ELSEVIER Journal of Volcanology and Geothermal Research 75 ( 1997) 25 l-270

The Pantelleria caldera geothermal system: Data from the

hydrothermal minerals
Paolo Fulignati, Giuseppe Malfitano, Alessandro Sbrana *
Dipartimento di Scienze della Terra, Universid di Piss, Via S. Maria, 53, 56126 Pisa, Italy

Received 8 September 1996; accepted 15 September 1996

Abstract

This paper proposes, on the basis of petrographic and mineralogic data on cutting and cores from two deep wells
(Pantelleria 1 and Pantelleria 2), the first model of the active hydrothermal system of the island of Pantelleria.
Phyllosilicates were studied in detail because they are considered key minerals in the identification of hydrothermal
processes. The results of these studies emphasize differences between the intracaldera and pericaldera areas of the island.
Within the 45 ka caldera there is a high-temperature (240-260C at 600-800 m depth) active hydrothermal system with five
zones of characteristic alteration minerals with increasing depth. Rocks are unaltered to a depth of 200 m, contain smectite
and mixed-layer chlorite-smectite (C/S) between 200 and 380 m, chlorite, illite, chalcedony and quartz from 380 to 500 m,
albite, adularia and saponite from 500 to 680 m, mixed-layer biotite-vermiculite from 680 m to the depth drilled (1100).
Outside the caldera, but near the rim, a low-temperature and low-permeability (< 140C) hydrothermal system is
characterized by smectite, dolomite and ankerite at depths of 390 to 650 m, chlorite and calcite at 650-900 m, and mixed
layers of chlorite-smectite, illite-smectite and iron carbonates (ankerite, siderite) from 900 m of the well at 1203 m. The
superimposition of hydrothermal mineral assemblages is evidence for cooling in the hydrothermal system both inside and
outside the caldera. We propose that a high-temperature hydrothermal system developed inside the caldera. In an early stage
in the area surrounding the subvolcanic body, biotite isograd is reached and an alkali-metasomatism zone develops inside the
body itself. This phase may also account for the development of a chlorite-albite-adularia zone extending to 400 m. A
cooling phase (nearly 50C) followed, resulting in the substitution of biotite by mixed-layer biotite-vermiculite and by the
crystallization of Fe-rich saponite instead of chlorite, within the currently active reservoir. A cooling phase has also been
identified in the well outside the caldera.

Keywords: hydrothermal alteration; phyllosilicates; saporite; chlorite; mixed layers; geothermal system; Pantelleria

1. Introduction channel. The subaerial portion of the island consists

of the eruption of pantellerite and trachyte lava-flows
The island of Pantelleria is a Pleistocene-Recent and domes, and ignimbrites from caldera-forming
volcanic complex in the continental rift of the Sicily pyroclastic eruptions between 300 ka and 4 ka. The
chemical composition of the erupted magmas is typi-
cal of a continental rift environment, and varies from
* Corresponding author. Fax: + 39-50-500675; e-mail: alkalic basalts, dominant in the northern part of the
sbrana@dst.unipi.it. island (Mahood and Hildreth, 1986; Civetta et al.,

0377-0273/97/$17.00 Copyright 0 1997 Elsevier Science B.V. All rights reserved.

PII SO377-0273(96)00066-2
252 P. Fulignati et al./ Journal of Volcanology and Geothemtal Research 75 (19971251-270

19881, to pantellerites and trachytes forming the
central-southern part of the island. The latter is
dominated by a polyphased nested caldera (Mahood
and Hildreth, 1986). This structure probably formed
during collapse following two major explosive erup-
tions in two main phases, the oldest occurring around
114 ka, and the youngest at around 45 ka (Mahood
and Hildreth, 1986). The caldera of Pantelleria has
an uplifted central part, because of resurgence inside
the caldera (volcano-tectonic horst of Montagna
Grande) in recent times, between 18 and 4 ka (Ma-
hood and Hildreth, 1983, 1986; Civetta et al., 1988).
A geological sketch map of Pantelleria is shown in
Fig. 1.
Steaming ground, mofettes and hot springs CT,,,
98C) are found throughout the island, for example,
in the Fossa de1 Russo, Montagna Grande, and Bagno
dellAcqua areas, and particularly in the intra- and
pericaldera zone. This is evidence of a still active
hydrothermal field.
In the period 1990-94, two deep exploration wells
were drilled (Fig. 1) as part of a geothermal research
project involving geophysical, thermal, geochemical
and geological surveys. The boreholes showed the
existence of a high-enthalpy geothermal field in the
central part of the island, in the youngest caldera
structure (Chierici et al., 1995a,b).
The aim of this paper is to propose a model of the
hydrothermal system, located in the subsurface of the
island, based on petrographic and mineralogical data.

0 1 2 3h-n P. Limani

Fig. 1. Strnctural sketch map of Pantelleria island (from Chierici et al., 1995a,b, modified). 1 = tectonic lineaments; 2 = main intracaldera
volcanic vents (trapdoor-hingeline volcanic vents of Mahood and Hildreth, 1986); 3 = Montagna Grande volcano-tectonic horst border
faults; 4 = La Vecchia caldera rim (114 ka); 5 = Cinque Denti caldera (Green Tuff caldera) rim (45 ka); 6 = thermal springs and steaming
ground areas; 7 = PpTl and PPT2 geothermal wells.
 P. Fulignati et al. / Journal of Volcanology and Geothemud Research 75 (1997) 251-270
2. Materials and methods
This work was developed using cuttings and cores
coming from the deep wells Pantelleria 1 and 2.
Petrographic study in thin section was followed
by diffractometric studies for the identification of the
phyllosilicates and by SEM-EDS microanalysis.
X-ray diffraction: Clay size (< 2 pm> fractions
from powdered cuttings were prepared by standard
sedimentation techniques for X-ray diffraction
(XRD). Seven analyses of oriented samples were
performed after the following treatments: (1) air
drying; (2-3) saturation with ions K+ and Mg2+; (4)
glycolation using ethylene glycol in a desiccator at
60C; and (5-6-7) heating at 100, 300, and 550C.
X-ray diffraction patterns were obtained using a
Philips diffractometer PW 1710 at 36 kV and 24 mA
using CuK (Y .
SEM-EDS: Polished thin sections were studied
using a SEM-EDS PV 9900 at 20 kV beam current
and about 10 nA. Quantitative analyses were ob-
tained using a Philips HAX software using ZAF
correction.
3. Petrography and authigenic mineral distribu-
tion
3.1. Well Pantelleria I
The deep well Pantelleria 1, located in the south-
em sector of the Pantelleria caldera (Fig. 11, cuts
through 700 m of ignimbrites and lavas which show
a trachytic-comenditic chemical composition; below
700 m the well is in a subvolcanic intrusive body,
which is a peralkaline-syenite with comenditic affin-
ity (Fig. 2). Petrographic study allowed the identifi-
cation of five different mineral alteration zones:
Zone (1) (O-200 m) unaltered
Zone (2) (200-380 m) smectite and mixed layers
of chlorite-smectite (C/S)
Zone (3) (380-500 m) chlorite, illite, quartz
Zone (4) (500-680 m> albite, adularia, saponite
Zone (5) (680-I 100 m> mixed layers of biotite-
vermiculite
3.1.1. Zone 1 (O-200 m)
In this interval the host rocks are represented by
unaltered porphyritic trachytic-comenditic lavas,
253
which can be correlated with the Monte Gibele lavas
filling the Cinque Denti caldera. Below 150 m there
are low-crystallinity smectites as an alteration of the
glassy groundmass of host rocks and also opal filling
the cavities of the lavas.
3.1.2. Zone 2 (200-380 ml
In this interval the primary rocks are trachytic
comenditic lava flows and the ignimbritic unit of the
Green Tuff, Fig. 2, with pantelleritic composition at
the base and comenditic at the top. Smectites and
mixed layers of C/S develop as alteration products
at the expense of the glassy groundmass and of the
clinopyroxene and anortoclase phenocrysts. In addi-
tion, pyrite is well developed and from 247 m down-
wards calcite occurs.
3.1.3. Zone 3 (380-500 rn)
The primary lithology is represented by a thick
comenditic ignimbritic unit (Fig. 2). Hydrothermal
alteration is widespread. The secondary minerals
characterizing this interval are chlorite (restricted to
400-460 m>, present both in veins and as an alter-
ation of phenocrysts, illite, present in the whole
interval, and adularia, appearing below 460 m. A
strong silicization of the ignimbrite is present in this
interval, chalcedony is present up to 450-470 m and
quartz develops below this depth with pervasive
style. Both chlorite and mixed layers occur in associ-
ation with calcite and sulphides in replacing the
anorthoclase, with only sulphides if alteration re-
places aegirine-augite. Sulphides are abundant, and
below 465 m, in association with pyrite, sphalerite
was found as small anhedral aggregates surrounded
by euhedral crystals of pyrite. Sulphides seem to
replace primary oxides of the ilmenite-magnetite
group. Illite is abundant in the interval 385-435 m
as replacement of anorthoclase. A quartz-adularia
assemblage was found in microfractures below 470
m. This zone could represent the cover of the
geothermal field developed by self-sealing processes.
3.1.4. Zone 4 (500-680 rn)
Below 500 m, the host rock consists entirely of
lavas, which appear strongly brecciated (core of
601-611 m) between 600 and 650 m. In this zone
there is the disappearance of chlorite and mixed
layers of C/S and the appearance of saponite as
254 P. Fulignati et al. /Journal of Volcanology and Geothermal Research 75 (1997) 251-270

Measured
Temperatures

600 - -t
I

600 -
I
I
900 -

lOOO-
t
I I
I
llOO-

w ignimbrites w laws q subintrusive body

Fig. 2. Distribution of authigenic minerals, hydrothermal zones and stabilized temperatures (from Chierici et al., 1995a,b) in Pantelteria 1
well.

dominant phyllosilicate. The saponite-sulphides as- groundmass is formed of feldspars, aenigmatite, ar-
semblage substitutes microphenocrysts and phe- fvedsonite, aegirine-augite and quartz; the chemical
nocrysts of aegirine-augite in part or completely. composition of this rock is similar to the trachytes of
When the alteration involves anorthoclase, the previ- the post Green Ignimbrite Monte Gibele volcanic
ous assemblages are associated with calcite. center (SiO, 65%, Ce 154 ppm, La 86 ppm,
The anorthoclase is less stable in this zone than at Sr87/Sr86 0.70345 + 2).
shallower levels; in some crystals there is total albiti- Hydrothermal alteration reaches a depth of 1000
zation. The quartz-adularia assemblage appears more m and decreases downwards; it is scarce in the last
developed than in the previous zone associated with 50 m probably due to the reduction in permeability
sphene. Pyrite is the most abundant sulphide; of the subvolcanic body. This zone is characterized
pyrrotite and sphalerite occur in smaller quantities. by the appearance of mixed-layer biotite-vermicu-
lite. This mineral is found, sometimes associated
3.1.5. Zone 5 (680-1100 rn) with sulphides and sphene, as irregular aggregates
In this zone there is a transition from trachytic- overlying anorthoclase and more rarely aegirine-
comenditic lavas to a sub-volcanic unit having a augite. Crystals of epidote are rarely present as an
mineral paragenesis consisting of anorthoclase, sani- alteration of anorthoclase. This mineral always shows
dine, aegirine-augite, fayalitic olivine in reaction to evidence of instability (resorption) represented by
clinopyroxene and arfvedsonite phenochrysts. The calcitic reaction rims. The presence of fractures and
 P. Fufignati et al. / Journal of Volcanology and Geothemtd Research 75 (1997) 251-270 25.5

veinlets filled by a quartz-adularia assemblage is we can find an alternation of pantelleritic ignimbritic

widespread to 850 m. Below this depth the crystals
of anorthoclase are influenced by a strong process of
hydrothermal albitization. The presence of high-tem-
perature hydrothermal minerals like biotite and the
appearance of chess board and veinlet structures,
caused by the base exchange reaction of Na for K in
the crystals of anorthoclase (albitization), are charac-
teristic of alkali metasomatism zones (Pirajno, 1992).
3.2. Well Pantelleria 2
The second well is located just north of the
caldera rim (Fig. 3). In the first 180 m of this well
units with interbedded pantelleritic pumiceous layers.
Below 180 m there is a totally different sequence
made up of alkali-basaltic scoriaceous lavas and
hyaloclastitic lavas intersected by doleritic dikes in
the lower part (Fig. 3).
The hydrothermal mineral association in the Pan-
telleria 2 drillhole is different from the other well,
reflecting both a lower thermal grade and different
host-rock lithology.
Four alteration zones have been distinguished
based on optical observation:
Zone 1 (O-390 m) unaltered rock
Zone 2 (390-650 m) smectite, dolomite, ankerite
association

hkawred
Temperalures
b Lilhology
a,

I
600 I I

900

Fig. 3. Distribution of authigenic minerals, hydrothermal zones and stabilized temperatures (from Chierici et al., 1995a,b) in Pantelleria 2
well.
256 P. Fulignati et al. /Journal of Volcanology and Geothermal Research 75 (1997) 251-270
Zone 3 (650-900 m> chlorite, calcite association
Zone 4 (900-1203 m> mixed layers, iron carbon-
ates (ankerite, syderite) association
3.2.1. Zone I (O-390 ml
The host rock here is mostly pantelleritic and
trachytic ignimbrite, and in this zone hydrothermal
alteration is almost completely missing. At about 270
m we observe some microcrysts of plagioclase in
basaltic lavas partially replaced by smectites and
carbonates. Chalcedony is present inside cavities and
microfractures.
3.2.2. Zone 2 (390-650 rn)
The beginning of this zone coincides with the
transition from scoriacious alkali-basaltic lavas to
lavas with interbeds of hyaloclastites. Generally, hy-
drothermal alteration becomes more pervasive in this
interval, particularly below 550 m.
As regards secondary mineral association, carbon-
ates occur as a substitution for the glassy ground-
mass and carbonates plus smectites as a substitution
for clinopyroxenes. There is noteworthy deposition
of mordenite, a hydrothermal mineral of the sodic
zeolites group. In this case, the mordenite is often
associated with carbonates. Near 600 m, fibrous
aggregates of illite replace plagioclase crystals. From
640 m on, quartz occurs.
3.2.3. Zone 3 (650-900 ml
The host rock is represented by basaltic hyalo-
clastites with minor interbeds of lavas and some
doleritic dikes. Hydrothermal alteration is very strong
and is characterized by well crystallized chlorite,
present at 710-750 m, associated with calcite and
corrensite. Corrensite, associated with mordenite, re-
places plagioclase microcrystals and hyaloclastite
clasts. Quartz and albite microveins occur as sec-
ondary minerals in this zone.
3.2.4. Zone 4 (900-1203 ml
The host rock seems to be like the previous zone
except for an increase in subvolcanic lithologies
(Fig. 3). This zone is characterized by the presence
of swelling chlorite and the lack of chlorite as a
secondary mineral in the hyaloclastites. Corrensite is
observed as far as a depth of 1000 m. In these
lithologies, the secondary mineral association is: car-
bonates + mordenite + corrensite + swelling chlo-
rite. Among the carbonates there is the association:
calcite + siderite + breunnerite + ankerite; illite is
present only at 900 m. In doleritic levels carbonates
and a smectite similar to zone 2 develop.
In the last 50 m, in the doleritic dikes rectorite, a
regular mixed-layer illite-smectite phyllosilicate ap-
pears; this mineral substitutes clinopyroxene crystals.
Quartz is abundant throughout this interval.
4. Chemistry of the hydrothermal minerals and
XRD data
The study of the minerals was carried out using
EDS microanalysis. The phyllosilicates group was
the object of particular study also by X-ray powder
diffractometry (XRD). The following minerals were
identified: feldspars, quartz, sulphides, carbonates,
sphene, barite, apatite and phyllosilicates.
4.1. Pantelleria I drillhole
4.1.1. Feldspar
Hydrothermal feldspars identified here are repre-
sented by albite and adularia. These phases were
found from 462 m to the bottom (Table 1). Both
albite and adularia in this well show a stoichiometric
composition which does not change with increasing
depth.
4.1.2. Carbonates
Calcite is the only carbonate identified and its
chemical composition is quite homogeneous (Table
2); Ca is always more than 90 mol% with rare
substitution of Mn, Fe.
4.1.3. Sulphides
The sulphides present are pyrite and sphalerite;
the first is more abundant and sometimes it shows
substitutions of Zn for Fe. At 462 and 600 m spha-
lerite was found; sphalerite analysis at 462 m indi-
cates little FeS (4 mol%), Ni and Mn. The amount of
FeS in the analysis of sphalerite at 600 m is less than
at 462 m, in fact, it remains under 1.5 mol% and
there are no traces of Mn and Ni.
 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270 257

Table 1
Average structural formulas of adularia and albite
Adularia Albite
Depth (m): 462 528 600 685 1035 462 600 765 1035
No. of deter-m.: 1 6 1 1 1 1 2 6 3
Na,O 0.00 0.52 0.35 0.52 11.93 11.70 11.53 11.92
AW, 18.46 18.24 18.52 18.51 17.56 19.40 19.37 19.73 19.18
SiO, 64.13 64.12 64.15 64.02 64.29 67.06 68.54 68.29 68.39
K2O 16.28 16.53 15.91 16.36 15.63 0.12 0.07 0.20 0.12
CaO 0.00 0.09 0.00 0.18 0.15 0.09 0.10 0.15 0.07
TiO, 0.35 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MnO 0.00 0.00 0.00 0.00 0.12 0.00 0.00 0.00 0.00
Fe@, 0.23 0.23 1.15 0.00 1.87 0.18 0.21 0.05 0.32
Sum 99.45 99.73 100.08 99.59 99.62 98.78 99.99 99.95 100.00
Si 2.98 2.98 2.97 2.97 2.98 2.97 3.00 2.99 2.99
Al 1.01 1.00 1.01 1.01 0.96 1.01 1.00 1.02 0.99
Ti 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mn 0.00 0.00 0.00 0.00 0.00
Fe3+ 0.01 0.01 0.04 0.00 0.07 0.01 0.01 0.00 0.01

Na 0.00 0.00 0.03 0.05 0.00 1.02 0.99 0.98 1.01

K 0.97 0.98 0.94 0.97 0.93 0.01 0.00 0.01 0.01
Ca 0.00 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.00

Structural formulas have been calculated on the basis of 8 oxygens

Table 2 4.1.4. Sphene

Average structural formulas of sphene
Sphene analysis indicates some substitution of Al
Sphene and Fe3+ for Ti and, more rarely, Na for Ca (Table
Depth (m): 610 685 2). The abundance of sphene seems correlated with
No. of determinations: 5 3 the high-Ti content of Pantelleria volcanics.
Na,O 0.00 1.69
MgO 0.00 0.47 4.1.5. Other secondary minerals
A1203 5.54 1.14
Besides the previously mentioned minerals, other
SiO, 32.35 31.42
K2O 0.05 0.24
neogenic phases were identified: such as a subordi-
CaO 28.49 24.99 nate amounts of stoichiometric barite and rare-earth
TiO, 27.20 28.93 rich apatite at 600 m.
Fe0 5.49 6.45

4.2. Clay minerals

Sum 99.12 95.33

Si 1.07 1.10 Five minerals of the phyllosilicates group were

identified: saponite, chlorite, mixed-layer chlorite-
Mg 0.00 0.02 smectite, illite, mixed-layer biotite-vermiculite. The
Al 0.22 0.05
XRD data are reported in Table 3.
Ti 0.68 0.76
Fe 0.15 0.19 To calculate structural formulas, 22 Ox was used
for saponite, illite and mixed-layer biotite-vermicu-
Na 0.00 0.11 lite; 28 Ox for chlorite and mixed-layer C/S.
K 0.00 0.01
Ca 1.01 0.93
4.2.1. Saponite
Structural formulas have been calculated on the basis of 5 oxy- Saponite was found from 500 m tn; this mineral
gens. has a characteristic d,, of 14.8 A after MgCl,
258 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 11997) 2.51-270

Table 3
XRD data

Depth d,, (A,

(ml WA Glicole etil. KC1 (550C) iden. phases

320 14.71 17.11 12.30 9.94 Sm, C/S

401 14.55 10.17 7.18 16.96 15.00-14.7-10.10 7.18 14.30-13.72 9.97 Ch, C/S, Ill, Sm
500 15.10 10.18 7.16 17.02 10.00 7.12 13.94 9.76 Sm, C/S, Ill
609 14.81 7.33 17.09 9.86 Sm
670 14.90 17.14 10.02 Sm
800 14.79 16.98 9.91 Sm
905 14.76 16.99 9.99 Sm
1000 14.78 13.23 16.96 13.17 12.71 9.97 Sm. Hyd
1100 13.88 16.69 10.09 Sm

Table 4
Average structural formulas of saponites
Saponites

Depth cm): 462 500 610 715 835 905 970 1035
No.of determ.: 8 6 21 6 13 16 5 I

SiO, 45.67 49.84 49.27 45.29 44.40 43.73 45.22 45.71

TiO, 0.00 0.00 0.00 0.00 0.15 0.14 0.13 0.00
Al,% 8.05 6.89 7.51 8.30 8.85 8.48 8.63 8.68
Fe0 * 33.35 25.62 25.59 34.74 33.52 35.89 31.64 29.24
MnO 0.19 0.00 0.59 0.33 0.41 0.21 0.61 0.37
Mg 9.64 15.09 14.09 8.08 8.44 8.48 9.61 11.93
CaO 2.46 2.14 2.13 2.27 2.25 2.50 2.18 1.88
Na,O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
K,O 0.37 0.37 0.24 0.67 1.94 1.59 1.94 I .88

Total 99.73 99.95 99.48 99.68 99.96 99.78 99.96 99.69

Si 6.66 6.93 6.89 6.66 6.54 6.53 6.60 6.59

Al(W) 1.34 1.07 1.11 1.34 1.46 1.47 1.40 1.41

Al(W) 0.04 0.06 0.14 0.10 0.08 0.02 0.08 0.06

Ti 0.00 0.00 O.Oll 0.00 0.02 0.02 0.01 0.00
Fe 4.07 2.98 2.99 4.28 4.13 4.48 3.86 3.53
Mn 0.02 0.00 0.07 0.04 0.05 0.03 0.07 0.04
Mg 2.09 3.13 2.94 1.77 1.85 1.61 2.09 2.56

Total 6.22 6.17 6.14 6.19 6.13 6.16 6.11 6.19

Ca 0.38 0.32 0.32 0.36 0.36 0.40 0.34 0.29

Na 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
K 0.07 0.06 0.04 0.13 0.36 0.30 0.36 0.35

Total 0.45 0.38 0.36 0.49 0.72 0.70 0.70 0.64

Total cat. 14.67 14.55 14.50 14.68 14.85 14.86 14.81 14.83

Fe/Fe + Me 0.66 0.49 0.50 0.7 1 0.69 0.74 0.65 0.58

Structural formulas have been calculated on the basis of 22 oxygens; total iron has been considered as ferrous.
 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270
treatment. This expands to 17 & with ethylene glycol
solv$ion and collapses at 13 A and between 9.8 and
10 A after treatment with KC1 and after heating at
55OC, respectively.
Analysed saponites (see Table 4) are Fe-rich and
poor in Al like those described in the groundmass of
rhyolitic tuffs at Oya, Japan (Kohyama et al., 1973);
these were defined by this author as Fe-saponites. K,
Ca and, in a smaller quantity Mg, are the interlayer
cations.
Below 650 m smectites show a progressive in-
crease of interlayer cations. In particular, there is an
increase of K+(X) and a noteworthy substitution of
A13+ for Si4+ in the tetrahedral sites. Such a substi-
tution is supposed:
K+(X) + A13+(IV) * Si4+(IV)
The increase of A13+(IV) and K+ seems to be
related to a rise in temperature. We think this substi-
tution was not produced by a variation in rock
chemistry because chemical analyses showed quite a
homogeneous composition throughout the well. The
increase of cations in (X) sites with increasing depth
(Table 4) shows an increase of layer charge: We pass
from a charge of 0.43-0.46 at 600 m to 0.70-0.73
between 835 and 905 m. At the bottom of the well
intermediate layer charges such as 0.60-0.65 (these
values are calculated on the basis of the Mg,(Si,
21-
q chlorite (401m)
l mixed layers c/S (401m)
0 mixed layers US (462m)
20~ 0 sapcmite (500.1000m)
n smectite (528m)
16-
151 I r
0 1
Fig. 4. PPTl well. Sum of the major non-interlayer cations (Si + Al + Fe + Mg) versus Al. All analyses recalculated
on a diagram proposed by Schiffman and Fridleifsson (1991).
259
Al),O,,(OH), formula unit) were found. According
to the classification of Suquet and PCzerat (19881,
based on layer charge values (saponites X < 0.5 and
vermiculites X > 0.7; in the interval between 0.5-0.7
it is not possible to distinguish saponites and vermi-
culites), a transition from saponites (600 m) to ver-
miculites (835-905 m) was observed. Intermediate
terms occur from 905 m and at the bottom of the
well. However, XRD study never identified vermi-
culite; therefore, if we consider that we are not sure
of the difference between high-charge smectites and
low-charge vermiculites based on chemical data, we
can consider all these phyllosilicates as high-charge
trioctahedral smectites. As regards the saponites of
this well, the Fe/Fe + Mg ratio is another parameter
which changes with depth. This ratio is equal to
0.48-0.52 at 600 m, increases to 0.74-0.76 at 905 m
and then it decreases to 0.58-0.59 at 1035 m. Below
835 m, saponite has a small amount of Ti. At 528 m
and up to 350 m, there was also identification of
dioctahedral smectites, probably interstratified with
saponites (Fig. 4).
4.2.2. Chlorite
Chlorite as a discrete phase was oaly identified at
401 m. Chlorite has d,, of 14.5 A after MgCl,
treatment. This value undergoes very small varia-
tions both after ethylene glycol solvation and after
chlorite
I
2 3 4 5 6 7
Al128 Ox
on 28 Ox basis. Based
260 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270

heating at 550C (14.3 A). The limited variation in
d,, after ethylene glycol treatment probably repre-
sents a combination of discrete chlorite and chlorite-
rich mixed-layer C/S (Schiffman and Fridleifsson,
1991; Purvis, 1990). EDS analyses of chlorite are
shown in Table 5.
Considering the classification of Bayliss (Bayliss,
1975) these chlorites are defined as Fe-clinochlore or
Mg-chamosites. Chemical analyses show Fe/Fe +
Mg and Al/Al + Fe + Mg relations of 0.69 and
0.3 l-0.33, respectively. The chlorites analyzed show
octahedral vacancy of 0.3-0.5 mo1/28 Ox. This
vacancy in the octahedral sites represents a common
characteristic of chlorites of hydrothermal origin
(McDowell and Elders, 1980; Bettison and Schiff-
man, 1988; Cathelineau, 1988; Schiffman and Fri-
dleifsson, 1991; Shau and Peacor, 1992).
4.2.3. Mixed-layer chlorite-smectite
Mixed-layer C/S were identified between 320
and 500 m. XRD study of this interlayered C/S
showed wider and less defined peaks than discrete
chlorite; this means these are random interlayers.
The d,, is 14.5 A after MgCl, treatment, which

Table 5
Average structural formulas of chlorites, mixed layers C/S, phengites and mixed layers biotite-vermiculite

Chlorites Mixed-layer C/S Phengites Mixed-layer biotite-vermiculite

Depth (m): 407 407 462 407 1035 835 970 1035
No. of determ:. 3 6 7 2 1 3 5 3

SiO 2 32.13 34.39 37.71 57.88 60.75 43.39 42.93 44.47

TiO, 0.00 0.00 0.06 0.00 0.00 0.22 0.22 0.31
A203 18.25 17.86 12.80 18.07 14.36 8.22 10.32 10.62
Fe0 * 37.88 36.44 36.93 12.40 9.33 32.21 27.69 27.89
MnO 1.89 2.27 0.86 0.00 0.23 0.53 0.34 0.33
MgO 9.24 7.89 10.29 2.32 3.90 8.94 11.55 10.73
CaO 0.55 0.61 1.04 0.20 0.21 1.20 1.11 1.05
Na,O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
K2O 0.00 0.47 0.25 8.95 10.36 5.25 5.70 4.55

Total 99.94 99.93 99.94 99.82 99.14 99.96 99.86 99.95

Si 6.24 6.62 7.21 7.60 7.98 6.49 6.30 6.44

Al(W) 1.I6 1.38 0.79 0.40 0.02 1.51 1.70 1.56

AI 2.42 2.67 2.10 2.40 2.20 0.00 0.08 0.25

Ti 0.00 0.00 0.01 0.00 0.00 0.02 0.02 0.03
Fe 6.15 5.87 5.91 1.36 1.02 4.03 3.40 3.38
Mn 0.31 0.37 0.14 0.00 0.03 0.07 0.04 0.04
Mg 2.67 2.26 2.93 0.45 0.76 1.99 2.53 2.32

Total 11.55 11.17 11.09 4.21 4.01 6.11 6.07 6.02

Ca 0.11 0.13 0.21 0.03 0.03 0.19 0.17 0.16

Na 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
K 0.00 0.11 0.06 1.50 1.73 1.00 1.07 0.84

Total 0.11 0.24 0.27 1.53 1.76 1.19 1.24 1.oo

Total cat. 11.66 19.41 19.29 13.74 13.77 15.30 15.31 15.02

Fe/Fe + Mg 0.70 0.72 0.67 0.75 0.57 0.67 0.57 0.59

Structural formulas have been calculated on the basis of 22 oxygens for phengites and mixed layers biotite-vermiculite, and 28 oxygens for
chlorites and mixed layers C/S; total iron has been considered as ferrous.
 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 2.51-270
expands to 15 A after ethylene glycol solvation, and
ultimately collapses to 13.7 A after heating at 550C
with an asymmetrical peak. This asymmetry indi-
cates the presence of smectite in the mixed-layer
C/S (Bettison-Varga et al., 1991). The percentage of
chlorite in the mixed-layer C/S was derived approx-
imately by using the diagram of Fig. 5. In this case,
a dcm, of 15 A represents 80% chlorite.
Table 5 shows EDS analyses of these interlayers.
It is possible to distinguish the mixed-layer C/S
from chlorite (Fig. 6) due to their greater number of
interlayer cations (Na, K, Ca > 0.10 cations/28 Ox)
and to a greater amount of Si(IV) cations (> 6.25
cations/28 Ox) (Bet&on and Schiffman, 1988). The
diagram of Fig. 4 represents compositional differ-
ences between smectite, chlorite and their interlayer
terms. Along the straight-line between saponite and
chlorite there are terms that are more stable with
increasing temperature. Along the saponite-beidel-
lite straight-line, terms are stable with decreasing
temperature (Schiffman and Fridleifsson, 1991). The
spots corresponding to phyllosilicate analyses at 407
m fall near the saponite-chlorite straight-line and
they are very near the chlorite composition. Analyses
of interlayers at 462 m fall in the middle of the
saponite-chlorite straight-line, showing a higher
amount of saponite than chlorite analyzed at 407 m.
At 500, 528 and 600 m our analyses indicate almost
discrete saponites; the EDS data therefore confirm
the results of the XRD study. In this well we note
quite a progressive transition from chlorite to saponite
with depth, contrary to other geothermal wells stud-
% chlorite
Fig. 5. Peak migration curves for ethylene glycol solvated, ran-
domly interstratified 001 chlorite/O01 smectite (after Reynolds,
1980).
261
Fig. 6. PPTl well. Sum of interlayer cations (Na + Ca + K) versus
Si content of smectite, saponite, C/S and chlorite. All analyses
recalculated on a 28 Ox basis.
ied (McDowell and Elders, 1980; Cathelineau et al.,
1985; Schiffman and Fridleifsson, 1991). The
Fe/(Fe + Mg) ratio varies from 0.48 to 0.75 and
does not seem correlable with saponite-chlorite tran-
sition. In fact, some saponites have the same Fe/Fe
+ Mg value as chlorite and mixed-layer C/S.
4.2.4. Illite
Illite was found between 400 and 500 m and at a
depth of 1000 m. XRD analyses give a d,, of
10.1-10.2 A in the sample treated with MgCl,; after
K+ treatment and heatirtg at 550C d,, collapses to
approximately 9.8-10 A. This is perhaps caused by
the presence of smectite layers inside the illite
structure. EDS analyses on illites show some substi-
tutions of Fe*+ and Mg* for A13+ in the octahedral
sites, so we can consider these micas as phengites.
The amount of K is always less than 2 (22 Ox). At
407 and 1035 m illites were found with K of 1.5 and
1.73 cations, respectively. The filling of interlayers
of illites and particularly the amount of K, generally
present a good positive correlation with the tempera-
ture of crystallization (Cathelineau, 1988). This
agrees with the thermometric log of the well.
4.2.5. Biotite-vermiculite
Mixed-layer biotite-vermiculite was identified
below 685 m. The X-ray investigation shows a d,,
of 13.3 A in the sample saturated with Mg*+. It does
not change after ethylene glycol treatment, while it
collapses to 12.7 A after K treatment and heating at
550C.
262 P. Fulignati et al./Joumal of Volcanology and Geothermal Research 75 (1997) 251-270

interval. The analyses show little substitution of Ca

for Na (K is always absent) and Fe3+ for A13+
(Table 6).

4.3.2. Calcite
In the Pantelleria 2 well, calcite occurs at depths
between 600 and 1100 m. Particularly between 700
. and 900 m calcite is the only carbonate which was
0.0
0.0 0.5 1.0 1.5 2.0 found. The calcite analyzed shows little substitution
K of Fe, Mg and Mn for Ca.

W 4.3.3. Dolomite
Dolomite occurs only at a depth of 500 m; the
analyses show a stoichiometric composition with
small amounts of Fe per Mg.

4.3.4, Siderite
Siderite is rarely found as a pure phase. The most
1
. .
I common cations which substitute Fe+ are Mn+
0.0 0.5 1.0 1.5 2.0 and Mg2+ and there is a totally solid solution be-
K tween siderite and rhodocrosite and between siderite
Fig. 7. PPTl well. Variation diagrams of Ca and Fe + Mg versus and magnesite. In this well pistomesite is found
K for biotite-vermiculite mixed layers. (30% < MgCO, < 50%) from 400 m of depth except
in the interval of 750-900 m. Sideroplesite (5% <
MgCO, < 30%) is quantitatively subordinate to the
EDS study revealed the presence of Ca (Table 5)
in the structure of this interlayer. Ca shows a nega- Table 6
tive linear correlation with K (Fig. 7a), whereas Average structural formulas of albite and mordenite
(Fe + Mg) has an almost constant value with varying Mordenite Albite
K (Fig. 7b). For this reason we may affirm that Ca is
Depth (m): 1100 750 900
the dominant interlayer cation in the vermiculite No. of determinations: 6 2 3
layers, while Mg occurs in small quantities (Mc-
Na,O 5.65 10.81 10.94
Dowell and Elders, 1980). As regards biotite, the K MgO 0.26 0 0
leaching and Ca enrichment trend is usually corre- Al,% 13.03 20.19 22.64
lated with an increase of vermiculite alteration (Craw, SiO, 78.77 68.47 64.74
K,O 0.80 0 0
1981; Craw et al., 1982; Moon et al., 1994). There-
CaO 1.15 0.32 0.16
fore, these investigated phyllosilicates can be consid- Fe&+ 0.08 0.16 0.14
ered as biotites partially transformed into vermi-
Sum 99.74 99.95 98.62
culites. A similar case was observed for mixed-layer
biotite-vermiculite in a Salton Sea geothermal well Si 40.16 2.98 2.87
(McDowell and Elders, 1980). The Mg/(Mg + Fe) Mg 0.20 0 0
Al 7.83 1.04 1.18
value generally increases with depth.
Fe3+ 0.04 0 0

4.3. Borehole Pantelleria 2 Na 5.58 0.91 0.94

K 0.52 0 0
Ca 0.63 0.01 0.01
4.3.1. Albite
Albite is the only hydrothermal feldspar identified Structural formulas have been calculated on the basis of 8 oxy-
in this well and it was found only in the 750-900 m gens for albite and 96 oxygens for mordenite.
 P. Futignafi et af. / Joumat of VoJcanology and Geothermal Research 75 f1997)251-270 263

Table 7
Average structural of calcite, dolomite, breunnerite, siderite and ankerite
Calcite Dolomite Breunnerite Siderite Ankerite

Depth (m): 600 750 900 1100 500 600 500 1100 1200 500 1100 1200
No. of determ.: 3 3 3 2 3 4 4 6 1 4 7 1

MO 1.49 0.19 0.81 1.21 42.79 45.79 24.27 19 26.35 29.87 28.75 28.63
CaO 94.01 97.84 97.3 92.9 55.4 15.3 4.22 7.38 3.98 48.52 5 1.23 46.27
MnO 1.63 1.13 1.02 2.54 0 0 2.26 4.33 0 1.22 0.83 1.16
Fe0 2.85 0.71 0.84 3.32 1.77 37.75 68.39 69.27 69.66 20.37 18.53 23.92

Sum 99.98 99.87 99.97 99.97 99.96 98.84 99.14 99.98 99.99 99.98 99.34 99.98

0 1 1 1 1 2 1 1 1 1 2 2 2

Mg 0.02 0 0.01 0.02 1.02 0.59 0.36 0.29 0.39 0.78 0.75 0.75
Ca 0.94 0.98 0.97 0.94 0.95 0.14 0.05 0.08 0.04 0.91 0.96 0.88
Mn 0.01 0.01 0.01 0.02 0 0 0.02 0.04 0 0.02 0.01 0.02
Fe 0.02 0.01 0.01 0.03 0.02 0.27 0.57 0.59 0.57 0.3 0.27 0.35

pistomesite and was identified only at a depth of
1100 m (Table 7).
4.3.5. Magnesite
Magnesite forms a completely solid solution with
siderite while the substitutions of Mn and Ca for Mg
are limited. Magnesite-rich Fe is defined as breun-
nerite and it can contain Fe between 5 and 50 mol%
(Deer et al., 1967). Breunnerite was found at 600
and 1100 m depth. The amount of FeCO, in these
analyses varies from 17 to 35 mol% without any
relation with depth.
4.3.6. Ankerite
In the Pantelleria 2 well we found ankerite in the
500-600 m and 1085-1200 m intervals. The compo-
sition of this mineral results uniform, showing lim-
ited substitution of Mn and Mg (max. 2 mol%).
4.3.7. Mordenite
This silica-rich zeolite is abundant between 1000
and 1115 m. The X-ray investigations reveal a char-
acteristic reflection (020) at 9.07-9.08 A. The chem-
ical composition of mordenite from the EDS analy-
ses shows a high Na content (average Na/K = 9.71).
The content in tetrahedral atoms, which can be ex-
pressed by the (Si/Si + Al) ratio, varies from 0.83
to 0.84, in agreement with the range (0.80-0.85)
known for this zeolite (Passaglia, 1975).
4.3.8. Sulphides and other minerals
Sulphides are not abundant in this well and the
only phases identified are: pyrite, in the 600-1200 m
interval and chalcopyrite, analyzed only at 750 m
depth. Other hydrothermal minerals were identified
in small quantities: anhydrite at 750 m and apatite.
4.4. Clay minerals
In the Pantelleria 2 well, five types of phillosili-
cates were identified using X-ray investigation:
smectite, corrensite, rectorite, chlorite and swelling
chlorite. X-ray analysis data are shown in Table 8.
Structural formulas are calculated on the basis of 22
Ox for smectite and rectorite; 28 Ox for chlorite and
25 Ox for corrensite.
4.4. I. Smectite
Smectite was identified throughout the well ex-
cept at 700-750 m.
In the samples of the fir$ 650 m, XRD analysis
reveals a d,, at 15.0-15.3 A after MgCl, treatment,
while below 700 m smectites have a d,, between
14.6 and 15 A. The d,, expands to 17 A after
ethylene glycol solvation for the samples from the
first 600 m. This expansion is smaller (d,, = 16.7
A) between 650 and 1000 m. Incomplete expansion
of smectite is probably caused by some percentage
264 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270

Table 8
XRD data

Depth d,, (A,

(ml M&l, Glicole etil. KC1 (550C) Iden. phases

305 15.36 17.04 9.96 Sm

385 15.54 17.17 13.51 9.75 Sm
601 14.90 17.76 9.61 9.78 Sm, Ill(?)
650 15.29 16.78 9.93 Sm
700 29.87 14.56 7.11 31.19 16.83 15.04 7.14 22.96 13.99 11.94 9.79 Ch, Co, Sm
800 29.62 14.86 7.18 30.97 16.53 14.74 7.16 13.75 12.01 9.69 Ch, Co, Sm
900 29.70 14.60 7.17 30.44 16.77 7.18 23.26 13.84 11.90 9.72 SCh, Co, Sm
1005 29.32 15.00 1.20 31.75 16.74 7.27 23.28 13.97 12.20 9.68 SCh, Co, Sm
1115 15.11 7.21 17.12 7.23 14.12 9.73 SCh, Sm
1203 24.94 14.79 12.32 7.17 26.79 17.06 13.48 7.19 22.26 10.98 10.26 Rect, Sm

of chlorite within the mineral structure. At the bot-
tom d,, corresponds to 17 A.
For eve? sample, the basal peak collapses to
about 9.8 A after KC1 treatment and heating at
550C.
Both dioctahedral(1 lo-1203 m) and trioctahedral
(900 m) smectites were identified. Trioctahedral
smectites are characterized by an Al amount higher
than saponite (Fig. 81, due to the presence of limited
chlorite interlayers in their structures. The Fe/(Fe +
Mg) ratio is very low, from 0.34 to 0.38. At 460,
600, 1100 m we found smectites with a number of
cations in the octahedral site intermediate between a
dioctahedral and a &octahedral smectite. In fact,
octahedral cations vary from 4.5 to 5.1 per formula
unit. These phyllosilicates represent dioctahedral
smectite interlayers (Fig. 8).
4.4.2. Chlorite
Chlorite was found0 between 700-800 m and it
has a d,, of 14.5 fi after MgCl, treatment; it
expands to 14.7- 15 A after ethylene glycol treat-
ment. This limited expansion means that in the chlo-
rite there are minimal amounts of expandable phyl-
losilicates such as smectites (Purvis, 1990; Schiff-
man and Fridleifsson, 1991). In the sample treated

21
Al chlorite(750m) ,
l corrensib (750.900m)
D seponite (900,1lOOm)
20- 0 chlorite
smecGte (460,600,1100,1200m)

154. 1.I. I'

0 1 2 3 0x4 5 6
Al128
Fig. 8. PPT2 well. Sum of the major non-interlayer cations (Si + Al + Fe + Mg) versus Al. All analyses recalculated on a 28 Ox basis.
Based on a diagram proposed by Schiffman and Fridleifsson (1991).
 P. Fulignatiet al./ Journal of Volcanologyand Geothemal Research 75 (1997) 251-270 265

with KCl, d,, collapses to 13.8 A after heating at
550C. By means of the diagram in Fig. 5, we can
estimate a quantity of chlorite from 80 to 95%.
EDS analyses are shown in Table 9. The chlorites
analysed can be classified as Mg-Si-chamosite, fol-
lowing the classification of Bayliss (1975).
As seen for the Pantelleria 1 chlorites, these chlo-
rites also have some octahedral vacancy of 0.50-0.35
cations. As regards the chlorites of the Pantelleria 2
well, we can not exclude, however, that the octahe-
dral vacancy in their structure could be correlated
with the presence of some smectite layers (Schiff-
man and Fridleifsson, 1991). In fact, structural for-
mulas of these chlorites have Si > 6.25 cations/28
Ox, which represents the highest value for a discrete
chlorite (Bettison and Schiffman, 1988). The Fe/(Fe
+ Mg) ratio is between 0.46 and 0.50.
4.4.3. Swelling chlorite
This particular type of chlorite typically expands
after ethylene glycol solvation but does not collapse
after heating to 550C (Bain and Russel, 1981; Wil-
son, 1987). By X-ray diffraction the presence of
swelling chlorite between 900 and 1115 m was
discovered. In the sample: treated with MgCl, d,,
corresponds to 14.6-15.1 A. It expands to 16.7-17.1

Table 9
Average structural formulas of chlorites, corrensites, saponites, smectites and rector&es
Chlorites Corrensites Rectorites Saponites Smectites

Depth (m): 750 750 900 1100 1200 900 460 600 1100 1200
No. of determ.: 2 3 2 2 7 7 2 4 5 3

SiO, 34.78 37.29 38.82 36.79 56.31 50.44 60.99 62.91 62.50 67.92
TiO, 0.00 0.00 0.00 0.00 0.00 0.00 1.14 0.03 0.00 0.00
A1203 18.25 18.04 16.17 18.33 32.11 11.68 16.93 17.14 19.98 22.04
Fe0 * 28.89 27.60 14.42 26.89 1.69 17.83 12.50 10.23 6.72 4.87
MnO 0.15 0.21 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.00
MgO 17.49 15.59 19.53 16.87 0.95 17.22 4.94 6.51 5.75 3.21
CaO 0.36 0.74 0.79 0.70 1.16 1.84 1.87 2.19 1.45 0.45
Na,O 0.00 0.00 0.16 0.23 0.15 0.37 0.00 0.39 0.77 0.00
K,O 0.00 0.29 0.00 0.04 6.90 0.42 1.Ol 0.47 1.86 1.19

Total 99.77 99.76 99.89 99.85 99.27 99.80 99.38 99.87 99.06 99.68

Si 6.39 6.06 6.19 5.95 6.96 6.74 7.71 7.80 7.72 8.00
Al(IV) 1.61 1.94 1.81 2.05 1.04 1.26 0.29 0.20 0.28 0.00

Al(W) 2.34 1.51 1.23 1.44 3.64 0.58 2.23 2.30 2.63 3.09
Ti 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.00 0.00 0.00
Fe 4.44 3.75 3.26 3.63 0.17 1.99 1.32 1.06 0.69 0.48
Mn 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mg 4.79 3.77 4.64 4.06 0.17 3.43 0.93 1.20 1.06 0.57

Total 11.57 9.06 9.13 9.13 3.98 6.00 4.59 4.56 4.38 4.14

Ca 0.07 0.13 0.13 0.12 0.15 0.26 0.25 0.29 0.19 0.06
Na 0.00 0.00 0.05 0.07 0.04 0.10 0.00 0.09 0.18 0.00
K 0.00 0.06 0.00 0.01 1.09 0.07 0.16 0.07 0.29 0.18

Total 0.07 0.19 0.18 0.20 1.28 0.43 0.41 0.45 0.66 0.24

Total cat. 19.64 17.25 17.45 17.35 13.26 14.43 13.00 13.01 13.04 12.38

Fe/Fe + Mg 0.48 0.50 0.41 0.47 0.50 0.37 0.59 0.47 0.39 0.46

Structural formulas have been calculated on the basis of 22 oxygens for smectites, saponites and rectorites; 25 oxygens for corrensites; 28
oxygens for chlorites; total iron has been considered as ferrous.
266 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270

A after ethylene glycol treatment and ultimately it
presents limited contraction to 13.9 A.
4.4.4. Corrensite
Corrensite is defined as a 1: 1 regular interstratifi-
cation of trioctahedral chlorite with trioctahedral
smectite or trioctahedral vermiculite (Bailey, 1981).
Distribution of corrensite in the Pantelleria 2 well is
limited to the interval of 700-1005 m.
XRD analyses show jhat this phyllosilicate has
the d,, of 29.32-29.87 A in the sample treated with
MgCl,; it expands to 30.44-3 1.75 after ethylene
glycol solvation and collapses to about 23 A after
KC1 treatment and heating at 550C. The peak of this
last d,, is generally not clear; we note, however,
the appearance of a clear peak at 12 A, which should
be the (002) reflection (Blatter et al., 1973; Wilson,
1987; Shau et al., 1990). Corrensite data are reported
in Table 9. Fig. 9 illustrates some differences of
composition between smectite, saponite, chlorite and
corrensite. Data reported in this diagram do not show
0.8
0.7
0.6
fO.5
9 0.4
a! 0.3
0.2
0.1
0.0
0.5 0.6 0.7
Sii Si+AI
0.8
(W
0.7
0.6
a regular smectite-chlorite transition with increasing
depth, as has been found in other geothermal wells
(McDowell and Elders, 1980; Cathelineau et al.,
1985; Schiffman and Fridleifsson, 1991). At 1100 m,
for example, corrensite, swelling chlorite and diocta-
hedral smectites co-exist. This transition is probably
hidden by retrohydrothermalism which influenced
this zone.
Moreover, regarding differences of composition
between saponite, chlorite and corrensite, we note a
general increase of the Fe/(Fe + Mg) ratio with a
decrease of the Si/(Si + Al) ratio and the sum of
interlayer cations, passing from saponite to corrensite
to chlorite (Fig. 9a-b). These phyllosilicates show an
analogous trend in the analyses of hydrothermal
oceanic association of the Costa Rica rift and off-
shore Taiwan (Shau et al., 1990; Shau and Peacor,
1992).
4.4.5. Rectorite
Rectorite consists of a regular 1: 1 illite-smectite
interstratification (Wilson, 1987). It was found only
at the bottom0 of the well (1203 m). Rectorite has
d,, of 24.9 A after MgCl, treatment. The dO02ff
12.3 A is also very0 clear. d,, expands to 26.8 A,
while d,, to 13.5 A after ethyltne glycol solvation.
Finally, d,, collapses to 22.3 A and do,, to 11 A
after KC1 treatment and heating to 550C. The ap-
pearance of rectorite in the last 50 m of the Pantelle-
ria 2 drillhole is simultaneous with the disappearance
of mixed-layer C/S. The structural formula calcu-
lated by EDS analyses indicates, for this mineral, a
0.8 0.9 1 .o
relatively uniform composition (Table 91. A repre-
sentative structural formula calculated on the basis of
rectorite analyses is the following:
q chlorite
. corrensite
0 saponite

z 0.5
This mineral is K-Al rich and Na-Mg poor. It can
i
IA 0.4 be considered, therefore, as a regular interstratifica-
z 0.3 tion between K-mica layers and beidellite layers
0.2 (Kawano and Tomita, 19911.
0.1

0.0 ^,
U.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0:s 5. Chlorite geothermometer
Ca+K
Fig. 9. PPT2 well. Saponite-corrensite-chlorite compositional Chlorite composition was used to estimate the
variations in Fe/Fe + Mg versus Si/Si + Al and Ca + K diagrams. temperature of crystallization by means of a geother-
 P. Fulignati et al./ Journal of Volcanology and Geothemud Research 75 (1997) D-270
mometer proposed by Cathelineau (1988). The corre-
lation between temperature and number of Al(IV)
cations is the following:
T (C) = -61.92 + 321.98(Aliv)
based on a structural formula such as: (Fe, Mg),(Si,
Al),O,,(OH),.
Thisgeothermometer was applied to the chlorites
of 407 m for Pantelleria 1 and 750 m for Pantelleria
2. The following values of temperature were derived:
210-242C in the Pantelleria 1 well and 183-213C
in the Pantelleria 2 well. In both cases, these values
are greater than those measured by direct thermomet-
ric tests reported in Figs. 2 and 3. If this geother-
mometer is considered to be valid, then in the past
the temperature in both the wells must have been
greater than now.
6. Discussion
The geothermal wells drilled on Pantelleria island,
which led to the discovery of a geothermal field on
the island, give information about the hydrothermal
system present in the subsurface of the volcanic
complex. The structural setting of Pantelleria can be
divided into two distinct main sectors, the central
south, dominated by a resurgent active nested caldera,
the northwest dominated by basaltic eruptions (Ma-
hood and Hildreth, 1986; Civetta et al., 1988). The
results of these boreholes emphasized the differences
between the two areas, showing the presence of a
high-temperature active hydrothermal system within
the caldera and of a low-temperature, low-permeabil-
ity hydrothermal system which has developed just
outside of the caldera.
In the southern sector of the Cinque Denti caldera
(PPTl drillhole) there is a very high temperature
anomaly. Temperatures measured were 240C at 600
m and 270C at 1100 m. On the northern caldera
edge, the temperature anomaly is much smaller.
90C was measured at 600 m and 125C at 950 m
(Figs. 2 and 3).
6.1. Intracaldera area
The upper part of the geothermal field identified
is composed of rocks self-sealed by silica and clay
minerals, which represent the cover of the field.
267
These rocks develop between 200 and 500 m, on
previous ignimbritic lithologies. The reservoir is a
water-dominated type, with temperatures near boil-
ing point (Chierici et al., 1995a,b). It develops in
trachitic-comenditic lavas which are very fractured
and hydrothermalized. The reservoir, within trachitic
lavas crossed by dikes, is characterized by an associ-
ation with albite, adularia, calcite, quartz, sphene,
sulphides. Fe-saponite is the stable phyllosilicate in
this permeable zone. The simultaneous crystalliza-
tion of adularia and calcite may suggest that there
are boiling fluids, according to the measured temper-
atures (Fig. 2) in agreement with observations made
regarding other geothermal systems (Browne and
Ellis, 1970; Browne, 1978).
The permeable zone extends for several hundred
meters within a microsyenitic body strongly hy-
drothermalized to 1000 m. In this lower part of the
reservoir we can observe a change of composition of
saponite; in fact there is an increase of the layer
charge with depth and temperature.
This should suggest a probable transition from
saponite to vermiculite, defining a characteristic hy-
drothermal zone. Vermiculite has been found in lay-
ers of transition from chlorite zones to biotite zones
in other hydrothermal systems (Salton Sea, McDow-
ell and Elders, 1980) and in metamorphic settings
(Velde, 1978). The equilibrium temperatures indi-
cated by these authors completely agree with the
measured temperature of the PPTl well for the sta-
bility zone of these phyllosilicates (250-270C). The
coexistence of mixed-layer biotite-vermiculite and
high-charge saponite (vermiculite) below 680 m con-
firms the presence of a well defined hydrothermal
zone.
In a previous paper De Vivo et al. (1992), study-
ing intrusive and subvolcanic xenoliths, suggest the
lack of well developed hydrothermal systems in the
subsurface of the island. The results of our study
partially contrast these conclusions. A hydrothermal
system develops above a microsyenitic subvolcanic
body. Moreover, the outer portion of the intrusion is
affected by hydrothermal circulation.
6.2. Pericaldera area
The lithologic profile of the pericalder hydrother-
mal system is very different from that seen in the
268 P. Fulignati et al. / Journal of Volcanology and Geothermal Research 75 (1997) 251-270
previous area, showing that the drilling crosses a
sector of the volcanic complex uninfluenced by vol-
cano-tectonic collapses.
The PPT2 well, in the northwest area of Pantelle-
ria, shows a low-temperature hydrothermal alteration
( < 2OOC),similar to low-temperature areas of other
hydrothermal systems (Browne, 19781, developed
within basaltic-hyaloclastitic lithologic sequences.
The PPT2 well was drilled in a sequence self-sealed
by pervasive argillization of hyaloclastitic units and
lavas and by deposition of carbonates. This is con-
firmed by the stabilized thermic profile of the sur-
vey. The monotony of the above-mentioned hy-
drothermal system, Fig. 3, is interrupted at about 700
m by the appearance of a chlorite, corrensite, albite
and calcite association in the doleritic dikes. This
mineral association indicates the development of hy-
drothermal reactions with temperatures higher than
the low-temperature association of the rest of the
well. In particular, crystallization of calcite instead
of Fe-carbonates is correlated to a higher tempera-
ture of deposition (Browne and Ellis, 1970; McDow-
ell and Elders, 1980). This restricted hydrothermal
zone could have been created by the intrusion of the
doleritic dikes mentioned above. The prevalence of
stable Fe-carbonates in the cooling zones of the
geothermal systems (Reyes et al., 1993; Simmons
and Christenson, 1994) suggests that this pericaldera
area represents a flow area of cold fluids at the
interface with the intracaldera hydrothermal plume.
7. Hypothesis of evolution of the hydrothermal
system
The discussion of the previous paragraph con-
cerns the mineral association in equilibrium with
present temperatures referred to the cover and reser-
voir units of the intracaldera geothermal field. Some
considerations can be made about the evolution of
temperatures and about the changes in permeability
of the hydrothermal system suggested by the super-
imposition of contrasting mineral associations.
The hypothesis concerning the history of the hy-
drothermal system is the following. There is a phase
where, near the subvolcanic body, biotite isograd is
reached and a probable alkali-metasomatism zone
(trioctahedral micas and chess-board albitization) de-
velops, which influences the subvolcanic body itself.
The occurrence of alkali-metasomatism processes in
the subsoil of the island is also suggested by the
presence of high-T brines in fluid inclusions in
granitoid rocks studied by De Vivo et al. (1992).
This initial phase could be correlated with the devel-
opment of a chlorite-albite-adularia zone extending
to 400 m. After this phase, a diffused cooling phase
(nearly 50C) of the hydrothermal system follows.
This is confirmed by the substitution of biotite by
mixed-layer biotite-vermiculite and by the crystal-
lization of Fe-rich saponite instead of chlorite, within
the currently active reservoir (500-750 m). Saponite
is found as typical phyllosilicate of a high-T reser-
voir also in other geothermal fields (Miles, Greece
and Chipilapa, El Salvador); it is considered as a
characteristic metastable phase of a newly-formed
geothermal reservoir where high fracture permeabil-
ity and boiling fluid are present (Papapanagiotou et
al., 1995; Patrier et al., 1996).
The zone from 400 to 500 m, sealed by high-T
phases and silica mineral deposition, did not undergo
a re-equilibrium of temperatures of around 160C to
present temperatures probably because of the almost
total impermeability of the rocks. Chlorite-saponite
transition (Fig. 4) occurs through a zone of deposi-
tion of mixed-layer C/S at 465 m, which should
represent the transition to the currently permeable
zone.
Retrohydrothermalism is also observed in the
PPT2 well. This is evident from the coexistence of
low-T dioctahedral smectites and a corrensite-recto-
rite-swelling chlorite association. Such retrohy-
drothermalism phenomena have been observed in
several geothermal systems (Hulen and Neilson,
1986; Flexser, 1991) and they can be simply justified
by the short geological life of the hydrothermal
systems. From the point of view of connection be-
tween volcanological evolution of the island and
hydrothermal system evolution, the first phase could
date back to the 44-37 ka period, in which the
isostatic readjustment of the volcanic system after
the caldera forming Green Tuff eruption occurred.
The intrusion in the bottom of PPTl could go back
to that age, if we consider that the sub-volcanic rocks
have the same composition of the rocks erupted in
that period, as reported in the paragraph on petrogra-
phy. In this case, the cooling phase could be corre-
 P. Fulignati et al. / Joumal of Volcanology and Geothemtal Research 75 (1997) 251-270
lated to the volcano-tectonic rising of the Montagna
Grande horst between 18 and 3 ka and to subsequent
strong fracturing of the central area of the caldera,
which could have played the role of an infiltration
area for cool fluids. The possibility that the early
stage of hydrothermalism could be correlated to the
recent phase of activity (18-3 ka) is, in our opinion,
remote. This is because there is an excessively short
time interval for a phase of increasing hydrotbermal-
ism to be followed by a phase of retrohydrothermal-
ism. Moreover, the composition of the sub-volcanic
body does not match the composition of the younger
erupted products, which are pantelleritic in composi-
tion.
Acknowledgements
The authors are indebted to Gail Mahood and to
Roberto Scandone for the review of the manuscript
that greatly improved its quality. We thank Agnese
Bilancieri for the drawings. The authors gratefully
acknowledge CESEN Spa and the Ente Minerario
Sicilian0 for the permission to study the samples and
to publish the data collected in the framework of a
Research Contract between Pisa University and CE-
SEN Spa. In particular, we thank R. Nannini and R.
Chierici for the friendly collaboration and discus-
sions during the drilling of the boreholes.
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