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The Larderello geothermal field: a review

Article  in  Earth-Science Reviews · August 1991

DOI: 10.1016/0012-8252(91)90018-B

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Earth-Science Reviews, 3l (1991) 133-151 133
Elsevier Science Publishers B.V., Amsterdam

The Larderello geothermal field: a review

Angelo Minissale
Centro di Studio per la Mineralogia e la Geochimiea dei Sedimenti del C.N.R.,
c / o Dipartimento di Scienze della Terra, Via La Pira 4, 50121 Florence, Italy
(Accepted after revision September 10, 1990)

ABSTRACT

Minissale, A., 1991. The Larderello geothermal field: a review. Earth-Sci. Rev., 31: 133-151.

This paper reviews published geological, geophysical, petrological and geochemical data, together with reservoir engineer-
ing parameters, of the Larderello geothermal reservoir of southern Tuscany, Italy. Some theories are proposed on the deep
origin, evolution in time, and natural state of this geothermal field prior to its exploitation.
The interaction between the vapor-donfinated reservoir and surrounding aquifers is discussed. Analysis of hydrogeochem-
ical data suggests that meteoric waters from shallow external aquifers contribute little to the production of steam. The
vapor-dominated system and the cold external aquifers are separated by areas of very low permeability where physical
conditions change greatly over short distances.
The presence and significance of liquid phases in the peripheral areas of the vapor-dominated reservoir are interpreted as
being due to steam condensation. The latter is a consequence of: (a) low permeability conditions in the deep buried parts of
the carbonate reservoir formations in the north-northwestern sector of the field, and (b) by the mixing of ascending
superheated steam from depth with cold CaSO4 meteoric waters circulating in unconfined shallow aquifers within the outcrops
of the carbonate reservoir formations in the south-southeastern parts of the field. The presence of steam below these
liquid-dominated sectors of the reservoir seems possible.
The limited natural recharge of the system, the constant steam production rate for geothermal power generation (3000 t
h 1, since 1951), the persistence of natural thermal features, and the fact that reinjection has had little effect on the
characteristics of the fluid discharged, seem to indicate a steady state for the Larderello field. The main contribution to
production seems to be from superheated steam ascending from depth and the in situ evaporation of water stored in the small
pores of the rocks present in Larderello, in a system that is much larger than the one known at present.

INTRODUCTION
T h e g e o t h e r m a l f i e l d at L a r d e r e l l o is o n e o f
t h e few s y s t e m s p r o d u c i n g s u p e r h e a t e d s t e a m .
Various authors have studied the mechanisms
of s t e a m s u p e r h e a t i n g in n a t u r a l c o n d i t i o n s
( G o g u e l , 1953; F a c c a a n d T o n a n i , 1964;
J a m e s , 1968; S e s t i n i , 1970; W h i t e et al., 1971),
a n d a n exhaustive analysis of these mecha-
nisms can be found in Truesdell and White
(1973). It is n o w g e n e r a l l y a c c e p t e d t h a t the
s u p e r h e a t e d s t e a m a t L a r d e r e l l o is p r o d u c e d
by the massive transfer of heat from the rocks
to the f l u i d . W i t h the e x c e p t i o n o f t w o wells
in the s o u t h e r n p a r t of the field that discharge
a t w o - p h a s e f l u i d , all t h e o t h e r s p r o d u c e su-
p e r h e a t e d s t e a m . T h e r e is n o e v i d e n c e f r o m
t h e d i s c h a r g e o f t h e wells, o f l i q u i d w a t e r
b e i n g p r e s e n t in the reservoir. A mass b a l a n c e
b a s e d o n the total c u m u l a t i v e p r o d u c t i o n of
t h e f i e l d (26 M t / y s i n c e a t l e a s t 1 9 5 1 ; C h i e r i c i ,
1961), h o w e v e r , s u g g e s t s t h a t t h e s t e a m p r o -
d u c e d at L a r d e r e l l o m u s t be stored in the
r e s e r v o i r as w a t e r ( M a r c o n c i n i et al., 1977),
unless the steam reservoir e x t e n d s b e l o w the
M o h o , as p r o v o k i n g l y r e p o r t e d b y J a m e s
(1968).
In their conceptual model of v a p o r -
d o m i n a t e d s y s t e m s , W h i t e et al. (1971) s u g -
gested that water r e m a i n e d t r a p p e d in the
rock m a t r i x a n d in the smaller fractures, even
t h o u g h steam was the p r e s s u r e - c o n t r o l l i n g

0012-8252/91/$06.65 ~:~1991 - Elsevier Science Publishers B.V.

134
phase in the larger fractures. After analyzing
the production data of Larderello and The
Geysers (USA), Truesdell and White (1973)
calculated that 30-50% was the highest per-
centage of volume of water in the small pores
in the vapor-dominated reservoir at Larde-
rello. In this condition of water saturation the
vapor is still the pressure-controlling phase.
Following studies on numerical simulation in
systems with a two-phase fluid flow in a
fractured porous medium, Pruess and Nara-
simhan (1982) state that, for matrix permea-
bility of less than 3-5 #darcies, conditions for
the persistence of a vapor-dominated regime
may exist even in the presence of 100% water
saturation in the reservoir.
Another critical point as regards vapor-
dominated systems is the recharge of the sys-
tem in the absence of hydrodynamic regimes.
Goguel (1953), Bozza (1961) and Sestini
(1970) proposed that the main contribution to
the production of a vapor-dominated re-
servoir comes from deep fluids at supercriti-
cal conditions. As early as 1963, however, the
meteoric origin of the steam produced at
Larderello (Craig, 1963; Ferrara et al., 1965)
had been identified by analysis of the isotopic
composition of steam condensate. As a logi-
cal consequence it was assumed that this
meteoric contribution came from the out-
crops of carbonate reservoir formations in the
southern part of the field (Cataldi et al., 1963).
Further studies on the hydrological balance
of the Larderello area, however, concluded
that only one third of the total production of
ii~il
A.MINISSALE
steam could be accounted for by the water
from these areas (Petracco and Squarci, 1975).
As regards the water reserves in the system,
White et al. (1971) assumed in their model the
presence of a deep boiling brine below the
vapor-dominated reservoir. Exploitation of
this brine would provide the greatest contri-
bution to production. In their model of the
Larderello field, D'Amore and Truesdell
(1979) regarded the high chlorine content of
some of the wells as being due to increased
contributions of steam derived from evapora-
tion of this brine. Evaporation would increase
after exhaustion of the condensates present in
the reservoir before exploitation.
The literature available on the Larderello
field has been reviewed in order to place this
field within the framework of the post-oro-
genic hydrothermal activity of the entire geo-
thermal region of Tuscany, to contribute to
our understanding of the physical limits of
the vapor zone, and, finally, to reconstruct
the evolution of the field in time.
GEOLOGICAL BACKGROUND
The Larderello geothermal field is located
in the pre-Apennine belt of southern Tuscany
(Fig. 1). This area has been characterized by
extensional tectonics since the Late Miocene.
Sporadic compressive stages occurred in the
Pliocene. The result of these tectonic phases is
a block faulting structure with N W - S E trend-
ing horsts and basins. Small post-orogenic
granitic stocks were emplaced along the main
Angelo A. Minissale, born December 25, 1954 in
Florence, Italy. Graduated in Geology in 1979 at
the University of Florence. From 1981 to 1985
researcher in Geothermics at the National Geo-
thermal Unit (Italian Electricity Agency) in Pisa.
Since 1985 researcher in Geochemistry at the
Italian National Research Council (C.N.R.) c/o
Earth Science Department, University of Florence.
 THE LARDERELLO GEOTHERMAL FIELD 135

axes of the uplifted structures. The anoma- The stratigraphic sequence (Cataldi et al.,
lous heat flow that marks the Larderello area 1963) consists of the following tectonic units
is likely to be related to one of these intru- in descending order:
sions (Abbate et al., 1970; Kligfield, 1979; (a) post-orogenic sediments, mainly alter-
Puxeddu, 1984; for comprehensive reviews of nating clays, sands, and conglomerates
the Apennine geology). (Miocene-Present);

~ / -~-°o;+~x
~ .,-4

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ZZZ
--
o ,ok.,

~~-~W=
~. ~,
~:LARDERE LLOL4
l~8~'~'~'~:!~
.'.'.'.'.'.'.'.','.-.'," '.'"
:::::::::::::::::::::::
~q.R/VALE~
'~

-- Pb

;~I'Pb -Zn

A LLOOHTHONOU$ ~ ~ ~ ~ ~

[ff~ ~ s ~ v o , ~ . ~ -\/-" -ARO~R~u.o \

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_

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~¢) M O N T E R O T 0 N OC)~ ~ * " ~ ~ , ¢ ' - ~ *..~L..,~_I'-I'-T~

~

~';,

~-/" i ~ ~', : :':,':: ','!

?; :::::::::::::::::::::: ::i
Fig. 1. Schematic geological map of the Larderello-Travale geothermal region. In the upper part of the figure the
Larderello and Travale geothermal fields, the outcrop areas of the carbonate reservoir formations as well as the main
mineralized areas in southern Tuscany are reported.
136
(b) allochthonous Ligurian nappes, mainly
pelitic, with e m b e d d e d ophiolite blocks
(Jurassic- Eocene);
(c) Tuscan nappe, mainly carbonatic at the
bottom, clastic at the top (Middle Triassic-
Oligocene);
(d) regional polymetamorphic basement
composed of phyllites, mica schists, and
gneisses (Paleozoic).
Units (a) and (b), in the Larderello area,
act as cap-rock formations for the geothermal
reservoir. The carbonate parts of unit (c) and,
to a lesser extent, unit (d), form the main
reservoir.
BRIEF HISTORICAL OUTLINE OF THE LARDE-
RELLO REGION
The natural thermal manifestations of the
Larderello region ( k n o w n also as the
"boraciferous region"), have been well known
since R o m a n times (Fiumi, 1943). Remains of
a R o m a n thermal bath can still be seen near
Monterotondo. Products of the thermal
manifestations (sulfur, alum, boric acid,
vitriol, coloured clays, etc.) were used in the
Middle Ages for pharmaceutical and pottery
(Marinelli, 1963).
The modern history of Larderello is traced
from the beginning of the last century when
Count Francois De Larderel left France, as a
refugee from the French Revolution, and be-
gan the industrial exploitation of the boric
acid discovered at the end of the eighteenth
century in the areas of natural steam vents.
There are no precise data on the nature of the
fluid in the reservoir and at the surface at that
time. We do know that, in 1850, De Larderel's
sons realized that boric acid was mostly asso-
ciated with steam vents, rather than with the
associated water in the vent pools, the latter
being dependent on steam condensation and
on weather conditions (Nasini, 1930). It is,
however, very likely that in some areas of the
field, the natural fluid emerging at the surface
was superheated steam. Lotti (1910) reports
that steam emerged at 190°C from a well
that could not have been deeper than 50-100
A. MINISSALE
m considering the drilling technology of that
time. Since equilibrium pressure at this tem-
perature is around 12 bars, a liquid phase is
not likely to have been present at that depth.
So it is probable that the natural boiling
pools ("lagoni") often contained meteoric
water and bubbling steam ("soffione").
Travellers passing through the Larderello
region in past centuries (Targioni-Tozzetti,
1769) were probably impressed by the large
quantities of steam erupting violently from
the ground, which accounted for the name
"soffioni". Today, after over a century of
industrial exploitation, only a few areas pro-
duce weak jets of steam naturally. Some of
these jets have died a natural death, but most
of them have been artificially drained to pre-
vent the formation of dangerous pools. Shal-
low wells have also been drilled in the "lag-
oni" areas. Some of these wells are still pro-
ducing, and probably they have trapped most
of the steam that would have reached the
surface directly.
It is worth noting that the areas that pro-
duced, and still to some extent produce, steam
are the ones where the carbonate reservoir
either crops out or lies at shallow depth
(Cataldi et al., 1969). These natural steam
vents were never stable features on the
landscape, appearing in different spots, espe-
cially in the Sasso area, because of self-sealing
phenomena. Self-sealing was mostly caused
by the boric acid and ammonia bicarbonates
present in the steam, as well as by the various
carbonates, sulphates and phyllosilicates of
calcium, magnesium, ammonium, etc. that
formed after dissolution of CO 2 in the pools,
oxidation of associated H2S by atmospheric
oxygen, and alteration of country rocks. The
vents moved around so frequently that when
someone wanted to wish bad luck on a
neighbour, he would say: " m a y a vent spring
out in your field". Thus, large fossil zones of
alunitization, kaolinization, silicification, etc.
are scattered over vast areas of the boracifer-
ous region.
Many thermal springs can be found in this
area. As reported by Duchi et al. (1986), they
THE LARDERELLO GEOTHERMAL FIELD
are mostly low-salinity, neutral-pH, C a l i C O 3
waters, whose origin is meteoric, and whose
thermal characteristics are a result of the very
high thermal gradient in the Larderello area.
Besides steam, large quantities of gas were,
and are still to some extent, emitted in the
areas of the "lagoni". No recent data are
available on natural gas/steam ratios, Nasini
(1930) reported a maximum 10% gas content
in the natural steam vents. This ratio was not
constant, and varied from zone to zone owing
to the different condensation rates of steam
in local low-permeability zones, as well as to
precipitation.
GEOPHYSICAL O U T L I N E OF T H E LARDERELLO
REGION
Geophysically, the boraciferous region is
characterized by a negative gravity anomaly
(Mouton, 1969; Cataldi et al., 1970), despite
the fact that the crystalline metamorphic
basement at Larderello is in a position of
relative structural height. According to
Calamai et al. (1976) this and other negative
anomalies in central Italy (e.g. Mt. Amiata
geothermal region) are located in areas with
maximum values of heat flow and geothermal
gradient. This anomaly has led to the assump-
tion that in the Larderello there may be a
granite mass at moderate depth (Marinelli,
1963, 1969). In support of this theory, Villa et
al. (1987) have reported the existence of some
aplitic veinlets in a recently drilled deep well.
In the last few years seismic prospecting
has been carried out to explore deep produc-
tive horizons in the metamorphic basement
(Bernardi et al., 1976). These surveys have led
to the identification of a continuous reflecting
horizon, from 3 to 7 km in depth (Batini et
al., 1978, 1985a; Batini and Nicolich, 1984).
The nature of this horizon is still being de-
bated, whether it is the top of an Hercynian
granite, or an Alpine granite, a mineralized
horizon, or a particular fractured zone con-
taining supercritical fluid (Batini et al.,
1983b). However, as reported in Cappetti et
al. (1985), it is certainly the best candidate for
137
future exploration for very high enthalpy
fluids.
Recent data on natural seismic activity in
the Larderello area (Batini et al., 1980, 1984,
1985b) have indicated the release of elastic
energy throughout the region, with particular
intensity near Monterotondo.
The whole of southern Tuscany, including
the Larderello area, is characterized by a shal-
low Moho (about 20-25 km depth; Boccaletti
et al., 1986), compared to that of the Apen-
nine ridge (about 35-40 km; Nicolich and
Pellis, 1979; Calcagnile and Panza, 1979;
Giese et al., 1981).
ORE DEPOSITION, M E T A M O R P H I S M A N D RE-
SERVOIR H Y D R O T H E R M A L ACTIVITY
Apart from fluid inclusions in hydrother-
mal minerals (Belkin et al., 1983, 1985), no
deep liquid phase has ever been observed in
the middle of the Larderello geothermal field.
Nevertheless, many hydrothermal mineral as-
semblages are present in the main carbonate
reservoir rock and in the metamorphic base-
ment. Early investigations on this subject were
carried out by Marinelli (1969). Recent data
from deep drilling begun in 1974 (Bertini et
al., 1980) have led to the following recon-
struction of hydrothermal activity.
Two Hercynian metamorphic events oc-
curred (Batini et al., 1983b): the first reached
medium grade, with quartz, muscovite, chlo-
rite, kinked biotite, andesine plagioclase, and
almandine, with tourmaline, apatite, zircon,
and ilmenite as accessories. The second re-
ached higher temperatures (500 ° C) at lower
pressures (Abukuma type), with andalusite,
cordierite, and newly formed biotite. All these
assemblages underwent retrogressive meta-
morphism during the Apennine orogeny. Both
relict wollastonite and andradite crystals have
been interpreted as evidence of the thermo-
metamorphic Hercynian event (Del Moro et
al., 1982; Batini et al., 1983a, b).
Hydrothermal mineral assemblages formed
during the Apennine orogeny, and reported
by Cavarretta et al. (1980a,b, 1982, 1983), are
138
grouped into three assemblages of increasing
temperature. The first is found where the
temperature is from 150 ° to 250°C, and is
characterized by the presence of calcite,
anhydrite, pyrite, and quartz in the overlying
flyschoid formations, in the upper part of the
carbonate reservoir, and in the most periph-
eral zones of the field. The second assemblage
is found where the temperature is from 200 o
to 300 ° C and comprises the same minerals as
the first, plus K-feldspar, K-mica, hematite,
and sphene, and can be found in the main
carbonate reservoir. The third group is found
where the temperature is from 250 o to 350 o C
and is comprised of K-feldspar, epidote, chlo-
rite, sphene, and sulphides which are preva-
lent, with prehnite, datolite, diopside-heden-
Fig. 2. Map of the upper surface of the main carbonate reservoir or basement (elevation in m above sea level) in the
Larderello-Travale geothermal region.
A.MINISSALE
bergite solid solution, tremolite-actinolite so-
lid solution, and albite as minor phases. These
minerals characterize the deepest and hottest
part of the field. Recent papers (Batini et al.,
1983a; Cavarretta et al., 1983; Bertini et al.,
1985) describe minerals of an Alpine meta-
morphic aureole in St. Pompeo 2 and VC 11
wells. Chiastolite, corundum, and tourmaline
are the main phases. The presence of xenob-
lastic rims of sanidine around c o r u n d u m
crystals was ascribed by Batini et al. (1983b)
to the breakdown of muscovite according to
the reaction (Chatterjee and Johannes, 1974):
muscovite = sanidine + c o r u n d u m + H 2 0
The physical conditions for such a reaction
are temperature of 6 0 0 ° C and pressure of
THE LARDERELLO GEOTHERMAL FIELD
1000 bar. This last paragenesis, like the aplitic
veinlets, suggests the proximity of an Alpine
granite, as does the widespread occurrence of
abundant tourmaline, which is commonly
found in the contact aureoles of the Tuscan
granite intrusions.
As can be concluded from this brief out-
line, hydrothermal activity in the Larderello
area was extremely complex. Much of south-
ern Tuscany was, throughout the Pliocene
and later, involved (see Fig. 1) in P b - C u - Z n
sulfides, pyrite, skarn, and H g - S b ore deposi-
tion (Tanelli and Lattanzi, 1983; D e h m et al.,
1983).
SPATIAL DISTRIBUTION AND TEMPORAL
EVOLUTION OF T E M P E R A T U R E S A N D PRES-
SURES IN T H E FIELD
This section describes the distribution of
temperature, pressure, and permeability
within the geothermal system before its ex-
ploitation, and the evolution of these parame-
ters with time.
Figure 2 (from Bertini et al., 1984) is a map
of the top of the main potential carbonate
reservoir (or basement when carbonates are
lacking), which descends from outcrops in the
southern and eastern parts of the field to over
1500 m in depth in the newly explored west-
ern part of the field. Two structural highs can
be identified: the Serrazzano-Monterotondo
and Larderello-Castelnuovo ridges. The nat-
ural steam emissions are located on the
structural tops of Serrazzano, Larderello,
Castelnuovo, Sasso, Monterotondo, Lago, and
Lagoni Rossi (Fig. 2). Drilling for the boric
acid industry and later for steam for electric
power generation both started in these areas.
Fluid temperatures in the more than 500
wells drilled in the Larderello area are as
follows:
1 2 0 ° - 1 4 0 ° C in the very shallow wells of
200-300 m depth in the Castelnuovo "lagoni"
area (wells type 3);
150 °-170 ° C in the Sasso, Lago, Montero-
tondo, Lagoni Rossi, and Serrazzano "lagoni"
areas (wells type 3 of 300-500 m depth);
139
2 0 0 ° - 2 6 0 ° C in the wells of 500-1200 m
depth at Larderello, Castelnuovo, and Serraz-
zano (wells type l a and lb);
300 °-400 ° C in the deep wells (up to 4000
m) drilled in the last few years (Bertini et al.,
1980; Batini et al., 1983a) (wells type 4).
Fluid pressure is 1.5-3 bar in the shallow
wells at Castelnuovo, 5-10 bar on the Serraz-
z a n o - M o n t e r o t o n d o and Larderello-Castel-
nuovo structural highs, 10-35 bar in recently
drilled wells in structurally low areas skirting
the previous ones, and 60-80 bar in the newly
drilled wells in the western part of the field.
Opinions vary on rock and fluid tempera-
tures, as well as on the mechanism of fluid
superheating during ascent. In the author's
opinion, which is by and large similar to that
of Sestini (1970), the situation can be sum-
marized as follows.
Temperature before exploitation of a new
well and before exploitation of the field in
general:
Well type la. Their main steam-producing
horizon is in the high permeability parts of
the carbonate reservoir (structural highs)
(Celati et al., 1975a; Baldi et al., 1980). Origi-
nally fluid temperature was higher or much
higher than rock temperature. Condensation
of steam, as a consequence of conductive heat
loss, caused the rock to reach the same tem-
perature as the fluid (Sestini, 1970), generally
at the m a x i m u m enthalpic saturated-steam
values of 2360C and 32 bar (as reported by
Elder, 1966; James, 1968; Truesdell and
White, 1973). Fluid temperature in these wells
is now about 250 ° C with shut-in pressures of
5-10 bar.
Well type lb. These are located in the
structural lows of the carbonate reservoir. Al-
though temperature in these wells is now the
same (250 o C) as in type la, pressure is higher
because exploitation began at a later date
(Celati et al., 1975b).
Well type 2. These wells are located in the
low permeability areas of the carbonate re-
servoir and in some marginal areas of the
field. Rock temperature in these areas was
initially much lower than fluid temperature,
140
and condensation was greater than in wells l a
and lb because of the lower permeability and
consequently smaller quantity of circulating
fluid. Temperatures now range from 100°C
(at the free top surface in boiling-point-per-
depth (B.P.D.) well conditions) to 250°C.
Some wells are productive, others have pres-
sures in the liquid-dominated regime. These
wells can be found around the margins of the
field, but are mainly concentrated in the
north-northwestern sector (Atkinson et al.,
1978; Baldi et al., 1980).
Well type 3. These are the shallow wells
drilled next to the "lagoni" areas. Tempera-
tures and pressures are low, though still in the
superheated steam regime (120°C and 1.5
bar are the lowest values south of the Castel-
nuovo area).
Well type 4. These are located in the central
and marginal areas of the field, in the crystal-
line basement. Temperatures up to 390°C
have been measured in some of these recently
drilled wells during 24-h drilling breaks, using
the methods described by Manetti (1973) and
Barelli and Palama' (1981). Boiling-point-
for-depth (B.P.D.) conditions are reported by
Pruess et al. (1987).
Well type 5. These two-phase producing
wells are extremely rare and are located next
to the southern outcrops of the reservoir
(Ceccarelli et al., 1985. 1987).
Well type 6. These wells are located in or
near the carbonate reservoir, and produce
mostly neutral-pH, Ca-sulfate meteoric
waters. Convective temperatures of 90 ° -
99°C with zero thermal gradient are present
at all well depths (Ceccarelli et al., 1987).
The temperatures of types 5 and 6, and
some of types 2 and 3, have remained more or
less constant with time. In the productive
wells, on the other hand, the pressure and
temperature variations depend on a variety of
factors, including exhaustion of drilling water
a n d / o r steam condensates, drilling of a new
well in nearby areas, changes in exploitation
parameters (Gennai and Sestini, 1964), and
reinjection (D'Amore et al., 1987). The situa-
a. MINISSALE
tion has evolved roughly along the following
lines:
Well type la and lb. Pressure of 5-10 bar
and temperature of 250°C temperature (su-
perheated steam);
Well type 2. More or less steady state, both
in pressure and temperature;
Well type 3. Temperature and pressure have
either remained unvaried in time, as in the
Monterotondo area (Ceccarelli et al., 1987),
or changed abruptly with the inflow of shal-
low cold waters as at Travale (Cataldi et al.,
1970; Batini et al., 1985c);
Well type 4. These wells are mainly located
in the newly explored western sector of the
Larderello field. They have not yet started
producing, but their behaviour can be com-
pared to similar wells in the Travale field.
Travale 22 well, which produced saturated
steam at 60 bar and 260 °C in the 70's is now
producing superheated steam of same condi-
tion as type la and lb wells at Larderello.
Well type 5. Their conditions are more or
less stable, although some have seasonal in-
flows of waters from outcrops of the carbonate
reservoir formations in the southeastern part
of the field;
Well type 6. Conditions are very stable in
these wells, because they are fed by a shallow
meteoric water circulation in the unconfined
parts of the reservoir. They are not affected
by steam production at Larderello (Minissale,
1984).
The absence of a clear correlation between
temperature and depth in the producing wells,
with the exception of the shallow type 3 wells,
indicates that the carbonate reservoir is iso-
thermal as a result of fluid convection, and
that it is the reservoir rock that controls the
fluid temperature.
FLUID CHEMISTRY
Steam condensates in productive wells con-
tain ammonia and boric acid in quantities of
100-300 and 50-500 mg kg -1, respectively
(D'Amore et al., 1977). Minor chlorine (5-30
THE LARE)ERELLO GEOTHERMAL FIELD 141

ppm) is also present (D'Amore and Pruess, The compositions of the waters present in
1986). Chlorine in a vapour phase un- the liquid-dominated parts of the field are
saturated by sodium has been interpreted by highly variable. Two different sectors can be
D'Amore and Truesdell (1979) as a clear indi- identified: a northwestern sector where the
cation of the presence of a boiling NaC1 brine compositions vary from NaC1 to N a H C O 3
at depth. More recently this chlorine was (Panichi et al., 1974; Manganelli, 1987) and a
attributed to the formation of HC1 in the southeastern sector where CaSO 4 waters are
deepest and hottest part of the field (Trues- predominant (Ceccarelli et al., 1985, 1987).
dell et al., 1989). In the author's opinion The apparent contrast between the NaC1-
(Minissale, in prep.) chlorine (like ammonia HCO 3 and CaSO 4 chemistry of the liquid
and boron) in the vapor phase might also be phases in the carbonate reservoir rock is im-
interpreted as a product of vaporization, in- portant for understanding the hydrogeology
duced by the depressurization of the of the geothermal system. In the author's
carbonate reservoir, of water stored in the opinion this difference could be explained in
rock matrix both in the basement schistose terms of rock dissolution after steam con-
formations and in the pelitic cover forma- densation. In the northern part of the field,
tions. condensates in wells drilled in the Neogene
The gas (more than 90% C O 2 ) / s t e a m ratio sediments may acquire NaC1 through dissolu-
varies in the reservoir with transmissivity, re- tion of evaporites or mixing with perched
aching maximum values in the structural lows, fossil seawater. On the other hand, con-
low transmissivity areas (D' Amore et al., densates in wells bottoming in flysches and
1977), and areas with high steam con- ophiolites may become enriched in N a H C O 3
densation (D' Amore et al., 1983). through cation extraction from shaly sedi-

0 2KM ~---~0 0 2KM

100

~eO00~
"%,°o i %°0,°% \1~
II LARDERELLO 0

SERRAZZANO ~ ~ ~ _ j ? O 0
• / ~0 o

100

MONTEROT
ooZ>"~ e h:~\
~o ° ~ '-'z

ao,., "~ )~-- L - L z t - C _ z : : ; ' ~ -

(A) (B)
Fig. 3. Two different representations of the aquifer (s) which is considered the 'liquid' boundary of the field (elevation
in m above sea level) [(a) from Cappetti et al., 1982; (b) from Celati et al., 1976].
142
ments, caused by the increased aggressiveness
of the condensates after the solution of H2S
and CO 2.
The southern parts of the field are char-
acterized by thick sequences of anhydrite-
carbonate reservoir formations (Lazzarotto,
1967), and the condensates are enriched in
CaSO 4. There may also be a contribution of
shallow meteoric waters from the unconfined
CaSO 4 aquifer (Calore et al., 1982) located in
the carbonate reservoir formations (type 6
wells).
RELATION BETWEEN THE STEAM RESERVOIR
AND S U R R O U N D I N G AQUIFERS
Using data from type 2 and type 6 wells
with liquid-dominated regimes, Cappetti et al.
(1982) and Celati et al. (1976) compiled maps
of the piezometric levels of the aquifer(s)
bordering the field (Fig. 3). As early as 1963,
Cataldi et al. (1963), proposed that this aquifer
recharged the steam field. However, Petracco
and Squarci (1975) doubted that field re-
charge came mainly from this aquifer, and
evaluated its contribution at one-third of the
total production.
Oxygen and hydrogen isotopic ratios, which
have proved to be a valuable tool for defining
the boundaries of shallow recharge aquifers in
other geothermal fields, gave contradictory
evidence at Larderello. The ratios 180/160
and 2 H / H (Panichi et al., 1974; Panichi and
Gonfiantini, 1978) indicate an inflow of
meteoric water from the eastern and southern
boundaries of the field, but negligible tritium
contents (Celati et al., 1973; D'Amore et al.,
1987) have been found in the central part,
despite the large quantities of steam that have
been withdrawn for over a century. The ab-
sence of tritium, which has been present in
meteoric waters since the nuclear explosions
of the 1950's and 1960's, indicates that the
steam is at least 40 years old. In a recent
paper on the distribution of 222Rn and 3He,
Nuti (1984) estimated the age of the gas stored
in the rock pores in the central areas at more
than 1,700 years.
A. M I N I S S A L E
The presence of meteoric water on the
southern and eastern boundaries of the field
(CaSO4 aquifer), in the unconfined parts of
the carbonate reservoir (wells type 6), corrob-
orates the hydraulic heads in Fig. 3 and sug-
gests that the steam produced by the wells in
the central areas of Larderello is derived from
the evaporation of these meteoric waters. The
lack of tritium and the age of the gas phase
suggests, on the contrary, that these hydro-
logic circuits are very long. On the basis of
this striking contrast, it is therefore unlikely
that these waters feed the steam field and it is
most likely that they are separated by power-
ful self-sealing barriers (Minissale, 1984).
While assuming that these marginal
aquifers in the southern sector of the field are
a physical boundary of the steam field, at
least at the depth of the carbonate reservoir,
Ceccarelli et al. (1985, 1987) nevertheless re-
port that, beneath the carbonate reservoir, the
thermal gradient increases to the same tem-
perature as in the center of the field.
By comparing the trend at the top of the
carbonate reservoir in Fig. 2 (from Bertini et
al., 1984) with the hydrological maps of Fig. 3
we can observe that the piezometric lines
approximately follow the top of the reservoir
itself. In the author's opinion these piezomet-
ric levels in marginal areas could be consid-
ered liquid column manometers of an un-
derlying vapor zone, at least in the northern
and northwestern parts of the field.
The fact that the static levels of drilling
mud balanced vapor pressure in the central
productive parts of the reservoir, had already
been reported by Celati et al. (1976). The
spread of condensation throughout the north-
ern part of the field could be attributed to the
very low permeability in the reservoir in this
area, which leads to large conductive heat
losses of the steam in the wells (most type 2
wells). Because the temperature of the rock is
much lower than that of the fluid, the former
absorbs heat from the steam as it rises. The
thermal exchange occurring along the well
casing brings about condensation of the
steam, which percolates down-hole to form
THE LARDERELLO GEOTHERMAL
the manometric level in the well. According
to the amount of this exchange, conditions in
the casing (if broken, shallow cold meteoric
waters may enter), and at well-head (open,
closed or partly closed), the fluid may remain
in a vapor-saturated condition, or definitely
move into a liquid condition, still maintaining
the pressure of the rising steam. This pressure
is typical of wells before exploitation in the
low-transmissivity parts (lb type wells) of the
carbonate reservoir. In the same area some
wells may be productive if the quantity of
steam is sufficient, that is, if permeability is
high enough. The presence of producing and
liquid-dominated wells within the same re-
stricted area, makes it difficult to draw the
hydrological map in the northern part of the
field (dashed lines in Fig. 3).
The situation in the southern margin of the
field differs from that in the northern part.
There is certainly an influx of cold meteoric
water at shallow depth here, but in some
areas the rock temperature is very high (about
100°C at the surface in the large zone of
natural manifestations from Sasso to Monte-
FIELD 143
rotondo). Superheated steam can be found in
wells at 130 °C and 1.5 bar of pressure in the
Castelnuovo area, at 170°C and 6 bar at
Monterotondo, and at 150°C and 5 bar near
Lagoni Rossi. These wells, located in lower
enthalpy areas but producing superheated
steam, are always close to zones with natural
manifestations. At a short distance from these
shallow productive areas, there are type 6
wells (Fig. 4) producing CaSO 4 waters that
have a uniform convective temperature distri-
bution (90 ° - 9 9 ° C) at depth, cooled by mix-
ing with meteoric waters (Ceccarelli et al.,
1985). Similar extreme variability in hydro-
logic and thermodynamic conditions within
such a narrow area in the old shallow Travale
field (which is similar to the southern
boundary of the Larderello field), led Facca
and Tonani (1967) to propose the concept of
a self-sealing geothermal field.
In the presence of this sealing mechanism,
and in the absence of a normal hydrodynamic
regime, cold water may exist above the steam,
both from a thermodynamic (Bozza, 1961)
and a geological point of view. The CaSO 4

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144
aquifer hosted in the carbonate reservoir rock
on the southern boundary of the field could,
in fact, mask any underlying vapor phase.
E V O L U T I O N OF H Y D R O T H E R M A L ACTIVITY IN
T H E FIELD
According to the age attributed by De1
Moro et al. (1982) to biotite and muscovite
crystals sampled in hydrothermal veins in two
deep wells in the metamorphic basement, the
Larderello geothermal field should be at least
three million years old, an age span compara-
ble to that of the magmatic activity near
Roccastrada (Borsi et al., 1967) and Boccheg-
giano (Mazzuoli, 1967), not far from
Larderello. If a hot, and probably highly saline
hydrothermal phase had been present for such
a long time, it would in all likelihood have
filled and sealed all the existing fractures at
Larderello, depositing large quantities of hy-
drothermal ores, such as those quarried in the
Tuscan mining areas skirting a large portion
of the Larderello field (Fig. 1). Mineraliza-
tion, on the contrary, seems scarce at
Larderello and is found only at the margins
of the field. Any mineralizations existing in
the area would probably have been dissolved
by acid condensates and re-deposited in pe-
ripheral areas when the field passed from a
liquid-dominated to a vapor-dominated reg-
ime.
EVIDENCE OF STEADY-STATE VAPOR FLUX
F R O M DEPTH
Any reconstruction of the natural state of
the field prior to exploitation in the last cen-
tury must of necessity be an inductive model,
because of the lack of data of the very early
years of exploitation of the field. On reading
the papers by Targioni-Tozzetti (1769), Savi
and Meneghini (1851), Lotti (1910), Ginori-
Conti (1928), Nasini (1930) and Fiumi (1943),
which give detailed descriptions from Roman
times, it would appear that the field was
vapor-dominated before exploitation started.
Had the main reservoir been almost full of
A. MINISSALE
condensates, the deep steam could possibly
have risen through the fractures in the "lag-
oni" areas, becoming superheated in places.
Today this no longer occurs but the presence
of the shallow low-enthalpy wells suggests
that it is a mistake to regard the lagoons as
having disappeared. Exploitation has un-
doubtedly depressurized the system, but it
has not prevented steam from reaching the
surface as in the natural state.
The stationary condition of the field had
already been noted by Gennai end Sestini
(1964), who estimated the maximum flow of
the field as 3000 t h-1 from analysis of well
production data. This value was apparently
independent of the number of new wells being
drilled. Further proof of the stationary condi-
tion of the steam flow towards the surface
was given by Lenzi (1928) in an article on the
quality and quantity of boric compounds in
the main Larderello area. He reported a pro-
duction of 1000 t h - 1of steam from the steam
condensation domes of the lagoons in the
original Larderello field. Because these steam
vents were the most spectacular and powerful
of the boraciferous region, it can be estimated
that about 3000 t h-1 of steam was the total
natural production rate of steam from all the
lagoons, including those at Castelnuovo,
Sasso, Serrazzano, Le Prata, Lago, Montero-
tondo, Carboli, and Lagoni Rossi. Nowadays
the total flow of steam in the Larderello field
for electric power is still 3000 t h-~ (Carella
et al., 1985).
PHYSICAL S I G N I F I C A N C E OF T H E B O U N D A R Y
AREAS
Before exploitation, the temperature of the
carbonate reservoir and the fluid was the
same, coinciding more or less with the maxi-
m u m enthalpy values for saturated steam. As
observed by Sestini (1970), however, this con-
dition is different from that of liquid-
dominated systems. The permeability in the
most productive parts of the field is high
enough to keep the reservoir isothermal. At
the same time, under very low permeability
THE LARDERELLO GEOTHERMAL FIELD
conditions, condensation creates the decep-
tive water-levels in the wells. Actually, steam
is still the pressure-controlling phase. The true
temperature of the little steam that enters
from the fracture, and condenses along the
well, is still unknown. In most cases the fluid
lies on the water-saturation curve, reaching
100°C at the free top surface. Consequently,
the north-northwestern part of the field, where
these conditions exist, does not seem to be a
continuous liquid boundary of the field, but
is still conceptually a vapor-dominated part
of the field. In this area, pressure in most of
the liquid-dominated wells is about 30-35 bar
(Ceccarelli, pers. commun.), which is more or
less the same pressure of wells in the center of
the field before exploitation.
In the south-southeastern part of the field
there is a cold water influx from the outcrops
of the reservoir formations (Ceccarelli et al.,
1987). In spite of this, the wells located in this
liquid and two-phase part of the field still
have 30-35 bar of pressure. Figure 5 (from
Minissale, 1984) reports the pressure mea-
sured at the fracture for producing (super-
heated), two-phase, and some liquid-
dominated wells in this area. Since the pres-
sure in this area is independent of the type of
well considered, we can hypothesize that this
I I
.Ig
.i
311
[]
• []
[]
2o b
I I
300 500
Fig. 5. Pressure versus depth of productive fracture for some wells located in the southern part of the Larderello field
(from Minissale, 1984).
145
boundary might also be a condensed vapor
margin, caused by excessive interference of
cold meteoric waters with underlying rising
steam. The difference in elevation between
the hypothesized aquifer in the northern part
and in the southern part of the field is due
only to the different height of the top of the
carbonate reservoir (Figs. 2 and 3). This dif-
ference in elevation also explains why the
natural manifestations are located mostly in
the eastern and southern parts of the field,
where the carbonate formations are at shal-
low depth.
Meteoric water in the south-southeastern
reservoir rocks does not appear to form a
field boundary. The hydraulic heads shown in
Fig. 3 are generally inconsistent with an
aquifer in carbonate formations. Accordingly,
we can hypothesize that the vapor zone ex-
tends at depth without encountering an
evaporating water-table in the center of the
field. Considering that the pressure in the
fractures is approximately the pressure of
saturated steam at its maximum enthalpic
point, steam at the same condition as in the
central part of the field before exploitation
might be present in the marginal areas be-
neath the unconfined (suspended?) CASO 4
aquifer. Figure 4, which is an idealized and
I I I I
e
ee • •
• -
0 superheated
[] two phases
• liquid- dominant --
I I I I
700 900 1100 1300 DEPTM (m)
146
schematic N - S cross-section through the
Larderello field, illustrates this hypothesis.
CO N C L US I ONS
The steam produced at Larderello during
the early life of a well, and before the exploi-
tation of the field, was at maximum enthalpic
point for saturated steam on the Mollier di-
agram (about 32 bar and 236 o C). Steam be-
came superheated as exploitation progressed.
This suggests that the steam ascended directly
from depth along fissures, as assumed by
Goguel (1953) and Sestini (1970), and that it
condensed in the main carbonate reservoir
mostly when in contact with the flysch cover
formations, where it found rock temperatures
lower than that of the fluid. The steam re-
leased heat to the host rocks and remained
superheated in places. The final adiabatic ex-
pansion towards the lagoon areas probably
resulted in a steam temperatures of 130 ° -
170 ° C a t / o r near the surface, similar to the
present-day temperatures of the producing
wells in the lagoon areas. Following this same
line of reasoning, in the very early history of
the field, the shallow aquifers in the uncon-
fined part of the reservoir formations and in
the pelitic cover formations could have been
exhausted by heating and vaporization caused
by the rising steam from depth. As early as
the last century, the descendants of Count De
Larderel effectively came to the conclusion
that if they wanted to increase boric acid
production they had to condense the steam,
rather than use the thermal water pools. The
presence of boron (along with ammonia) in
the vapor phase in the natural steam vents is
further proof of the presence of superheated
steam at the surface, which no underwent
large-scale condensation phenomena during
its ascent. We have, therefore, reason to be-
lieve that the water in the pools was mainly
meteoric and largely d e p e n d e n t on weather
conditions.
The analysis of published data and histori-
cal events leads to the following evolutionary
A. MINISSALE
model of the Larderello geothermal field for
the last three million years:
(a) 3 My ago the field (and a large part of
southern Tuscany) was in a liquid hydrother-
mal stage, which deposited all the mineral
assemblages observed at present in the main
fractures of the basement, and in the struct-
ural top of the permeable carbonate reservoir;
(b) continuous flow of heat from depth
eventually boiled off the hydrothermal fluid
and transformed it into steam. The phreatic
explosions that Marinelli (1969) believed
formed certain deposits and crater-like struc-
tures can probably be attributed to this sec-
ond stage;
(c) the third stage can also be observed
today, and could be termed pneumatolitic. It
has remained below critical steam conditions,
where the only liquid phases in the reservoir
seem to be steam condensates.
Figure 6 is a scheme of the sequence of
these events. The persistence of these very
particular conditions, which lead to the'rarity
of vapor-dominated systems like Larderello,
is mostly due to the particular tectonic situa-
tion inside and below the main carbonate
reservoir, as well as to the very low permea-
bility surrounding the system. The boundaries
of this system have not been defined, and
may not coincide with the boundaries identi-
fied today. Indeed, the deep wells that have
been drilled so far in the Larderello region
have not encountered deep liquid phases. The
temperature above 390 ° C measured at 2900
m in depth in St. Pompeo 2 well (Pruess et al.,
1987), which might be the rock temperature
measured during drilling after the drilling m u d
had heated, makes the existence of a deep
liquid phase very unlikely. The rims of sani-
dine, which approximate conditions of con-
tact metamorphism with a granitic intrusion,
are similarly incompatible with a deep liquid
phase.
The model proposed for the present state
of the field is very similar to that formulated
by Sestini (1970) and Goguel (1953). It as-
sumes, as Sestini hypothesized, that the steam
ascended to the carbonate reservoir from su-
THE LARDERELLO GEOTHERMAL FIELD 147

3My. Little of the Larderello steam, therefore,

THERMAL
derives from the recharge outcrops of the
I

,1
carbonate formations. Although convective
movements exist in the upper part of the
'3
field, as described in D ' A m o r e and Truesdell
(1979), Larderello has more the characteris-
0 0 0 0
,5~'n
tics of a conductive system in a steady state
than a convective system. Contributions to
X X ~ x ~ x x X X X X X X
steam production probably come for the most
part from a very large deep metamorphic
"PHREATIC" EXPLOSION
ACTIVITY (?)
system, that spreads horizontally and verti-
Today
cally to a far greater extent than has been
envisaged so far.

ACKNOWLEDGMENTS

o o o -3
I wish to thank Drs. G.C. Stefani, A. Cec-
o ( S U P E R C R I T I C A L PHASE ) carelli, A. Ridolfi, and G. Bertini of E N E L
o o ~,5krr
o . o /
L
(Italian National Electricity Agency, Pisa,
~ ~ M
x x ~Ax x x × x ~~ x° ~ x
Italy) for continuing discussion on vapour-
dominated systems and Prof. F. Tonani (Uni-
versity of Palermo, Italy) and Drs. P. Muffler
i
and A. Truesdell (U.S.G.S. Menlo Park, Cali-
Fig. 6. Scheme of the evolution in time of the Larderello
fornia) for the critical revision of the
geothermal field. The phreatic explosion stage is mainly
to be considered as a period of time in which, after the manuscript. Mrs I. Faulkner's and M. Dik-
exhaustion of shallow aquifers, steam no longer found son's contributions for the revision of the
"cold obstacles' in its pathway to the surface. English translation is acknowledged.

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