Chemical and Isotopic Compositions of The Shallow Groundwater System of Vulcano Island, Aeolian Archipelago, Italy: An Update

Boschetti T, Cortecci G, Bolognesi L (2003) - Chemical and isotopic compositions of the shallow groundwater system of Vulcano Island, Aeolian
Archipelago, Italy: an update. GeoActa 2, 1-34
Chemical and isotopic compositions of the shallow groundwater system of

Vulcano Island, Aeolian Archipelago, Italy: an update
by
Tiziano Boschetti1, Gianni Cortecci2* and Luca Bolognesi3
Dipartimento di Scienze della Terra, University of Parma, Parco Area delle Scienze 157a, I43100 Parma, Italy
Dipartimento di Scienze della Terra e Geologico-Ambientali, University of Bologna, Piazza

San Donato 1, I-40126 Bologna, Italy.
3
CNR- Istituto per i Processi Chimico-Fisici, Via G. Moruzzi 1, I-56124 Pisa, Italy.
*Corresponding author: tel. +39-051-2094944; fax: +39-051-2094904

E-mail address: cortecci@geomin.unibo.it
erratum/corrigendum version (2014-12-22 update) for info: Tiziano Boschetti (work@tizianoboschetti.com)
Abstract
Cold and thermal waters were sampled on Vulcano Island from shallow wells in June 1995,
June 1996 and January-February 1997; additional samples refer to a thermal spring, meteoric
water from domestic cisterns and local seawater.
The chemical and isotopic (hydrogen, oxygen, tritium and strontium in water, and sulfur
and oxygen in sulfate ions) compositions measured in the samples showed that: 1) the shallow
hydrothermal system is formed by the mixing of waters of meteoric origin and various ages
with crater-type fumarolic steam and gases (phreato-volcanic waters), with water rising from
the geothermal reservoir expected to exist at depth (sulfate-chloride waters), and with steam
and gases released from the geothermal reservoir itself (steam-heated waters); 2) a major
seawater contribution occurs only in water from a well exploited in the Togo-Togo Camping,
that is located very close to the shoreline; 3) dissolved sulfate mostly derives from oxidation
of fumarolic/magmatic sulfur species, with minor sporadic contributions from seawater or
from dissolution of secondary anhydrite; and 4) major changes in the chemical and isotopic
compositions of the bulk groundwater system were not observed during the study period, and
the appreciable variations in waters from few wells may be interpreted as due to changes in
the mixing proportions of the endmembers or to direct rainwater dilution.
Based on the present study and previous ones from literature, an updated geochemical
model is proposed for the groundwaters system at Vulcano and its relations with the crater
and beach fumarolic fluids.
Keywords: Vulcano Island; groundwater system; oxygen and hydrogen isotopes; tritium;
sulfur isotopes; strontium isotopes.
1. Introduction
Vulcano Island belongs to the Aeolian Islands, a volcanic archipelago located in the
southern Tyrrhenian Sea, off the northern coast of Sicily (Fig. 1). Tectonic, structural
evolution and caldera formation of Vulcano are described in Gabbianelli et al. (1991) and
Ventura (1994). The magmatic activity of Vulcano began during the Upper Pleistocene and
generated a variety of deposits from leucitic tephrites to high-potassic trachytes; alkalirhyolitic obsidian erupted in historic times (Keller, 1980). The last eruption took place during
1888-1890; after that event, the island was and is the site of fumarolic and seismic activities
only.
High-temperature fluids are discharging from fumaroles on the rim of the active crater of
Vulcano, named Gran Cratere or La Fossa (392 m a.s.l.), and mainly consist of H2O;
major components of the dry fraction are CO2, SO2, H2S, HCl, HF and N2. Low-temperature
fumaroles at Porto di Levante beach release CO2, H2S and N2 as major components of the
dry fraction. The origin of fumarolic fluids was debated in many papers (e.g. Cortecci et al.,
2001 and references therein).
Geothermal fluids at Vulcano were encountered only by the VU2/bis borehole (236 m deep;
Fig. 1) during 1952-1953. Aquifers were found at 7-14 m (T = 101C), 90-110 (T = 136C)
and 185-236 m (194-198C). Other boreholes (VP-1, 1000 m deep; IV-1, 2050 m deep)
drilled in the 1980s close to the volcanic cone were unproductive (Silvano, 1985; Gioncada
and Sbrana, 1991). Hydrothermal minerals found in these wells, including anhydrite and
pyrite, were described by Sommaruga (1984) and Fulignati et al., (1996 and 1998).
Several models were proposed to explain the genesis of the thermal waters in the shallow
wells located in the Vulcano Porto plain to the northwest of Gran Cratere (see Cortecci et al.,
2001 for a review). The piezometric level in the southern part of the plain is about 2 m a.s.l.
and decreases to sea level toward the north, with a radial flow of meteoric groundwater from
the volcanic cone to the sea (Bolognesi, 1997). Some information on the bottom depth of the
studied wells are reported in Cortecci et al. (2001).
Almost all the authors agree that meteoric water is the main component of the shallow
groundwater system of Vulcano, with local contributions from condensates of magmatic
origin. Steam, gases and heat from the geothermal reservoir produce the steam-heated waters
located at the foot of the volcanic cone (Bolognesi and DAmore, 1993; Cortecci et al., 2001).
Bolognesi and DAmore (1993) proposed that the geothermal reservoir mainly consists of
magmatic condensate evolved via water-rock reaction; the composition of the geothermal
water varies with time (Bolognesi, 2000) depending on new earthquake-induced contributions
from the magmatic source to the reservoir and subsequent water-rock interactions. The only
known major upflow of geothermal water from the reservoir occurs in well W2 (Fig. 1), that
supplies water to the camp-site Camping Sicilia (Bolognesi and DAmore, 1993; Bolognesi,
1997 and 2000; Capasso et al, 1999; Cortecci et al., 2001); in this well, the geothermal
endmember mixes with a steam-heated component of meteoric origin (Bolognesi and
DAmore, 1993). Temporary changes in W2 water from geothermal to steam-heated character
were related to stress build-up prior to seismic events and stress reduction afterwards
(Bolognesi, 1997). Direct contribution from magmatic gases to a few shallow groundwaters
was also proposed to occur (Aiuppa et al., 2000; Cortecci et al., 2001). According to Capasso
et al. (1999), rainwater that contributes to the refilling of the shallow waters system is drained
in the subsoil of the La Fossa caldera and the Piano caldera, the latter being located in the
southern part of the island where it reaches an elevation of 400 m a.s.l.. The contribution from
the Piano caldera should be predominant with respect to that from the La Fossa caldera
(Favara et al., 1997).
According to Bolognesi and DAmore (1993) and Cortecci et al. (2001), the involvement of
seawater as contributor to most shallow groundwaters of Vulcano Porto should be excluded.
In the present study, new chemical and isotopic (hydrogen, oxygen tritium and strontium in
water, and sulfur and oxygen in sulfate ions) results on cold and thermal groundwaters from
Vulcano Island are reported and discussed. The chemical and isotopic compositions of
samples collected in June 1995 (Cortecci et al., 2001) are included in the study for
comparison. The main aim of the work was to increase the number of data with time, in order
to check the geochemical variability of the groundwater (phreatic) system and to provide
further constraints on the major sources of water and chemicals. A preliminary discussion of
the whole data set is reported in Cortecci and Boschetti (2001).
2. Sampling and analytical procedures

Water samples were collected in June 1995, June 1996 and January-February 1997 from 22
to 32 wells located in the Vulcano Porto plain (Fig. 1). Sampled wells were numbered
following Bolognesi and DAmore (1993), Bolognesi (1997 and 2000) and Cortecci et al.
(2001). Sampling was carried out using a stainless steel sampler lowered to well bottom or by
an electric pump. Additional samples of local seawater, rainwater from domestic cisterns and
thermal springs (from Vulcano and Lipari islands; see inset in Fig. 1) were also collected.
Temperature, pH, electrical conductivity and carbonate alkalinity were measured in the
field. Sodium, potassium, calcium and magnesium were determined by atomic absorption
spectrometry following the procedures proposed by Bencini (1977); the relative accuracy of
these methods is in the range of 3 to 5%. Chloride was analysed by Volhards volumetric
method and sulfate by turbidimetry/spectrophotometry with relative accuracies of 7 to
10%. Boric acid was determined by colorimetry using azomethine-H reagent (Bencini,
1985), with an accuracy of 3%. Bromide was analysed by ion chromatography, with an
accuracy of 10-15%.
The concentration of silicic acid was measured by spectrophotometry after filtration through
0.45 Millipore and dilution in the field; in laboratory, water was reacted with ammonium
molybdate and concentration measured with an accuracy of 3-5%.
The 2H and 18O of waters are determined, respectively, by reaction of water with metallic
Zn at 500C (Kendall and Coplen, 1985) and by equilibrating CO2 with water at 25C
(Epstein and Mayeda, 1953), then analysing H2 and CO2 in the mass-spectrometer. The results
are relative to the V.SMOW standard. Duplicate preparations and analyses agreed within
1 for hydrogen and 0.1 for oxygen. The tritium (3H) measurements were carried out
using the method of Cameron (1967). The concentration is reported in tritium units (TU), that
is the number of T atoms relative to 1018 H atoms. The analytical accuracy was within 1 TU.
Aliquots of waters were sampled for sulfur and oxygen isotopic analyses of dissolved
sulfate. In the field, a spatula pit of calomel (Hg2Cl2) was added to all samples in order to stop
the sulfate-reducing bacteria. In laboratory, the water samples were filtered through a 0.45 m
Millipore filter. Aqueous sulfate was precipitated as barium sulfate, and then thermally
decomposed to yield sulfur dioxide for the mass-spectrometric sulfur isotope analysis
(Yanagisawa and Sakai, 1983) or reacted with graphite at about 1000C (and using Pt to
oxidize CO) to yield CO2 for the mass-spectrometric oxygen isotope analysis (Rafter, 1967).
The results are expressed in terms of 34S and 18O values, in per mill, relative to Canyon
Diablo Troilite (CDT) standard for sulfur and V-SMOW standard for oxygen. Duplicate
preparations and analyses agreed within 0.2 for sulfur and 0.3 for oxygen.
Sr isotopic composition was determined in 1-3 g water evaporated to dryness and
redissolved in 2.5 M HCl. Then, Sr was extracted from the hydrochloric solution by
conventional cation exchange technique. The blank for the whole procedure was of 0.7 ng Sr.
The
87
Sr/86Sr ratio was measured by means of a Finnigan MAT 262 mass spectrometer, and
normalized to a
86
Sr/88Sr value of 0.1194 in natural strontium. Repeated analyses of NIST
SRM 987 standard during the period of interest yielded an average
87
Sr/86Sr value of
0.710224 0.000006 (n =26).
3. Results and discussion

The results from the chemical and isotopic analyses are reported in Tables 1 to 3. To permit
a direct comparison, the analytical data from our 1995 sampling are reported along with those
from the more recent samplings in 1996 and 1997. Let us begin with the observed timevariation of temperature in the studied waters.
3.1 Temporal changes in the temperature values

The temperature of water in a number of wells even greatly varied depending on sampling
time. Variations were up to 11C in the shallow waters and up to 7C in the steam-heated
waters. In sulfate-chloride waters, temperature did not vary more than 3C. Large temperature
variations in individual wells are reported also in previous studies (e.g. Capasso et al., 1991
and references therein).
Both lower and higher temperature values were observed in June 1996 with respect to June
1995. Positive variations were not higher than 3C, whereas negative variations were larger
with drops in the range 1 to 8C. Substantial drops of 5 to 8C in W17, W24, W31 and W32
wells were accompanied by a considerable decrease of TDS and lower 18O and 2H values in
W17 well or by nearly constant chemical and isotopic compositions in W31, W32 and W24
wells. These features are difficult to be punctually explained, as many factors are involved
including exploitation of the wells by the population. However, dilution effects should be
excluded in W17 well due to dry weather reasons, whereas a lowering of the volcanomagmatic component may be invoked.
All but one temperature variations observed in January-February 1997 with respect to June
1996 are negative, with differences of 3 to 11C. On the contrary, temperature rose by 11C
in the water W33, passing from 28 to 39C. In spite of a slightly lower salinity, boron and
bicarbonate concentrations in this well increased from 22 to 48 mg/kg (as H3BO3) and from
340 to 430 mg/kg, respectively. This behaviour suggests enhanced contribution to the aquifer
of hot deep fluids before the sampling date, even if the isotopic composition of water kept
nearly constant. Negative temperature variations were notable in some wells, but univocal
relations are not found with chemical and isotopic variables. In keeping with the winter
season, only the drops of 10-11C observed in W20 and W34 wells can be simply attributed
to dilution effects by infiltrating rain. By these effects, all ions and heavy isotopes are largely
depleted in water W20, whereas comparable isotopic compositions but by an order of
magnitude lower salinity are observed in water W34. In the latter, the high Br content in 1996
(36 mg/kg) compared to that in 1997 (14 mg/kg) testifies the increased proportion of the
meteoric component relative to the marine component of the water feeding this well.
3.2 Chemical results

The major hydrochemistry basically confirms the results of recent studies (Bolognesi and
DAmore, 1993; Aiuppa et al., 2000; Cortecci et al., 2001; Capasso et al., 2001). Three
groups of groundwaters can be distinguished in terms of HCO3-, SO42- and Cl- relative
concentrations (Fig. 2):
1. Shallow groundwaters (W1, W3, W3b, W5, W5b, W9, W12, W13, W14, W16, W17,
W18, W19, W20, W21, W22, W23, W25, W26, W27, W29, W30, W31, W32, W33, W33b,
W34; T= 20 to 48C in June-July 1995-96, and 14 to 44C in January-February 1997), which
hereafter will be denoted as SGRW; see Cortecci et al., 2001). These waters can be
subdivided in bicarbonate-type (W1, W3, W5, W13, W14, W16, W19, W21, W23, W27,
W29, W30, W31; W33b; TDS = 335 to 2,822 mg/kg), which represent meteoric recharge or
waters affected by uprising anomalous CO2 degassing; sulfate/chloride-type (W3b, W5b, W9,
W12, W17, W18, W22, W26, W32; TDS = 967 to 3431 mg/kg), which interact directly with
uprising volcano-magmatic gases; and chloride-type (W34), whose high TDS (9,050 mg/kg in
1997 and 24,017 mg/kg in 1996) is due to lateral seawater contribution. Water W20 changed
from sulfate/chloride in 1995 (TDS = 4,432 mg/kg) to chloride in 1996 (7,201 mg/kg) to
bicarbonate in 1997 (994 mg/kg). Similarly, water W33 was sulfate/chloride in 1996 (TDS =
1,780 mg/kg) and bicarbonate in 1997 (1,576 mg/kg).
2. Sulfate-chloride groundwaters (W0, W2, W4; hereafter reported also as geothermal and
denoted as GGRW), characterized by high temperature (49 to 75C) and high salinity (3,775
to 8,839 mg/kg). The thermal spring water SF (Sorgente Federico; T = 44C; TDS = 7,422
mg/kg) belongs to this group. These waters fit the compositional field of local volcanic
waters, and should be fed by a geothermal reservoir at 200-300 m depth, with temperature of
200-250C, and then mixed with meteoric water (Bolognesi and DAmore, 1993; Cortecci et
al., 2001; Cortecci and Boschetti, 2001). According to these authors, the geothermal fluid
derives from condensation of SO2-HCl rich magmatic fluids like the crater-type fumarolic
ones. These sulfate-chloride waters are located at the base of the volcanic cone, and the
notable chemical (and isotopic) variations, showed especially by water W2 from the 1980s,
may attributed to variable mixing between the deep geothermal component and the shallow
water component, or to temporal fluctuations of the chemical composition (and fluxes) of the
magmatic fluids feeding the geothermal aquifer at depth. Due to water-rock interaction
effects, the pH of these waters is nearly neutral with values from 6.3 to 7.8.
Acidic sulfate-choloride springs (named Pozza and Istmo; not sampled in this study)
outflow at Vulcano from the Porto di Levante beach along with low-temperature fumaroles.
These springs, fumaroles and other submarine thermal springs lie on a N-S structural
lineament which extends from La Fossa crater to Vulcanello (e.g. Sedwick and Stben, 1996).
Springs are basically fed by local volcanic water, with some contributions of seawater and
steam-heated water; the temperature of the Pozza spring was found to be largely variable with
time in the range 20 to 90C (Fontes et al., 1993; Amend et al., 1998; Aiuppa et al., 2000).
3. Steam-heated groundwaters (W6, W7, W8, W15, W24, W28, W29b; hereafter denoted as
SHGRW), i.e. groundwaters heated by H2S or CO2 rich vapours released from deep boiling
water. Water W29b is included in this group, following the Aiuppa et al.s (2000) study
relative to samples collected in 1997. They are considerably enriched in SO42- relative to Cl-,
with TDS values of 2,005 to 4,043 mg/kg, and their temperatures are in the range 21 to 57C.
The chloride contents in these waters vary between 134 to 353 mg/kg, that is unusual for this
kind of waters. These concentration values are unusual for steam-heated waters. At Vulcano,
however, shallow and steam-heated groundwaters interact with rocks that may be quite rich in
chloride as observed in rhyolites (1150 to 3000 ppm; Goff and McMurtry, 2000).
As far as the cation composition is concerned, the great majority of waters are alkalienriched, with some SGRW (W19 and W25) and W29b) and SHGRW (W8, W24 and W29b)
being calcium-enriched. Wells W8 and W24 are located at the base of the Forgia Vecchia
slope, and may exploit aquifers fed by meteoric water flowing from the volcanic cone and
enriched in calcium and sulfate by dissolution of supergenic gypsum occurrences (see forward
section on sulfur isotopes). The Ca2+ to SO42- molar ratio in wells W8 and W24 are close to
unit with values ranging from 0.8 to 1.1. In well W25, the Ca2+/SO42- varied from 0.8 in 1995
to 1.5 in 1996 to 4.2 in 1997, this trend suggesting increasing contribution of shallow water
highly enriched in Ca2+ relative to SO42- like that exploited by the W19 well (molar
Ca2+/SO42- ratio of 11). This component may be present also in the W29b well, thus
explaining the observed Ca2+/SO42- molar ratio of 1.3. Solubility reasons do not preclude for
the majority of studied waters dissolution of gypsum or anhydrite. Only hot waters W8, W24,
W4 (96) and W7(96) are definitively saturated or very near to saturation relative to these
minerals (Boschetti, 1998).
All groups of waters are far from chemical equilibrium with host rocks both for anions (Fig.
2) and cations (Fig. 3), i.e. all analysed waters are immature. The cation compositions lie
between the isochemical rock dissolution line and the incongruent rock dissolution curve,
testifying the great control of both processes on the chemical composition of the studied
waters. Shallow groundwater W19 is the most immature one, and the sulfate-chloride W0 the
less immature one.
A sodium-chloride plot can reveal the waters contaminated by seawater. In Fig. 4, only
groundwater W34(96) appear to be significantly affected by seawater. The contribution of
seawater to this water calculated from the chloride contents results to be about 55% and 20%
in 1996 and 1997, respectively. Similar contributions are calculated taking into account Na
and Mg and to a lesser extent also SO4. However, we cannot exclude that seawater may have
mixed with another water more saline than W19. Along with the freshwater-seawater mixing
trend, other two main trends can be envisaged from Fig. 4, i.e. shallow groundwaters SGWR
couple with some steam-heated waters with minor sodium (W8, W24 samples), and sulfatechloride waters GGWR are tied with more concentrated SHGWR waters.
3.2.1 Classification of the waters by the statistical approach

The Principal Component Analysis (PCA) was applied to the studied waters. This
multivariate analysis reduces the dimensionality of the data set, while retaining the
information present in the data. Previous applications to hydrochemical data (e.g. Razack and
Dazy, 1990; Gler et al., 2002) include geothermal systems (Nicholson, 1993).
The data set of Vulcano refers to eighty samples, and fifteen variables both chemical and
isotopic, i.e. tC, Ca, Na, K, Mg, Cl, SO4, HCO3, H3BO3, Br, SiO2, 18O(H2O), 2H(H2O) and
34S(SO4), were considered in the statistical treatment. The data set appears to be convenient
for the factorial analysis, as it obeys to the Keiser-Meyer-Olkins sampling adequacy and the
Barletts sphericity tests. In addition, the covariance matrix method to extract the principal
components from the data set was preferred to the correlation matrix method; in fact, the
former method explains 97% of the variance with only 2 components, whereas the other one
explains only 86% of the variance with 4 components. The correlation coefficients (factor
loadings or factor weights) of PC1 and PC2 with variables are graphically shown in Fig. 5,
and the factorial scores for individual water samples are reported in the PC1 vs PC2 plot of
Fig. 6. Three groups of waters are defined in the plot, and their classification matches that
based on the ternary diagrams of major anions (Fig. 2). When outliers suspected to be affected
by seawater, i.e. W20(97), W34(96) and W34(97), are removed from the PCA plot, waters
classified as steam-heated are clearly defined by PC1<-0.2 and PC>0.0 values. Some waters
(W1, W3 and W25), which are areally close to the steam-heated water zone, lie in the shallow
groundwater group, possibly due to mixing with volcanic condensate (W1) or dilution by
meteoric water (W3, W25). To be noticed that water W29b, sampled from the Bambara well
in 1997, is statistically classified as steam-heated, but it falls out the steam-heated field
depicted in the ternary plot (Fig. 2).
3.2.2 Boron and bromine

Boron in the studied waters positively correlates with temperature pointing out to a close
relation with the outflow of hot crater-type fluids (see also Capasso et al., 2001). In addition,
the B/Cl ratio in thermal waters can be used to investigate mixing between different water
reservoirs. The B vs Cl diagram in Fig. 7 excludes any relationship between groundwaters and
seawater, thus pointing to fumarolic/magmatic condensate and water-rock interaction as
sources of boron and chloride in the studied waters. During the period of survey, a mean B to
Cl by weight ratio of 0.0057 was measured in the crater fumaroles (Martini, 1995, 1997,
1999). Exceptions are the W34 (96 and 97) and W20 (96) waters, for which a substantial
proportion of seawater can be concluded, along with the volcanic proportion. Interestingly,
almost all waters with B > 1 ppm lie on the same trend between a steam-heated endmember
and a fumarolic endmember.
In principle, seawater contamination may be constrained from the Br/Cl ratio of waters (Fig.
8). Waters W34 (96 and 97) and W20 (96) fit a mixing line with seawater as an endmember.
The Br contents (9 to 36 mg/kg) of these cold waters are the highest ones measured in the
studied wells, and in particular they are much higher than those in hot waters like W0, W2
and W4 (0.3 to 5.7 mg/kg), as well as in fumarolic condensate during the same period (about
5 mg/l Br in the highest temperature fumarole FA; Aiuppa et al., 2000). The Br content of
local seawater was measured to be on average 67 mg/kg (Cortecci et al., 2001 and this work).
It is noteworthy that all studied waters lie within a field delimited by the highest and lowest
Br to Cl ratios (5.810-3 and 0.610-3) measured in crater fumaroles, the range of values being
in keeping with that observed in andesites (110-3 610-3; Fuge, 1974).
3.2.3 Chemical geothermometry

The K/Na thermometer cannot be applied to the groundwaters at Vulcano, as they appear to
be totally immature in the Giggenbachs (1988) diagram of Fig. 3. Immaturity may be
ascribed to Na rather than to K and Mg, the latter ions exchanging rapidly with rock even in
10
low temperature hydrothermal systems (Giggenbach, 1988). Therefore, the application of the
K2/Mg-thermometer to uprising geothermal fluids provides usually shallow temperature
estimates (last equilibrium) rather than the reservoir ones. The SiO2 thermometer behaves
similarly. In Fig.9, the studied groundwaters are plotted in the log(SiO2) vs log (K2/Mg)
space, where are compared with the thermometric relations of different forms of SiO2.
When applied to the 1995, 1996 and 1997 samples of the geochemically less immature W0
water, the K2/Mg-thermometer yields concordant estimates of 187 to 194C. These values are
by 29 to 44C higher than those obtained from the quartz-thermometer (150 and 158C). The
silica thermometric estimates likely feel the effects of silica precipitation during cooling.
Concurrently, the original K2/Mg value in the geothermal reservoir may have been lowered
due to mixing of the rising fluid with steam-heated water (see data from Fontes et al., 1993)
enriched in Mg from advanced argillic alteration (see Cortecci & Boschetti, 2001); this type
of alteration in quite common in the Vulcano Porto area (e.g. Fulignati et al., 1996 and 1999).
Waters W20, W21, W34 depict a trend that may be interpreted as due to mixing of shallow
groundwater with seawater accompanied by interaction with rocks leading to the increase of
the K-content in solution and precipitation of amorphous silica. For instance, water W34(96)
presents a K-excess with respect to the potential mixing between seawater (41%) and water
like spring SF (59%). All these three waters show high PCO2 values of 10-2.6 to 10-1.2 atm
(calculated by PHREEQCI 2.8 software; Parkhurst and Appelo, 1999), that enhance the
incongruent dissolution of K-feldspar and the precipitation of silica. The thermal submarine
springs (110-120C), sampled by Sedwick and Stuben (1996) close to the shoreline at the
beach, match the seawater-SF mixing model; these springs lie on a N-S tectonic lineament
that extends up to the crater.
The data points of the acid sulfate-chloride springs are shifted towards the amorphous silica
line (Fig. 9), as a consequence of water-rock interaction and alteration processes. These
waters are totally immature and the majority of them fits the isochemical dissolution line in
the K-Na-Mg diagram of Fig. 3. Due to its position in the graph of Fig. 9, the SF-spring water
may be supposed to be an intermediate term along the neutralization path of an acid sulfatechloride water by interaction with rocks.
The steam-heated waters lie around the chalcedony thermometric line (Fig. 9), the highest
data point corresponding to 140C, i.e. the estimated temperature of this aquifer (Bolognesi
and DAmore, 1993). The other data points correspond to lower temperatures and are
influenced by dilution effects. Exceptions are waters W8 and W24 which are shifted towards
11
amorphous silica saturation, and water W28 probably equilibrated with advanced-argillic
alteration minerals.
3.3 Isotopic results

3.3.1 Hydrogen and oxygen isotopes of water
The hydrogen and oxygen isotope compositions of studied well waters show a wide range
of values from 42.6 (W19 well) to 2.3 (W2 well) and 7.1 (W19) to +1.9 (W2),
respectively. The only one sample from the thermal spring SF has values of 26.7 for
hydrogen and 4.4 for oxygen. These data are compared in Fig. 10 with those of yearly
average rainwater at Vulcano Porto (Capasso et al., 1992) and rainwater samples from
domestic cisterns (Panichi and Noto, 1992; Goff and McMurtry, 2000; Cortecci et al., 2001
and this work), crater-type fumarolic condensates (e.g. Capasso et al., 1999), beach fumaroles
at Porto di Levante (Chiodini et al., 1995; 1996), and seawater (Cortecci et al., 2001). The
field of values presumed for magmatic water at Vulcano (Bolognesi and DAmore, 1993) is
also shown, along with that of andesitic magmatic water as featured by Taran et al (1989) and
Giggenbach (1992).
The isotopic trend and its interpretation remain basically the same as reported in Cortecci et
al. (2001) on the basis of the 1995 data. In short, groundwaters at Vulcano are mixtures, in
variable proportions, of meteoric water and volcano-magmatic water. Seawater appears to be
involved only in well water W34 sampled in 1996, this indication being in keeping with the
high sodium and chloride contents (and their ratios) and the high bromine content. The 2Hdepletion and the
18
O-enrichment in the W34 water sample of 1997, coupled with the
decrease of salinity, can be attributed to dilution effects by rainwater likely related to a heavy
event shortly before sampling.
Waters with a geothermal-magmatic component are enriched in 2H and
18
O relative to the
other types of water. The proportion of this geothermal water is highest in the W2 well, where
it increased considerably from 1995 to 1997. The W2 samples fit a mixing line between the
geothermal component and another component, that may be a steam-heated water largely
modified by loss of vapour. A geothermal-magmatic component is present also in W0 and W4
wells, but its proportion is low with respect to W2 well and kept nearly constant during 1995
to 1997. Isotopically, the spring SF falls within the steam-heated water group; however, its
chloride-sulfate chemical composition points to a partially geothermal character of this water.
12
3.3.2 3H content of water

Omitting for this moment the set of samples from well W0, the tritium contents in our 1995,
1996 and 1997 samples and those available for the W2 well from other sources even prior to
1995 (Bolognesi and DAmore, 1993; Goff and McMurtry, 2000) range between 3.5 and 15.3
TU. All these values are compared in Fig. 11 with the corresponding chloride contents in the
waters, as well as with the tritium and chloride contents measured in local rainwater and
seawater samples.
Main features from the plot are:
1.) The data from well W2 show a very good correlation (r = 0.96). In keeping with the
conclusions of Bolognesi and DAmore (1993), this correlation suggests that the water
samples are basically binary mixtures, the endmembers being geothermal-magmatic water
with 0 TU and an extrapolated chloride concentration of about 3900 mg/kg, and a steamheated water with about 100 mg/kg chloride and 17 TU (see also Cortecci et al., 2001).
2. The steam-heated waters lie within a mixing triangle, the endmembers being represented by
the above geothermal and steam-heated waters, and a third endmember constituted by modern
meteoric water (about 4-5 TU). The classified as geothermal water W4 and the thermal spring
SF are located within this triangle. The former can be interpreted as a ternary mixture,
whereas the latter behaves similarly to W2 and may be considered basically a binary mixture.
3. All but three phreato-volcanic waters are enclosed by the above mixing triangle. Well water
W17 of 1995 lies by far outside the triangle, suggesting that in this case old meteoric water
with about 21 TU is involved, as previously concluded by Cortecci et al. (2001). Well water
W20 of 1996 lies also outside, but its position may be influenced by some contribution of
seawater. Well water W34 represents a peculiar case. It is definitely outside the mixing
triangles: in 1996, this water appears to be substantially contaminated by seawater, the other
endmember being possibly a phreatic water close to W19; in 1997, dilution lowered the
chloride content from 11,083 to 4,321 mg/kg, but kept nearly constant the tritium within 5-6
TU.
Samples from the W0 well occupy a distinct area in Fig. 11. They show a trend from a
shallow water to a geothermal water free of tritium and relatively low in chloride. This
interpretation implies that separate geothermal water bodies may exist at different depths and
temperatures beneath the Vulcano Porto plain.
13
3.3.3 2H vs Cl- and 18O vs Cl- relations

These relations are shown in Figs. 12 and 13 for our samples, as well as for additional W2
samples from other works (Capasso et al., 1999; Goff and McMurtry, 2000).
Water samples from the W2 well arrange along mixing lines (r = 0.94), by which a 2H of
+4.9 and a 18O of +2.9 are calculated for the geothermal endmember, assuming a
concentration of 3900 mg/kg chloride and no 3H for the latter (see the Cl-3H correlation in
Fig. 11). For the steam-heated endmember, a 2H of 30 to -29 and a 18O of 3 to 2
are extrapolated in the range 0 to 100 mg/kg chloride. The isotopic values for the geothermal
component are considerably heavier than those (2H of -5 and a 18O of +1) calculated
by Bolognesi and DAmore (1993) on the basis of 1986-1988 samples from the same well.
This isotopic evolution may account for a number of factors, including the condensation in
the geothermal reservoir of fluids with a much higher proportion of the magmatic component,
as already reported by Bolognesi (2000). This interpretation agrees with the increase of the
microseismicity, temperature and CO2 degassing recorded at the crater in 1996, and related to
a concurrent increased magmatic activity at depth (La Volpe et al., 1999).
The W0 water data show a vertical array, that may be explained in terms of binary mixtures,
only assuming nearly identical 18O and 2H values for the chloride-rich component and the
chloride-depleted component. This seems to be a quite unrealistic possibility. A more realistic
interpretation is to imaging a buried water body which losses steam at temperature higher than
300C and the condensation of the steam in the W0 well. At this temperature, in fact, the
water-steam isotopic fractionation is close to zero for both oxygen and hydrogen (Horita and
Wesolowski, 1994) and the HCl behaves as a weak acid, so that partitioning of HCl into the
vapour can occurs from a low-pH and Cl-rich fluid (Ruaya and Seward, 1987; Simonson and
Palmer, 1993). Alternatively, W0 data trend may be explained by mixing between steamheated water and fumarolic gas, followed by separation of various proportions of steam. In
both cases, water acidity is neutralized by mineral dissolution processes in the aquifer.
The notable contribution of seawater in the W34 well is further on constrained in the 1996
water sample, the other component being a meteoric water. The dilution undergone by the
W34 well water in 1997 was operated by rainwater comparatively enriched in
18
O and
depleted in 2H, and probably related to the heavy rain event occurred just one day before
sampling.
Finally, some seawater would seem to be present in the 1995 and 1996 samples from the
W20 well. In 1997, autumn-winter rain caused strong dilution of this well water.
14
3.4 Sulfur and oxygen isotopes of sulfate

3.4.1 34S(SO42-) values
Sulfate from well waters chemically classified as shallow groundwaters (W1, W3, W3b,
W5, W5b, W9, W12, W13, W14, W16, W17, W18, W20, W21, W22, W23, W25, W26,
W27, W29, W30, W31, W32, W33, W33b, W34) shows 34S values from +2.5 to +12.9,
this large isotopic range suggesting that, along with oxidation of volcano-magmatic gases,
additional sources of sulfate may be appreciably involved in these waters. As reported in
Cortecci et al. (1996), reference 34S values are 2.7 to +3.7 for total sulfur in crater
fumaroles (+2.0 to +6.5 for SO2 and 7.2 to 1.8 for H2S), +7.2 to +16.5 for anhydrite
and 11.5 to 5.9 for pyrite coexisting in the hydrothermal paragenesis of borehole cuttings
from the VP1 well (see Fig. 1) and +20.2 for seawater sulfate off the Vulcano island.
Additional 34S data (this work) on soluble supergenic sulfate from the Forgia Vecchia site on
the northern flank of the volcanic cone are +3.7 (well crystallized gypsum) to +4 (white
incrustations). Hydrolysis of pyrite would seem to be excluded as significant source of
sulfate, due to the strong depletion in
34
S of the mineral relative to crater-type fumarolic
gases. On the other hand, the role of the supergenic sulfate via dissolution by infiltrating
rainwater is problematic to be constrained, the isotopic composition of this sulfate being
nearly identical to that of the crater-fumarolic sulfur. Vein anhydrite should derive from
hydrolysis of hypogene/magmatic SO2, followed by interaction with Ca-minerals in the rocks
(Fulignati et al., 1996) An anhydrite-pyrite mineral pairs from 620 m depth in the borehole
provides an isotopic temperature of 226 25C (using the fractionation factors in Ohmoto
and Rye, 1979), in keeping with the thermometric estimates from other methods (e.g.
Fulignati et al, 1996). Therefore, isotopic equilibrium can be assumed for this specific mineral
pair, and possibly for anhydrite and pyrite on the whole along the drilled core. In the case,
temperature and SO2 to H2S mole ratio in the fluids may be the factors controlling the wide
34S ranges observed for the two minerals (Taran et al., 1996; Kusakabe et al., 2000).
Analogously, mineral sulfates at Forgia Vecchia can be related to near surface oxidation of
crater-type fumarolic sulfur species.
Sulfates from waters classified as sulfate-chloride (W0, W2, W4, SF) and as steam-heated
(W6, W7, W8, W15, W24, W28, W29b) show comparable 34S values within the ranges +0.6
to +5.4 (mean +3.0 0.3) and 0.7 to +3.5 (mean +2.0 0.9), respectively. As
already concluded by Cortecci et al. (2001), these isotopic compositions match those of the
crater fumaroles and support a mostly deep-seated magmatic origin for sulfur and the
15
production of aqueous sulfate via hydrolysis of SO2 and oxidation of H2S in subsoil water
bodies. Incidentally, and based on the large depletions in
34
S and Cl- relative to waters W0
and W2, water W4 may be considered steam-heated rather than geothermal.

In Fig. 14, the 34S(SO42-) values in well waters are plotted versus the corresponding
Ca2+/SO42- weight ratios, and these data points are compared with those of seawater,
hydrothermal anhydrite and secondary gypsum, as well as with the 34S ranges of total sulfur
(SO2 + H2S) and SO2 in the crater fumaroles. The 34S range of crater H2S is omitted, as the
H2S undergoing oxidation in the shallow water system may be considerably enriched in 34S by
addition of H2S deriving from hydrolysis of SO2 in geothermal reservoir(s) at depth (see
Cortecci et al., 2001). The distribution of the repeated sampled sulfates in the graph and the
elaboration carried out can be interpreted as follows:
1. All sulfates lie within a mixing triangle, the endmembers being represented by i) volcanomagmatic condensate with 34S(SO42-) variable in the range 2.7 to +6.5, depending on
time and space beneath the Vulcano Porto plain, ii) meteoric waters with distinctly high
Ca2+/SO42- ratio, and iii) seawater.
2. Anhydrite and gypsum occurrences are within the triangle, but their sulfur should be totally
volcano-magmatic, with no contribution from seawater.
3. Inside the general mixing triangle, chloride-sulfate, steam-heated and the majority of
shallow groundwaters occupy a sub-space delimited basically by two of the three
endmembers reported above, i.e. meteoric shallow water and volcano-magmatic fluids, the
latter having variable 34S composition in the range 2.7 to +6.5, depending on space and
time. However, we cannot exclude variable Ca2+/SO42- and 34S(SO42-) values also for the
shallow-meteoric water endmember. In addition, gypsum and other supergenic soluble sulfate
may be involved in both steam-heated waters and shallow groundwaters, if their meteoric
recharge occurs from the volcanic cone.
4. The position of the thermal spring SF, which is probably fed by geothermal water, denotes
for dissolved sulfate an origin mostly from disproportionation of volcano-magmatic SO2
substantially enriched in 34S with respect to H2S. This may implies a reservoir at depth fed by
fluids relatively rich in H2S depleted in 32S by isotopic exchange with SO2.
16
5. Sulfate in the few shallow groundwaters outside the sub-triangle (W16, W20, W21, W27,
W34) can be interpreted in terms of possible contributions from anhydrite dissolution and/or
seawater ingression. The latter source would seem to be particularly manifest in well water
W34.
3.4.2 34S(SO42-) time-variations
Even if the data points for each water are few, a time-34S plot can give an idea on the
isotopic stability or instability of sulfate in the hydrologic system. In Fig. 15, sulfate-chloride
waters and all but one steam-heated waters show quite constant 34S values within 1.
Astonishing are the nearly identical 34S(SO42-) values of +3.0 0.2 in the W0 well during
eight months from June 1996 to January 1997. Exception is the steam-heated water W7; its
Ca2+/SO42- ratio kept nearly constant between 0.28 in 1996 and 0.25 in 1997, and therefore the
observed 34S-enrichment by 1.7 in 1997 with respect to 1995 and 1996 (+1.7 0.1) may
be attributed to a change of the isotopic composition of total sulfur in the magmatic-volcanic
gases entering and escaping from the geothermal water body at depth. Dissolution of vein
anhydrite agrees with the higher 34S(SO42-) value in W7, even if the Ca2+/SO42- ratio is only
slightly lower in 1997 (0.25 by weight) relative to 1996 (0.28 by weight).
Sulfate from the great majority of the shallow groundwaters also show quite constant 34S
values, with variations less than 1. Exceptions are represented by sulfate from wells W20,
W21, W25 and W29, its 34S variations being 3.6, 2.0, 1.5 and 1.4, respectively. Based on
Figs. 14 and 15, the
34
S-depletion in sulfate W29 in 1997 with respect to 1996 may be
attributed to a change in the 34S of the gases interacting with the aquifer, whereas the
34
enrichment of sulfate W21 in 1996 and 1997 with respect to 1995 may be due to some
contribution of heavy sulfate from dissolution of vein anhydrite. The isotopic and chemical
evolution of sulfate with time in well W20 requires a more articulated interpretation, by
which 1) the aquifer was significantly contaminated by seawater in late spring 1996 and 2)
afterwards the aquifer underwent a strong dilution by heavy rains during autumn-winter.
Water W25 displays in 1997 a 34S value by about 1.5 higher than the quite uniform ones
measured in 1995 and 1996 (+3.25 0.05). In addition, its Ca2+ to SO42- by weight ratio
passed from 0.3 in 1995 to 0.6 in 1996 to 1.7 in 1997. These isotopic and chemical changes,
along with a decreasing TDS during 1995 to 1997, are difficult to be explained, unless
imaging uptake of anhydrite-sulfate enriched in
34
S, followed by dilution with shallow
groundwater enriched in Ca2+ relative to SO42- like water W19 with a Ca2+/SO42- by weight
ratio of 4.6 (Fig. 14); the 34S(SO42-) of water W19 may be inferred to be close to zero when
17
the isotopic values measured for total sulfur in fumaroles and sulfate from cistern rainwater
are put together. A direct dilution by infiltrating rain would seem to be excluded, as the
Ca2+/SO42- ratio and the 34S(SO42-) value of the meteoric water on the island should be lower
than 1.7 and +4.7, respectively (see Table 1).
The isotopic constancy of sulfate from water W34 (34S = +12.8 0.1), when compared
with the strong dilution undergone in 1997 and the notable proportion of seawater sulfate both
in the 1996 and 1997 water samples (Fig. 16), deserves specific comments. The identical
34S(SO42-) values of 1996 and 1997 are problematic to be explained, considering the mixed
marine/magmatic-volcanic composition of sulfate and the quite different sulfur isotopic
composition of the two components. One may imagine that (1) the aquifer feeding well W34
in June 1996 was closed to further contribution of seawater up to at least February 1997, thus
preserving the 34S(SO42-) signature of 1996, (2) the dilution was promoted by infiltrating
rainwater very depleted in SO42- with respect to the phreatic water. Along with seawater,
another water rich in sulfate (2100-2200 mg/l) should have been present in the W34 water
sample of 1996, this second component being represented by steam-heated or geothermal
water or water like the SF spring. In the latter case, the calculated contribution of 40%
seawater to the aquifer under question represents a minimum estimate (Fig.16; see also
section 3.2.3).
As in the W34 well at Vulcano, a high 34S(SO42-) value of +14.7 was measured in the
AGIP well on the nearby Lipari Island (see Tab. 1). This isotopic signature points to a
significant contamination by seawater, in agreement with the vicinity of the well to the
shoreline and the sodium-chloride composition of the water. Again at Lipari, the 34S(SO42-)
of +4.3 measured in the San Calogero spring supports a mostly deep-seated origin of the
sulfur; the spring is located inland and its water is of sodium-sulfate type.
3.4.3 18O(SO42-) values
Sulfate from the hottest (44 to 73C) waters in 1995 and 1997 was analysed for the oxygen
isotope composition, along with sulfate from selected warm and cold (14 to 33C) waters
(Table 2).
The 18O(SO42-) values show a relatively narrow range between +7.1 to +10.5, without
any relation with temperature, sulfate concentration and 18O(H2O) values. The absence of
isotopic correlation even for the hottest samples can be interpreted in terms of a generalized
isotopic disequilibrium between dissolved sulfate and water, probably due to the mixed
character of the studied waters and the slow oxygen isotope exchange rate between sulfate
18
ions and water (Lloyd, 1968; Cortecci, 1974; Chiba and Sakai, 1985). The application of the
18O(SO42--H2O) thermometers of Lloyd (1968) and Mizutani and Rafter (1969) to the hottest
W0 water samples both in 1995 and 1997 yield concordant values of 158 to 173C, which are
significantly lower than the chemical K/Mg thermometric estimates of 187 to 194C. The
influence of the mixing effects on the sulfate-water isotopic fractionation is manifest in water
W2, i.e. its 18O(SO42-) of +9.4 is in equilibrium with water of 18O of +2.9 in the
geothermal reservoir at 254 3C, but subsequent dilution by shallow water during ascent
enlarged the original isotopic fractionation factor leading to a considerably lower
thermometric estimate of 188 3C when the measured 18O(H2O) value of 0.6 is
applied. In spite of the constancy of the 18O(H2O) parameter, the 18O(SO42-) time-variation
in water W0 from +9.4 in 1995 to +8.5 in 1997 appears to be significative, and may be
related to the concurrent lowering of the SO42- concentration, i.e. to dilution by aqueous
sulfate depleted in 18O.
Finally, the 18O(SO42-) of +7.5 in water W34 in 1997 (799 mg/kg SO42-) can be
explained in terms of a mixture of about 40% seawater (Tyrrhenian seawater sulfate: 3170
mg/kg; 18O of +9.5, Cortecci et al., 1974) with about 60% groundwater with sulfate
concentration and sulfate oxygen isotopic composition of about 2000 mg/kg and +5.5,
respectively (see sections 3.2.3 and 3.4.2, and Fig. 16). This mixed water may have been
feeding the W34 well in 1996, and then underwent dilution by very poor in sulfate meteoric
water.
3.5 Strontium isotopes

Sr isotope analyses were performed on water samples from selected wells fed by geothermal
water (W0, 1996; W2, 1996; W4, 1996), steam-heated water (W7, 1996; W28, 1996) and
shallow groundwaters (W17, 1996; W20, 1996; W21, 1996; W23, 1996; W34, 1996 and
1997).
Following the procedure of Pennisi et al. (2000), the
87
Sr/86Sr ratios were used in
combination with the 18O signature in order to model the isotopic effects on meteoric water
and fumarolic condensate at depth in the geothermal reservoir due to interaction with the host
volcanic rocks at 250C, and to constrain also by this approach the role of seawater in feeding
the selected wells. In Tab.3 the 18O and 87Sr/86Sr data on analysed waters are reported along
with the reference data used in the modelling for meteoric water, fumarolic condensate and
volcanic rocks, and the applied rock to water oxygen and strontium by weight concentration
ratios (Cr/Cw) and isotopic fractionations. Data sources other than this work are McArthur
19
(1994) for the seawater
87
Sr/86Sr ratio that is assumed to be equal also for sea-spray and
rainwater; Capasso et al. (1999) and Goff and McMurtry (2000) for the mean 18O value of
high temperature fumarolic condensate during the present survey; Ellam and Harmon (1990)
for the 18O value averaging most Vulcano basalt samples; De Astis et al. (1997) for the mean
87
Sr/86Sr ratio of rocks from the caldera La Fossa and the Lentia complex, as an
approximation of the isotopic ratio of the geothermal reservoir; Gioncada et al. (1995) for the
mean
87
Sr/86Sr ratio of the fumarolic condensate (approximated from the lava samples). The
strontium Cr/Cw ratio was approximated to 100000, as the Sr content in the rocks at Vulcano
averages 1000 ppm (De Astis et al., 1997) and is about 0.01 ppm in rainwater (Pennisi et al.,
2000). The oxygen Cr/Cw ratio is that reported in Pennisi et al. (2000; see also Richardson and
McSween, 1989) for the basalt-water system, and the water-rock oxygen isotope fractionation
factor (w-r) is approached by the K-feldspar-water one from ONeil and Taylor (1960). The
Sr isotope fractionation between water and rock is zero. The isotopic effects on water are
described by the following equation, where the water to rock ratio is indicated as N:
w,f = [N w,i + (Cr/Cw) r,i + (Cr/Cw) (w-r) ]/[N + (Cr/Cw)]
with = 18O or 87Sr/86Sr; w = water, r = rock, i = initial, f = final.
The main results from the modelling are (Fig. 17): 1) the geothermal water at depth is a
fumarolic condensate exchanged with rocks under a water to rock ratio close to unit, i.e. it is
largely magmatic, and its position on the model curve can be attributed to a shift towards a
depleted 18O value due to water-rock interaction effects (e.g. Giggenbach, 1992 and 1993);
2) the well waters W0, W2 and W4 are mixtures, in variable proportions, of geothermal water
and steam-heated water like W28; and 3) the shallow groundwater W34 appears to be a
mixture of isotopically exchanged meteoric water and normal seawater. In June 1996,
seawater Sr may have been present in the W20 and W17 wells and totally absent in the W21
and W23 wells.
4. Relations between groundwaters and volcanic fluids.

In Fig 18, the sulfate and chloride concentrations of studied groundwaters are compared
with those of crater fumarolic condensates, assuming oxidation of both SO2 and H2S in the
volcanic fluids, and the oxidation of the SO2 alone. The comparison includes also the
available data on the Pozza and Istmo springs (Mazor et al., 1988; Fontes et al., 1993; Aiuppa
et al., 2000). The main feature is the clear indication that all sulfate-chloride waters (SCW)
20
both neutral and acid derive from condensation of volcanic fluids, which undergo mixing with
steam-heated water. In details, neutral SCW show a nearly uniform SO4 to Cl ratio, as
expected for binary mixtures between chemically well established endmembers (geothermal
water and steam-heated water). On the other hand, acid SCW are scattered, probably due to
the involvement of additional sources of water like seawater and volcanic condensates
variously enriched in sulfur and chloride.
With respect to the neutral SCW, the acid ones should correspond to a lower maturation
degree in terms of mineral dissolution and related neutralizing effects. Other factors may be
also involved in controlling the pH values and their evolution with time (Mazor et al., 1988;
Fontes et al., 1993; Amend et al., 1998; Aiuppa et al., 2000), like: 1) the size of the aquifer
with respect to the flow of entering volcanic fluids, and 2) the pH of the latter fluids that in
turn depends on the uprising rate and the interaction degree with rocks.
In Fig. 19, the 2H vs 18O field of the steam escaping from the geothermal reservoir (250C;
2H = +4.9;18O = +2.9) as well as from mixtures in different proportions between the
rising geothermal fluids and rainwater at Vulcano Porto (2H = -34, 18O = -6; Capasso et
al., 1992) and Vulcano Piano (2H = -48, 18O = -8; as from data on cistern waters by Goff
and McMurtry, 2000). In the computation, the multistage steam separation method and the
water-steam fractionation factors of Truesdell et al. (1977) were used, assuming 250C for the
geothermal component and 18C for the meteoric component. It is noteworthy that (1) all but
one steam-heated waters lie between the 140 and 160 isotherms, in keeping with the SiO2thermometric estimates (see section 3.2.3); the different behaviour of the steam-heated W28 may
be interpreted in terms of
18
O-shift due to interaction with host rocks under low water to rock
ratio, and (2) the steam feeding the beach fumaroles lies on the 140-isotherm, close to the
temperature of 160C estimated by Chiodini et al. (1995; see also Capaccioni et al., 2001) for the
aquifer at depth.
According to Giggenbach and Stewart (1982), the steam-heated water sulfate content can be
related to the H2S content and the steam fraction of the gaseous convoy entering the aquifer,
when H2S is completely oxidized to SO42- in the aquifer:
(SO42-) = 5333 * (H2S) * [Yv/(1-Yv)]
with H2S in mmol/mol, SO42- in mg/kg and Yv being the vapor fraction. Based on this
equation, and applying the highest H2S content of 3 mmol/mol measured in the beach
fumaroles (Chiodini et al., 1995) and a Yv of 0.0421 calculated at 160C in the reservoir, a
SO42- content of 703 mg/kg is obtained for the steam-heated aquifer. This is a minimum
21
concentration value for sulfate, as the loss of secondary steam from the aquifer and
dissolution of sulfate minerals (e.g. in water W8; see section 3.2) should be considered. In this
respect, steam-heated waters at Vulcano show sulfate concentrations in the range 700 mg/kg
(W6 in 1996) to 1996 mg/kg (W8 in 1995).
Finally, the only available isotopic data on the acid sulfate-chloride waters refer to the
Pozza spring (Shinohara and Matsuo, 1986). According to Bolognesi and DAmore (1993),
the 18O of +9.4 and 2Hof -1.6 support a magmatic origin for this water.
5. Conclusions
Several concluding remarks derive from the present chemical and isotopic study on the
groundwater system of Vulcano:
1. Independently of the sampling date, all waters are far from chemical equilibrium with host
rocks. Their anion composition ranges from chloride to sulfate-chloride to bicarbonate,
whereas sodium or calcium are the major cations.
2. Three groups of waters are recognized: (i) shallow groundwaters, which are relatively rich
in chloride and bicarbonate. They derive from direct interaction of shallow meteoric water
with rising crater-type fumarolic/magmatic fluids; (ii) steam-heated waters, enriched in
sulfate and bicarbonate relative to chloride. Depending on the relative abundances, they
can be classified as sulfate-type or bicarbonate-type. These waters originate from
interaction of geothermal steam and gases with shallow aquifers. In turn, the geothermal
reservoir(s) is constituted by fumarolic/magmatic condensate; and (iii) sulfate-chloride
waters, which are mixtures of geothermal water and shallow water, the latter component
being possibly a steam-heated aquifer as shown for the Camping Sicilia well W2. These
waters issue at the base of the volcanic cone.
3. The shallow water component is meteoric both recent and old, that may be contaminated
by seawater. The only significant presence of seawater is testified in the Togo-Togo
Camping well W34 by chemical (sodium and chloride) and isotopic (sulfur and strontium
isotopes) data. Some seawater is suspected in the Scarcella well W20.
4. On the whole, the groundwater system kept rather stable over the period of survey both
chemically and isotopically. Notable chemical and isotopic variations observed in some
wells can be interpreted as due to changes in the mixing proportions of components or to
dilution effects by rainwater.
5. The sulfur isotopic composition of sulfate was particularly constant, testifying a unique
magmatic major source of sulfur in most aquifers from oxidation of crater-type fumarolic
22
sulfur dioxide and hydrogen sulfide. Appreciable variations refer to wells where sulfate
can derive from additional sources like seawater (W20 well) or dissolution in the subsoil
of secondary anhydrite (W16 and W21 wells).
6. The sulfate-water system in the studied wells is in oxygen isotope disequilibrium, due to
the mixed character of water and sulfate and the slow isotopic exchange rate between
these two compounds. Oxygen isotopes of sulfate in the Camping Sicilia well W2 should
be in equilibrium with water in the geothermal reservoir at the calculated temperature of
254C.
Acknowledgements
Many thanks are due to Sonia Tonarini of the Institute of Geosciences and Georesources
(CNR, Pisa) for the strontium isotope analyses. The research was supported by MURST-ex
60% grants (G. Cortecci) and by the CNR-International Institute for Geothermal Research
1995-1996-1997 ordinary grants (L. Bolognesi).
23
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32
Captions of figures
Fig. 1. Map of Vulcano Porto area (Vulcano Island) and locations of studied well waters (W). Well
waters are subdivided in three groups as defined in the text. Boreholes VU2/bis, VP-1 and IV-1 are
also shown, along with acid springs named Pozza and Istmo. Dashed lines depicts fractures, faults
and structural lineaments (Gabbianelli et al., 1991).
Fig. 2. Triangular diagrams for major anions and cations in well water samples collected in 1995,
1996 and 1997. Majority of waters are high in alkalies and low in chloride. In the anion diagrams,
no waters occur in the field (dashed box) expected for equilibrated (mature) geothermal waters
(Giggenbach, 1988). The sulfate to chloride ratios of fumarolic condensate (complete oxidation of
reduced sulfur to sulfate) and magmatic water (disproportionation of SO2) at Vulcano are calculated
from the limiting chemical compositions reported by Chiodini et al. (1995; see also Cortecci et al.,
1996). Vulcano magmatic waters correspond to the average compositions of the low pH sulfatechloride Pozza and Istmo springs (see caption of Fig. 1).
Fig. 3. Trilinear diagram showing the relative concentrations of Na, K and Mg in the studied waters,
compared with nonequilibrium to equilibrium fields as discussed by Giggenbach (1988). Waters
appear to be "immature", with samples from wells W19 (1995 sample) and W0 (1995 to 1997
samples) being the most immature and the most mature, respectively. The Vulcano volcanic rocks
isochemical dissolution line is based on data from De Astis et al. (1997). Large filled circle at the
intersection of the dotted lines identifies the most probable composition of the geothermal reservoir
(250C) beneath the Vulcano Porto plain (see Cortecci and Boschetti, 2001).
Fig. 4. Distribution of the Na-Cl data points from well waters compared to seawater. The data on
W0 include the monthly samples from July 1996 to January 1997 (see Table 1), and additional data
on W2 (small triangles) are from Bolognesi and DAmore (1993) and Capasso et al. (1999). The
solid line connects water W19 to seawater. This line and the two dashed lines delimitate the data
field, suggesting possible mixing trends.
33
Fig. 5. Plot of the factor loadings obtained from PCA (Principal Component Analysis) data
elaboration. Noteworthy is the good correlation between principal components and variables.
PCAs factor loadings are calculated by SPSS 11.0 software (Norusis, 2002).
Fig. 6. PC1 vs PC2 factor scores for groundwaters at Vulcano. In graph A, waters 20(96), 34(96)
and 34(97) appear to be outliers in the plot. In the re-scaled graph B, these waters are removed and
the subdivision of the other waters in three groups is manifest.
Fig. 7. B vs Cl logarithmic plot. Well waters are compared with the chemical composition of (1)
andesitic (Sanchez and Arnorsson, 1995) and basaltic rocks (Arnorsson and Andresdottir, 1995)
including volcanic rocks from Vulcano (Goff and McMurtry, 2000), (2) crater-type fumarolic
condensates (Martini, 1983, 1993, 1995, and 1997; Pennisi et al., 1997) and (3) seawater. Mixing
trends and endmembers are shown (see text).
Fig. 8. Br vs Cl logarithmic plot. Well waters, meteoric waters and seawater are compared with
crater fumarolic condensate (Coradossi et al., 1985; Martini, 1983; 1993; Martini and Cellini
Legittimo, 1984; Martini et al., 1986; 1989). Additional data on W2 well (small triangles) are from
Capasso et al. (1999).
Fig. 9. SiO2 vs K2/Mg plot. The data from studied waters are compared to the SiO2 (Fournier, 1991)
and K-Mg (Giggenbach, 1988) geotermometers. Data points from literature on water samples from
W0 well (small pentagons; Brondi and DallAglio, 1991; Fontes et al., 1993), submarine warm
springs (dashed area; Sedwick and Stuben, 1996), and Pozza and Istmo springs (Fontes et al., 1993)
are shown for comparison.
Fig. 10. 2H vs 18O plot of well water samples. Data are compared with the global meteoric water
line (deuterium excess d = 10) and the meteoric water line valid for the southern Tyrrhenian area (d
= 15; Panichi and Noto, 1992), the weighted yearly average rainwater at Vulcano Porto (Capasso et
al., 1992), rainwater from cisterns (Panichi and Noto, 1992; Goff and McMurtry, 2000; Cortecci et
34
al., 2001; this work), crater (e.g. Capasso et al., 1999) and beach (Chiodini et al., 1995 and 1996)
fumarolic vapor, geothermal and steam-heated endmembers (see text), Vulcano magmatic water
(Bolognesi and DAmore, 1993), andesitic water (Taran et al., 1989) and local seawater.
Fig. 11. Correlation of Cl - 3H in well waters. Samples with distinct chloride contents are identified.
Additional data on W2 are reported (Bolognesi and DAmore, 1993; Goff and McMurtry, 2000)
after tritium correction for the elapsed time. The shown range of values in crater fumaroles during
the study period is from Martini (chloride data; 1995, 1997 and 1999) and Goff and McMurtry
(chloride and tritium data; 2000). The majority of samples are enclosed by a triangle (solid lines)
with vertices occupied by young rainwater (~ 4 TU), geothermal water (0 TU) and steam-heated
water (~ 17 TU). The dashed lines may identifies the endmembers feeding the W0 well. See text for
other features. Water W2 from the Camping Sicilia well is a mixture between the geothermal and
the steam-heated endmembers. In the upper part of the diagram, well waters are compared with
seawater. Waters W20 and W34 appear to be distinct with respect to the other phreato-volcanic
waters; possibly, seawater is involved in these wells, especially in the W34 one
Fig. 12. Cl- vs 2H diagram in well waters. Isotopic composition of water in the geothermal
reservoir as in Fig. 9, and the Cl content of 3900 mg/kg as in Fig. 10. Sources of data on cistern
waters are as in Fig. 9. Additional data on W2 (small triangles) are from Capasso et al. (1999) and
Goff and McMurtry (2000). Sources of data on crater fumaroles are as in Fig.9. The effects on
steam-heated water Cl and 2H compositions due to progressive evaporation at 140C are shown by
the solid curve (using the isotopic fractionation factors for continuous steam separation reported in
Truesdell et al., 1977). The Camping Sicilia well water W2 may be a mixture between geothermal
water and the shown steam-heated endmember. Samples W0 do not fall within the dashed triangle
as in Fig. 10, probably accounting for additional processes as discussed in the text. The presence of
seawater in wells W20 and W34 would seem to be enforced.
Fig. 13. Cl- vs 18O diagram in well waters. Isotopic composition of water in the geothermal
reservoir as in Fig. 9, and the Cl content of 3900 mg/kg as in Fig. 10. Sources of data on cistern
35
waters are as in Fig. 9. Additional data on W2 (small triangles) are from Capasso et al. (1999) and
Goff and McMurtry (2000). Sources of data on crater fumaroles are as in Fig. 9. The effects on
steam-heated water Cl and 18O compositions due to progressive evaporation at 140C are shown
by the solid curve (using the isotopic fractionation factors for continuous steam separation reported
in Truesdell et al., 1977). The Camping Sicilia well water W2 may be a mixture between
geothermal water and the shown steam-heated endmember. Samples W0 do not fall within the
dashed triangle as in Fig. 10, probably accounting for additional processes as discussed in the text.
The presence of seawater in wells W20 and W34 would seem to be enforced.
Fig. 14. Plot of Ca/SO4 vs 34S(SO4) in well waters. The data are compared with the sulfur isotopic
composition of crater fumarolic SO2 and total fumarolic sulfur (SO2 and H2S) (Cortecci et al.,
1996), supergenic gypsum from the volcanic cone (Boschetti, 1998), anhydrite from borehole
cuttings (Cortecci et al., 1996). Mixing trends with cold meteoric groundwater greatly enriched in
calcium relative to sulfate (like W19, with a Ca/SO4 = 4.6 in 1995) are depicted. The dashed line
distinguishes aqueous
and
34S-enriched
34S-depleted
sulfate basically from oxidation of crater-type S-bearing gases
sulfate due to appreciable contributions from dissolution of anhydrite and/or
mixing with seawater.
Fig. 15. 34S(SO4) variations in the studied wells during 1995 to 1997, grouped according to the
genetic classification of the waters (symbols as in Fig. 1).
Fig. 16. Relation between 34S(SO4) values and SO4 concentrations in well waters, compared to
other S-bearing systems. Data fields of fumarolic sulfur are derived from Cortecci et al. (1996).
Mixing curves are shown, involving possible endmembers.
Fig. 17. Oxygen and strontium isotope compositions of selected well waters, compared to isotopic
effects related to water-rock interaction at 250C and for different water to rock ratios (N; by
volume). Data on rocks at Vulcano are from De Astis et al. (1997). In the model, the oxygen
concentration by weight Cr/Cw ratio of 0.5 is applied, as suggested by Pennisi et al. (2000) and
36
Richardson and McSween (1989) for the volcanic rock-water systems. For strontium, the Cr/Cw by
weight ratio should approach 100,000, considering the Sr content of about 0.1 weigth % (1000
ppm) in the rocks at Vulcano (De Astis et al., 1997) and about 0.000001 weigth % (0.01 ppm) in
rainwater in the Tyrrhenian Sea area (Pennisi et al, 2000). The 87Sr/86Sr ratio of 0.70918 in seawater
and rainwater was used in the computation (McArthur, 1994). The mixing line from back
extrapolation of W34 water samples and seawaters is shown.
Fig. 18. Cl- vs. SO42- logarithmic plot. Data points of studied waters are compared with those of
crater fumarolic condensates, and Pozza and Istmo acid springs (Mazor et al., 1988; Fontes et al.,
1993; Aiuppa et al., 2000). Sulfate in the fumarolic condensate is assumed to derive from
disproportionation of SO2 or oxidation of total sulfur. Data fields of fumarolic sulfur are derived
from Cortecci et al. (1996) and Chiodini et al. (1996).
Fig. 19. Isotopic composition of the steam evolved from the geothermal endmember (2H = +4.9;
18O = +2.9) and mixtures between the rising geothermal water and subsoil meteoric water, the
latter being recharged locally at Vulcano Porto (VulPt: 2H = -34; 18O = -6) or at Vulcano
Piano (VulPn: 2H = -48; 18O = -8; cisterns data from Goff and McMurtry, 2000). Data on the
steam discharged by fumaroles at the beach and on the feeding reservoir are from Chiodini et al.
(1995 and 1996). All but one steam-heated waters lie between isotherms 140 and 160C, the
exception being water W28.
Tab. 1. Chemical and isotopic compositions of Vulcano and Lipari Islands waters.
Tab. 2. Oxygen isotope composition of the sulfate from selected water samples.
Tab. 3. Strontium isotope composition from selected water samples and parameters used for the
water(condensate)-rock interaction models.
37
Boschetti T, Cortecci G, Bolognesi L (2003) - Chemical and isotopic compositions of the shallow groundwater system of Vulcano Island, Aeolian Archipelago, Italy: an update. GeoActa 2, 1-34
Fig.1
38
Fig.2
39
Fig.3
40
Fig.4
41
Fig.5
42
Fig.6
43
Fig.7
44
Fig.8
45
Fig.9
46
Fig.10
47
Fig.11
48
Fig.12
49
Fig.13
50
Fig.14
51
Fig.15
52
Fig.16
53
Fig.17
54
Fig.18
55
Fig.19
56
Tab.1-a
Chemical and isotopic compositions of Vulcano and Lipari Islands waters.

H
()
S(SO4)
H
(T.U.)
()
149
-2.68
-23.7
3.5 0.5
170
-2.76
-21.1
1.3 0.6
+3.3 0.1
-2.68
-21.6
2.9 0.9
+2.95 0.05
61
-2.78
-22.0
0.2 0.6
+3.2
43
-2.87
-21.3
2.7 0.7
+3.0
45
-2.88
-21.9
2.3 0.6
+2.9
1645
46
-2.84
-21.2
2.7 0.5
+2.7
1179
1495
46
-2.80
-21.9
2.0 0.7
+2.7
1746
1686
58
-2.71
-21.1
1.2 0.8
+3.1
1530
555
1233
1566
921
57
3.86
159
-2.73
-22.1
1.6 0.5
+2.8
69
740
316
438
927
1068
18
1.50
123
-5.12
-31.5
9.7 1.0
+2.6
62
731
262
433
741
977
19
1.50
123
-5.14
-30.2
8.7 1.0
+2.5
48
560
233
290
519
1149
16
0.85
78
-5.37
-31.9
8.0 0.8
+2.8
65
80
1511
463
1376
1944
518
50
3.50
124
-0.55
-15.6
10.2 0.9
+3.0
163
113
1972
478
2163
2252
447
74
5.71
114
+0.72
-6.4
6.2 0.8
+3.5
234
186
2058
591
2767
2398
437
112
4.31
117
+1.92
-2.3
5.0 0.7
+3.8
1610
109
68
284
216
160
494
882
0.40
92
-5.59
-32.9
10.0 1.1
+2.6
3431
1875
110
42
379
162
368
505
383
16
0.95
145
-4.68
-30.5
7.5 0.9
+4.2
date
T
(C)
pH
W0
04.06.95
73
6.87
8055
5302
40
1476
578
1050
1903
712
43
3.55
(Cratere)
04.06.96
74
7.03
124
9845
6328
64
11
1821
538
1743
1839
842
56
5.50
01.07.96
1659
1604
1618
57
01.08.96
1973
2074
1667
01.09.96
1317
1046
1474
30.10.96
1357
1001
1565
10.11.96
1387
1134
01.12.96
1401
01.01.97
1808
31.01.97
74
7.44
9633
5231
56
10
W1
06.06.95
48
6.38
4763
2822
46
(Lentia)
05.06.96
48
6.55
124
4347
2547
39
02.02.97
44
7.00
4150
1933
69
W2
05.06.95
52
7.26
8838
5751
(C. Sicilia)
04.06.96
52
7.26
141
10410
7600
31.01.97
49
7.79
14774
8839
04.06.96
36
6.57
186
2475
31.01.97
28
7.99
Eh cond.
TDS
Ca
Mg
Na
Cl
SO4 HCO3 H3BO3 Br
SiO2 O
()
34
18
sample
VULCANO ISLAND SAMPLES
W3
+3.1 0.2
(Le Calette)
W3b
(EAS)
W4
02.06.95
65
6.53
5461
3775
110
42
827
352
627
1525
391
29
1.00
135
-2.30
-19.3
8.3 0.9
+0.6
(Muscar 1)
04.06.96
66
6.60
150
5481
4233
194
62
866
382
759
1634
455
31
0.30
99
-1.94
-17.1
7.2 0.7
+0.7
W5
03.06.95
28
6.52
2472
1486
94
49
288
145
252
425
439
10
0.30
87
-5.62
-31.6
11.2 1.0
+4.5
(Scaffidi)
04.06.96
26
6.80
175
2319
1434
109
49
275
111
252
386
358
10
0.40
95
-5.84
-33.4
8.3 1.0
+3.8
01.02.97
20
7.55
2964
1510
118
49
293
96
300
408
236
12
0.42
85
-5.60
-33.9
6.5 0.7
+4.0 0.1
W5b
04.06.96
24
7.21
163
1912
1302
91
43
215
85
230
436
128
0.40
70
-5.33
-30.9
7.8 0.9
+4.6
(Ferlazzo 1)
01.02.97
20
6.19
2348
1132
72
34
252
77
269
291
180
12
0.38
85
-5.24
-31.2
8.2 0.7
+4.3
W6
02.06.95
32
7.25
3215
2158
129
29
443
238
175
864
562
10
0.30
133
-4.29
-28.3
11.4 0.9
+1.0
(Sacc)
05.06.96
29
6.95
138
2954
2034
103
81
393
217
196
700
711
10
0.35
128
-3.97
-27.2
13.0 1.1
+0.8
01.02.97
22
7.68
3648
2064
164
43
390
217
203
729
692
10
0.34
128
-4.52
-29.0
10.2 1.1
+1.0
57
Tab.1-b
sample
date
T
(C)
pH
W7
02.06.95
50
6.39
(Berenati)
04.06.96
47
6.51
-20
01.02.97
45
6.14
W8
02.06.95
36
(Rifici)
04.06.96
31
31.01.97
34
18
H
()
140
-4.59
-30.9
14.2 1.0 +1.65 0.05
142
-4.28
-25.5
13.4 1.1
+1.8
0.33
110
-4.19
-27.5
10.9 1.0
+3.5
0.35
145
-5.28
-33.0
9.3 0.9
+2.6
0.20
147
-5.66
-35.0
9.1 1.0
+2.5
410
0.24
144
-5.61
-33.8
7.1 0.8
+2.6
TDS
Ca
Mg
Na
Cl
SO4 HCO3 H3BO3 Br
3629
3142
339
19
441
162
134
1654
263
14
0.25
3536
2398
275
18
428
179
161
983
505
15
0.30
4298
2764
328
22
432
183
161
1290
543
17
6.48
4169
4043
665
85
249
169
230
1996
293
6.70
175
3816
2838
519
70
182
133
229
1141
504
26
6.50
4309
3486
661
74
145
109
205
1651
Eh cond.
SiO2 O
()
S(SO4)
H
(T.U.)
()
W9
03.06.95
29
6.80
2516
1491
45
32
346
134
357
412
325
14
1.20
76
-4.90
-30.1
11.9 1.0
+4.8
(O. Maggiore)
05.06.96
30
6.36
122
1918
1234
70
23
258
110
301
304
188
14
1.20
76
-5.37
-31.2
9.5 0.9
+5.2
W12
05.06.96
28
6.95
138
3140
2006
110
54
485
130
424
578
389
11
0.80
66
-5.46
-32.1
11.0 1.1
+2.8
04.06.95
26
6.10
2115
1211
83
41
250
115
271
215
471
0.40
103
-5.86
-34.6
7.1 0.9
+6.35 0.05
W14
04.06.95
26
6.12
2880
1754
174
78
288
153
324
416
482
0.50
90
-5.53
-32.8
6.8 0.8
+5.7
(Messina 2)
05.06.96
26
6.10
158
2860
1621
171
69
291
152
283
354
496
0.55
84
-5.30
-31.9
5.5 0.7
+5.2
31.01.97
22
6.87
3135
1462
132
65
270
148
267
290
453
0.48
95
-5.80
-35.4
4.4 0.6
+5.3
W15
04.06.95
38
6.92
4915
3804
244
38
709
230
311
1933
315
20
0.30
125
-3.26
-23.1
13.3 1.1
+1.2
(Pisci)
04.06.96
40
6.97
151
4555
3685
232
38
682
196
329
1898
149
16
0.50
96
-3.49
-23.9
11.6 1.1
+1.5
W16
02.06.95
23
6.98
1445
885
75
22
166
61
231
164
202
0.45
74
-5.81
-32.6
7.1 0.6
+6.5
(Natoli)
05.06.96
23
6.97
128
1314
738
74
22
138
48
181
111
195
0.45
72
-6.22
-36.0
6.8 0.9
+5.9
31.01.97
18
7.27
1186
612
47
14
115
29
146
110
183
0.48
82
-6.71
-41.8
4.9 0.8
+7.3
+4.8
(Frizza)
W13
(Messina 1)
W17
02.06.95
33
7.12
5653
3411
82
104
837
249
1070
780
653
20
3.50
74
-4.29
-28.0
15.3 1.2
(Natale 1)
05.06.96
25
7.06
134
3193
1894
60
43
499
141
418
556
554
18
1.00
62
-4.90
-29.5
12.3 1.1 +3.55 0.05
W18
04.06.95
23
7.00
1524
967
51
20
178
97
288
181
120
0.55
75
-5.41
-32.7
8.9 0.9
+5.4
(Eden Park)
05.06.96
25
7.21
117
1724
1037
69
30
171
92
294
204
116
0.70
75
-5.43
-31.4
9.5 1.1
+5.1
31.01.97
17
7.55
1892
997
63
23
177
84
305
172
112
0.58
82
-5.63
-33.6
7.1 0.8
+5.9
04.06.95
22
7.41
802
335
101
29
24
10
38
22
446
<1
0.10
13
-7.10
-42.6
9.0 0.9
W20
04.06.95
24
6.87
7260
4432
343
156
932
209
1315
1308
807
23
2.75
50
-5.78
-34.0
6.7 0.9
+5.7
(Scarcella)
05.06.96
25
6.96
119
10254
7201
409
161
1823
220
2921
1114
508
17
9.03
43
-5.58
-33.0
5.1 0.9
+9.3
01.02.97
14
8.07
2177
994
59
24
272
62
273
171
395
4.24
52
-6.32
-39.2
4.6 0.6
+8.0
W19
(Scrivo)
58
Tab.1-c
sample
date
T
(C)
pH
W21
02.06.95
21
7.25
(Conti)
05.06.96
20
7.34
26
02.02.97
17
7.94
W22
03.06.95
29
(Della Chiesa)
05.06.96
32
01.02.97
W23
(Scaffidi)
Eh cond.
34
18
H
()
S(SO4)
H
(T.U.)
()
40
-6.27
-38.0
7.7 0.9
+4.4
37
-6.63
-39.5
7.9 0.9
+6.4
0.95
72
-6.14
-38.3
5.6 0.7
+6.0
0.75
80
-5.36
-32.8
8.6 0.9
+4.7
10
1.15
64
-5.37
-32.3
6.8 0.9
+4.4
14
1.25
85
-5.67
-34.8
7.0 0.8
+5.3
837
25
0.10
123
-4.33
-30.2
12.2 1.1
+3.6
601
22
1.05
91
-4.49
-32.6
8.4 0.9
+3.6
572
541
25
0.90
118
-4.53
-31.1
8.6 0.8
+3.3
273
1591
262
0.3
103
-6.07
-34.1
10.7 1.1
+3.3
315
1566
181
0.45
103
-5.98
-34.8
8.1 0.9
+2.8 0.2
SO4 HCO3 H3BO3 Br
TDS
Ca
Mg
Na
Cl
3715
2128
116
49
494
169
544
573
612
12
1.30
2402
1377
106
36
333
115
351
279
517
1.10
2713
1368
107
30
303
72
400
263
400
6.75
1955
1279
43
29
275
117
347
302
184
6.84
128
2330
1375
58
31
299
136
361
330
189
24
5.96
2177
1136
51
26
229
94
322
239
151
03.06.95
41
6.87
4261
2562
55
52
673
226
439
852
04.06.96
39
7.06
161
3411
2001
54
28
574
171
362
621
31.01.97
32
7.50
3671
1907
50
32
493
170
361
W24
04.06.95
31
5.98
3891
3362
528
82
206
160
(Martello)
06.06.96
24
6.10
160
4150
3439
556
86
218
149
SiO2 O
()
01.02.97
21
6.74
5153
3616
615
95
241
167
353
1537
514
0.4
115
-5.57
-32.2
6.6 0.8
+3.0
W25
04.06.95
28
5.74
2012
1302
161
36
144
90
150
477
340
0.25
84
-5.82
-32.9
5.9 0.7
+3.3
(Capitti)
05.06.96
26
5.74
155
1583
1009
196
28
90
43
115
322
360
0.20
58
-5.89
-32.9
6.6 0.8
+3.2
31.01.97
21
6.27
935
434
103
12
60
10
69
59
326
0.22
40
-8.17
-54.4
3.6 0.6
+4.7
04.06.96
30
7.41
180
3089
1976
58
36
554
156
368
565
517
21
1.1
118
-4.86
-31.8
8.1 0.9
+3.7
11.06.96
22
6.8
2434
1287
118
41
320
70
336
198
597
13
0.65
63
-6.38
-37.3
12.9 1.2
+6.5
W26
(Gitto)
W27
(Tripepi)
W28
05.06.96
56
6.94
11
3609
2219
66
628
272
215
825
717
15
0.85
124
-3.58
-29.3
13.8 1.0
+2.4
(Vanaxel)
31.01.97
57
7.32
4013
2005
47
567
285
229
653
772
17
0.62
144
-3.70
-29.5
14.0 1.0
+2.6
W29
05.06.96
26
6.44
150
2382
1386
167
68
166
96
252
345
450
0.50
81
-6.42
-38.9
4.9 0.8
+3.2
(Ferlazzo 2)
31.01.97
19
7.23
2075
1132
156
55
120
59
168
296
308
0.45
90
-6.07
-36.6
4.3 0.8
+1.8
W29b
01.02.97
21
6.53
3739
2208
404
48
220
105
325
722
532
10
0.55
82
-6.30
-39.5
5.6 0.8
-0.7
05.06.96
30
7.22
132
3182
1859
63
49
495
154
486
404
601
18
1.15
77
-5.06
-31.4
10.2 0.8
+3.8
(Bambara)
W30
(Natale 2)
W31
05.06.96
30
7.02
70
2964
1855
33
75
460
148
362
527
538
11
0.70
91
-4.78
-32.5
11.7 1.1
+2.6
(Muscara)
02.02.97
25
7.42
3215
1594
66
67
374
136
307
393
598
13
0.60
88
-4.98
-31.7
9.3 0.9
+2.5
W32
05.06.96
27
7.30
124
1768
992
59
24
202
61
259
221
177
1.20
77
-5.53
-32.5
7.6 0.9
+5.4
(Mandarano)
01.02.97
22
7.95
2018
996
45
20
253
49
245
240
223
12
0.95
70
-5.96
-36.1
6.6 0.8
+5.5
59
Tab.1-d
sample
date
T
(C)
pH
Eh cond.
TDS
Ca
Mg
Na
Cl
SO4 HCO3 H3BO3 Br
34
18
H
()
S(SO4)
H
(T.U.)
()
SiO2 O
()
W33
05.06.96
28
7.29
128
2870
1780
52
32
521
119
357
495
340
22
1.30
98
-5.59
-35.0
8.1 1.0
+2.9
(Alongi)
31.01.97
39
6.91
3135
1576
50
40
392
119
351
378
430
48
0.85
122
-5.67
-33.5
6.5 0.9
+3.0
W33b
31.01.97
36
7.27
1334
627
14
10
151
99
112
105
292
0.22
88
-6.00
-35.4
11.3 1.0
+3.4
+12.9
(Distributore)
W34
06.06.96
24
6.79
105
173160
24017
438
700
5996
1445
11083
2493
781
26
36.15
32
-3.22
-18.3
5.2 0.6
(C. Togo-Togo)
01.02.97
14
8.22
16952
9050
219
270
2184
626
4321
799
441
14
14.07
28
-2.76
-22.7
5.8 0.7 +12.75 0.05
SF
06.06.96
44
6.33
9776
7422
404
291
1345
373
2032
2136
647
30
6.35
114
-4.38
-26.7
6.9 0.8
C6a
02.06.95
-7.46
-42.8
5.1 0.7
(rainwater from domestic cistern)
05.06.96
220
111
28
<1
14
18
20
79
<1
0.03
-7.28
-40.4
4.9 0.9
+2.9
+2.1
+5.4
(Federico's spring water)
01.02.97
14
5.41
308
127
36
<1
15
20
22
88
<1
0.03
-7.04
-40.5
4.8 0.8
C22a
05.06.96
272
134
18
<1
22
17
29
31
68
<1
0.08
-7.36
-44.9
3.8 0.6
-2.2
(rainwater from domestic cistern)
01.02.97
16
8.26
331
145
20
<1
26
18
29
33
66
<1
0.07
-7.29
-43.1
4.2 0.7
-2.15 0.05
SW1
05.06.95
7.48
77400
38945
471
1347 11582
380
19738
3190
164
27
65
<1
+1.23
+9.1
3.0 0.8
05.06.95
7.56
78200
39228
479
1355 11708
385
19884
3150
165
27
70
<1
+1.20
+8.8
2.4 0.6
+20.2
01.02.97
14
7.99
38932
418
1292 10768
438
19759
2741
180
32
65
(seawater Est 1)
SW2
(seawater Est 2)
SW3
(seawater West)
LIPARI ISLAND SAMPLES

SC
07.06.96
48
7.29
166
2662
1800
72
94
359
47
202
702
436
0.4
112
-5.14
-29.3
1.5 0.7
+4.3
07.06.96
51
6.72
-68
2673
1732
69
34
469
83
736
210
110
2.35
38
-6.08
-34.0
2.4 0.7
+14.7
(St. Calogero's spring water)

WL
(AGIP's well)
cond. = conductivity in s/cm at 25C; all other concentrations in mg/kg. - = not analysed.
60
Tab.2
Oxygen isotope composition of the sulfate from selected water samples.
18O(SO4) 18O(H2O)
()
()
34S(SO4)
()
sample
date
T(C)
SO4
(mg/kg)
W0
04.06.1995
31.01.1997
73
74
1903
1566
+9.4
+8.5
-2.68
-2.73
+3.1 0.2
+2.8
W1
06.06.1995
02.02.1997
48
44
927
519
+8.7
+8.1
-5.12
-5.37
+2.6
+2.8
W2
05.06.1995
52
1944
+9.4
-0.55
+3.0
W4
02.06.1995
65
1525
+7.1
-2.30
+0.6
W8
31.01.1997
36
1651
+10.5
-5.61
+2.6
W17
02.06.1995
33
780
+7.6
-4.29
+4.8
W28
31.01.1997
57
653
+9.0
-3.70
+2.6
W34
01.02.1997
14
806
+7.5
-2.76
+12.75 0.05
61
Tab.3
Strontium isotope composition from selected water samples and parameters used for the water(condensate)-rock interaction models.
Oxygen
Strontium
SAMPLES DATA
W0 (04.06.1996)
-2.76
0.704656
W2 (04.06.1996)
+0.72
0.704659
W4 (04.06.1996)
-1.94
0.704638
W7 (04.06.1996)
-4.28
0.704729
W17 (05.06.1996)
-4.90
0.706070
W20 (05.06.1996)
-5.58
0.706576
W21 (05.06.1996)
-6.63
0.708290
W23 (05.06.1996)
-4.49
0.704596
W28 (05.06.1996)
-3.58
0.704719
W34 (06.06.1996)
-3.22
0.707648
W34 (02.01.1997)
-2.76
0.707732
MODEL PARAMETERS
meteoric water
(w,i)
fumarolic condensate
(w,i)
Vulcano volcanic rocks
(r,i)
Cr/Cw
-6.4b
+6.36b
+4.5c +0.165673d
+7.7e -0.05321f
0.5
100000
-8g
isotopic fractionation
factors (250 C)
water-rock
a
b
c
d
e
f
g
Sr isotope -values are calculated as [(Rsample/0.7047) - 1] x 1000.

Data from McArthur, 1994.
Data from Capasso et al., 1999 and Goff and McMurtry, 2000.
Average value from La Fossa lava samples (Gioncada et al., 1995).
Data from Ellam and Harmon, 1990.
Average value from "Caldera di La Fossa" and "Complesso della Lentia" volcanostratigraphic units (De Astis et al., 1997).
Value calculated at 250C using water-feldspar reaction (ONeil and Taylor, 1960).
62

Chemical and Isotopic Compositions of The Shallow Groundwater System of Vulcano Island, Aeolian Archipelago, Italy: An Update

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Chemical and Isotopic Compositions of The Shallow Groundwater System of Vulcano Island, Aeolian Archipelago, Italy: An Update

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Boschetti T, Cortecci G, Bolognesi L (2003) - Chemical and isotopic compositions of the shallow groundwater system of Vulcano Island, Aeolian

Archipelago, Italy: an update. GeoActa 2, 1-34

Chemical and isotopic compositions of the shallow groundwater system of

Tiziano Boschetti1, Gianni Cortecci2* and Luca Bolognesi3

Dipartimento di Scienze della Terra e Geologico-Ambientali, University of Bologna, Piazza

*Corresponding author: tel. +39-051-2094944; fax: +39-051-2094904

erratum/corrigendum version (2014-12-22 update) for info: Tiziano Boschetti (work@tizianoboschetti.com)

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2. Sampling and analytical procedures

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Sr/88Sr value of 0.1194 in natural strontium. Repeated analyses of NIST

SRM 987 standard during the period of interest yielded an average

0.710224 0.000006 (n =26).

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3. Results and discussion

3.1 Temporal changes in the temperature values

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3.2 Chemical results

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3.2.1 Classification of the waters by the statistical approach

3.2.2 Boron and bromine

3.2.3 Chemical geothermometry

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3.3 Isotopic results

O-enrichment in the W34 water sample of 1997, coupled with the

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3.3.2 3H content of water

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3.3.3 2H vs Cl- and 18O vs Cl- relations

3.4 Sulfur and oxygen isotopes of sulfate

S of the mineral relative to crater-type fumarolic

S and Cl- relative to waters W0

and W2, water W4 may be considered steam-heated rather than geothermal.

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S-depletion in sulfate W29 in 1997 with respect to 1996 may be

S, followed by dilution with shallow

3.5 Strontium isotopes

Sr/86Sr ratios were used in

(1994) for the seawater

Sr/86Sr ratio that is assumed to be equal also for sea-spray and

4. Relations between groundwaters and volcanic fluids.

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Giggenbach, W.F., 1988. Geothermal solute equilibria Derivation of Na-K-Mg-Ca

Giggenbach, W.F., 1993. Reply to comment by P. Blattner: "Andesitic water": a phantom of

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Razack, M., Dazy, J., 1990. Hydrochemical characterization of groundwater mixing in

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Simonson, J.M., Palmer, D.A., 1993. Liquid-vapor partitioning of HCl(aq) to 350C.

Yanagisawa, F., Sakai, H., 1983. Thermal decomposition of barium sulphate-vanadium

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