rd Edition (ed. H. L. Barnes), pp. 517611, John Wiley & Sons,
New York.
Reyes A. G., Giggenbach W. F., Saleras J. R. M., Salonga N. D., and
Vergara M. C. (1993) Petrology and geochemistry of Alto Peak, a
vapor cored hydrothermal system, Leyte province, Philippines. Geo-
thermics 22, 479519.
Richet P., Bottinga Y., and Javoy M. (1977) A review of H, C, N, O,
S and Cl stable isotope fractionation among gaseous molecules.
Annu. Rev. Earth Planet. Sci. Lett. 5, 65110.
Rosi M., Principe C., and Vecci R. (1993) The 1631 eruption of
Vesuvius reconstructed from the review of chronicles and study of
deposits. J. Volcanol. Geotherm. Res. 58, 151182.
Rowe Jr. G. L., Ohsawa S., Takano B., Brantley S. L., Fernandez J. F.,
and Barquero J. (1992) Using crater lake chemistry to predict vol-
canic activity at Poas volcano, Costa Rica. Bull. Volcanol. 54,
494503.
Russo, M. (1995) Sorveglianza geochimica allOsservatorio Vesuviano
nel 1994: Campi Flegrei e Vesuvio. Giornate Poster sulle Ricerche
del Gruppo Geomineralogico, Atti V Conf. Sci. Ann. sulle attivita` di
ricerca dei Dipartimenti, 235236, 68 Aprile, Napoli.
Russo M. and Langella A. (1996) Ricerche in corso sui minerali
presenti alle fumarole del Vesuvio. Con. Sc. Ann. del G.N.V. - CNR
e Oss. Vesuv., 2729 marzo, Napoli.
Russo M. (1997a) Sorveglianza geochimica: Vesuvio. Rendiconto
sullattivita` di sorvglianza 1996. Osservatorio Vesuviano, 4546,
internal report, febbraio 1997, Napoli.
Russo M. (1997b) Nuovi ritrovamenti di minerali al Vesuvio: Alotri-
chite e Pickeringite. GMGN Notizie. 1, 11, Napoli.
Sano Y., Gamo T., and Williams S. N. (1997) Secular variations of
helium and carbon isotopes at Galeras volcano, Colombia. J. Vol-
canol. Geother. Res. 77, 255265.
Santacroce R. (1983) A general model for the behaviour of the Somma-
Vesuvius volcanic complex. J. Volcanol. Geother. Res. 17, 237248.
Sigurdsson H. (1977) Chemistry of the crater lake during the 197172
Soufrie`re eruption. J. Volcanol. Geotherm. Res. 2, 165186.
Sigurdsson H., Carey S. N., Cornell W., and Pescatore T. (1985) The
eruption of Vesuvius in A.D. 79. Natl. Geogr. Res. 1, 332387.
Stull D. R., Westrum E. F., and Sinke G. G. (1969) The Chemical
Thermodynamics of Organic Compounds, John Wiley & Sons, New
York.
Suleimenov O. M. and Krupp R. E. (1994) Solubility of hydrogen
sulde in pure water and in NaCl solutions, from 20 to 320C and at
saturation pressures. Geochim. Cosmochim. Acta 58, 24332444.
Takano B. and Watanuki K. (1990) Monitoring of volcanic eruptions at
Yugama crater lake by aqueous sulfur oxyanions. J. Volcanol. Geo-
therm. Res. 40, 7187.
Tanger IV J. C. and Pitzer K. S. (1989) Thermodynamics of NaCl-H
2
O:
A new equation of state for the near-critical region and comparison
with other equations for adjoining regions. Geochim. Cosmochim.
Acta 53, 973987.
Tedesco D. (1996) Chemical and isotopic investigations of fumarolic
gases from Ischia island (southern Italy): Evidences of magmatic and
crustal contribution. J. Volcanol. Geotherm. Res. 74, 233242.
Tedesco D. (1997) Systematic variations in the
3
He/
4
He ratio and
carbon of fumarolic uids from active volcanic areas in Italy: Evi-
dence for radiogenic
4
He and crustal carbon addition by the sub-
ducting African plate? Earth Planet. Sci. Lett. 151, 255269.
Tedesco D., Nagao K., and Scarsi P. (1998) Noble gas isotopic ratios
from historical lavas and fumaroles at Mount Vesuvius (southern
Italy): Constraints for current and future volcanic activity. Earth
Planet. Sci. Lett. 164, 6178.
Tedesco D. and Scarsi P. (1999) Reply to Helium isotopes in historical
lavas from Mount Vesuvius, a comment on Noble gas isotopic
ratios from historical lavas and fumaroles at Mount Vesuvius by D.
Tedesco et al. Earth Planet. Sci. Lett. 174, 245246.
Thompson G. (1798). Sur la nature des marbres vomis par le Vesuve et
sur letendue possible des inuences volcaniques. Bibl. Br. Lat. 7,
4085.
Truesdell A. H. (1991) Origins of acid uids in geothermal reservoirs.
Geotherm. Res. Counc. Trans. 15, 289296.
Valley J. W. (1986) Stable isotope geochemistry of metamorphic rocks.
In Stable Isotopes in High Temperature Geological Processes (ed.
J. W. Valley, H. P. Taylor, Jr., and J. R. ONeil) Rev. Mineral. 16,
445489.
Ventura G. and Vilardo G. (1999) Seismic-based estimate of hydraulic
parameters at Vesuvius volcano. Geophys. Res. Lett. 26, 887890.
Wilhelm E., Battino R., and Wilcock R. J. (1977) Low-pressure solu-
bility of gases in liquid water. Chem. Rev. 77, 219262.

Paper 1

Cargado por

Información del documento

Derechos de autor

Formatos disponibles

Compartir este documento

Compartir o incrustar documentos

Opciones para compartir

¿Le pareció útil este documento?

¿Este contenido es inapropiado?

Copyright:

Formatos disponibles

Paper 1

Cargado por

Copyright:

Formatos disponibles

PII S0016-7037(01)00583-X

Geochemical evidence for the existence of high-temperature hydrothermal brines at

0.9, corresponding to T 275C (R 0.997):

values. These discrepancies might be due to experimental

and T(C) for a specied NaCl concentration, log B

values. Assuming that these equations also

equations (Table 3).

También podría gustarte