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Evolution of the hydrothermal system at Los Azufres, Mexico, based on

petrologic, fluid inclusion and isotopic data

Article  in  Journal of Volcanology and Geothermal Research · December 2000

DOI: 10.1016/S0377-0273(00)00211-0

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 Journal of Volcanology and Geothermal Research 104 (2000) 277±296
www.elsevier.nl/locate/jvolgeores

Evolution of the hydrothermal system at Los Azufres, Mexico,

based on petrologic, ¯uid inclusion and isotopic data
E. GonzaÂlez-Partida a,*, P. Birkle b, I.S. Torres-Alvarado c
a
Unidad de InvestigacioÂn en Ciencias de la Tierra, Campus UNAM, Juriquilla, Oro., Mexico
b
Instituto de Investigaciones EleÂctricas, Unidad Geotermia, A.P.1-475, Cuernavaca, Mor., 62001 Mexico
c
Centro de InvestigacioÂn en EnergõÂa, UNAM, A.P. 34, Temixco, Mor., 62580 Mexico
Received 20 July 1999; revised 23 May 2000; accepted 23 May 2000

Abstract
The Los Azufres geothermal reservoir, formed in a fractured, Upper Miocene to Pliocene andesite and basalt base complex, is
sealed to the surface by a silicic, mainly rhyolitic sequence of Pleistocene age. Almost the entire sequence is affected by
hydrothermal alteration to varying extent. Petrological and ¯uid inclusion studies con®rmed vertical zonation of the reservoir
by secondary processes: Hydrothermal alteration processes under low temperature conditions (,1708C) caused argillitization
of the shallow zone of the reservoir (depth ,500 m). Smectite, zeolite, calcite, and chlorite predominate the mineral assemblage
in the shallow zone.
At a depth of 1200±1500 m, the maximum ice melting temperatures (Tmi) values of 20.7 to 248C and salinities of 6.4 wt%
NaCl eq. indicate boiling conditions of the geothermal brine in a vapor-rich zone. Chlorite, calcite, quartz, zeolite, anhydrite,
albite, sphene, pyrite, hematite, and illite form the hydrothermal mineral paragenesis with maximum temperatures of 2508C and
pressure conditions of 150 bar. Below 1500 m, Tmi reach maximum values of 20.18C and low salinities of 0.2 wt% NaCl eq.
The minerals epidote, amphibole, prehnite, and garnet indicate temperatures above 2508C and pressure conditions between 150
and 200 bar. The measured homogenization temperatures (Th) of ¯uid inclusions (FI) are consistently higher than the in-situ
measured temperatures, which indicates retrograde cooling of the Los Azufres geothermal reservoir since the time of the
hydrothermal mineral formation.
Updoming temperature isotherms at the center of the geothermal ®eld (below well Az-9, Az-23, and Az-25) indicate the
heating up of the ¯uids by a shallow magma chamber. Stable isotope data (d 18O, d D) of the geothermal brine indicates mixing
processes between meteoric water and a minor magmatic component. Secondary reactions forming sericite may have caused a
further positive shift in 18O in the shallow part of the geothermal reservoir. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: hydrothermal system; isotopic data; ¯uid inclusion data

1. Introduction well as their physico-chemical evolution through

The chemical composition of geothermal ¯uids, as
* Corresponding author.
E-mail addresses: egp@conin.unicit.unam.mx (E. GonzaÂlez-
Partida), birkle@iie.org.mx (P. Birkle), ita@mazatl.cie.unam.mx
(I.S. Torres-Alvarado).
0377-0273/00/$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0377-027 3(00)00211-0
time, is valuable information during exploration and
exploitation of an active geothermal ®eld. Fluid inclu-
sions (FI) in hydrothermal minerals provide important
data, as they are the only direct information source on
temperature during mineral formation and paleo¯uid
composition, which have circulated through the rocks.
FI studies may help to assess the temperature
278 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

30º Cerro USA

Prieto

Mexico

Gulf of
Mexico
Los Azufres
20º Los Humeros
Pacific
Ocean MVB

Morelia Mexico
City
0 200 400

km
Guatemala

110º 100º 90º W

Fig. 1. Location map of the Los Azufres geothermal ®eld in the central part of Mexico and western part of the Mexican Volcanic Belt (MVB).
Two other important Mexican geothermal ®elds (Cerro Prieto and Los Humeros) are also shown.

evolution with time in the ®eld, and estimate the cool-
ing rate or the physical state of the ¯uids prior to
exploitation. Furthermore, FI provide local informa-
tion on well-de®ned zones within the reservoir,
compared to the information given by geothermal
¯uids, which may originate from heterogeneous
sources or from a relatively large section of the reser-
voir. Fluid inclusion data, together with petrologic
and isotopic information, may provide complete
information for knowing the P±T±X evolution of a
geothermal ®eld.
This paper presents results from petrologic, isotopic
and ¯uid inclusion studies of the hydrothermal system
at the geothermal ®eld of Los Azufres, Mexico.
Mineralogical zoning, as well as temperature distribu-
tion pro®les and the D/ 18O isotopic ¯uid composition
are used to characterize the formation and determine
the origin of geothermal ¯uids at the Los Azufres
reservoir.
2. Geological setting
Los Azufres is one of several Pleistocene silicic
volcanic centers with active geothermal systems in
the Transmexican Volcanic Belt (TMVB) (Aguilar
et al., 1987). It is located approximately 200 km
NW of Mexico City and 80 km E of the MichoacaÂn
state capital Morelia (Fig. 1). With an electricity
production of 98 MW, it represents the second most
important geothermal ®eld in Mexico (Quijano LeoÂn
and GutieÂrrez NegrõÂn, 1995).
The volcanic rocks at Los Azufres have been
described by different authors (De la Cruz et al.,
1982; Dobson and Mahood, 1985; HuitroÂn Esquivel
and Franco Serrano, 1986; Cathelineau et al., 1987;
Razo Montiel et al., 1989; LoÂpez HernaÂndez, 1991).
Geologically, two principal divisions can be distin-
guished (Fig. 2):
(1) Silicic sequence of rhyodacites, rhyolites and
dacites with ages between 1.0 and 0.15 m.y. and
having a thickness up to 1000 m (Dobson
and Mahood, 1985). According to Razo Montiel et
al. (1989), ®ve different units can be differentiated:
Agua FrõÂa rhyolite, Tejamaniles dacite, Cerro Mozo
and San AndreÂs dacites and Yerbabuena rhyolite. This
sequence seals the geothermal aquifer from the
surface, allowing the geothermal system to pressurize.
(2) 2700 m thick interstrati®cation of lava ¯ows and
pyroclastic rocks of andesitic to basaltic composition
with ages between 18 and 1 m.y., forming the local
basement (Dobson and Mahood, 1985). This unit
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 279

Fig. 2. Geological map of the Los Azufres geothermal ®eld (based on Razo Montiel et al., 1989), the principal fault systems, and the pro®le
lines for Figs. 3 and 4. Legend abbreviations: (1) Quaternary±Pleistocene; (2) Pleistocene; (3) Pliocene±U. Miocene.

hosts the main geothermal aquifer. Fractures and
faults allow geothermal ¯uids to rise from this aquifer
to higher stratigraphic levels, sometimes reaching the
surface.
Fig. 2 shows a geological map of the mentioned
units, as well as fault systems and geothermal wells
of the Los Azufres ®eld and its surroundings. Three
different fault systems, which provide secondary
permeability to the geological units, can be distin-
guished in the ®eld (GardunÄo Monroy, 1988): NE±
SW, E±W and N±S. The E±W system is the most
important for geothermal ¯uid circulation. Geother-
mal manifestations (fumaroles, solfataras and
mudpits), geophysical anomalies and important
energy production zones are related to this fault
system. The pro®le in Fig. 3 shows a lithological
cross-section in a N±S direction, from the northern
MarõÂtaro zone towards the southern Tejamaniles
280 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Fig. 3. N±S directed geological cross section from the northern geothermal production area (MarõÂtaro) to the southern area (Tejamaniles). Also
illustrated are the principal fault systems and thermal surface manifestations.

zone. Fig. 4 shows a cross-section in E±W direction
through the Tejamaniles zone.
3. Hydrothermal aspects
Iglesias et al. (1985) suggest that the present hydro-
thermal system in Los Azufres is related to a deep
aquifer extending throughout the ®eld. Nieva et al.
(1986, 1987a) demonstrated the existence of a
pressurized, hot (3308C) liquid system at a depth of
3500 m in the Los Azufres reservoir. Rising towards
the surface along fractures, boiling related to the loss
of pressure and temperature favors increasing vapor-
ization and the formation of a two-phase system.
Close to the surface, the dominating vapor phase
and the liquid phase are mixed with meteoric water.
Giggenbach and Quijano (1981) proposed that the
geothermal ¯uid has a major magmatic contribution,
whereas Birkle (1998) indicated the existence of a
meteoric water component.
However, some important regional differences are
noted. In the northern part of the ®eld (MarõÂtaro zone),
geothermal ¯uids are formed by a mixture of gases
and liquid with T around 300±3208C. In the south
(Tejamaniles zone), the gas phase generally domi-
nates over the liquid phase (wt%) and temperatures
are lower than in the north (260±2808C). Regional
permeability and systematic pressure differences, as
well as different boiling rates may be the reason for
these divergences.
The thermal ¯uids are sodium chloride rich waters
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 281

Fig. 4. W±E directed, geological cross section through the southern geothermal production area (Tejamaniles). Also illustrated are the principal
fault systems and thermal manifestations at the surface.

with high CO2 and H2S contents (Moreno Ochoa,
1989), with a pH between 5.5 and 7.4 under reservoir
conditions (Nieva et al., 1987b). Average Cl 2
contents are 3100 mg/kg and CO2 can represent as
much as 90% of the total gas phase. Fluid tempera-
tures can reach values as high as 3208C, although
240±2808C are normal for the ®eld.
4. Petrological considerations
Studies of hydrothermal alteration which has
affected most rocks at Los Azufres, have been carried
out, among others, by Cathelineau et al. (1985),
Robles Camacho et al. (1987) Partida et al. (1989),
and Torres-Alvarado (1996). These studies have
shown partial to complete hydrothermal alteration of
primary rocks, consisting of propylitic mineral assem-
blages at higher temperatures (deeper zones) and
of important argillite assemblages within zones of
lower temperatures, as well as on the surface.
Systematically mineralogical changes occur with
increasing temperature and pressure (increasing
depth). Most important alteration assemblages are,
with increasing depth, argillitization/silici®cation,
zeolite/calcite formation, sericitization/chloritization,
and chloritization/epidotization. Calcsilicates are
important temperature indicators in the ®eld. Three
different zones may be de®ned, based on the observed
hydrothermal minerals:
Zone I: Smectites, zeolites (mostly stilbite),
calcite and chlorites predominate, but amorphous
282 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Fig. 5. Based on microthermometric analysis of the well cuttings and core samples from Az-27-A, Az-44, Az-9, Az-23, and Az-16, four zones
with different ice melting temperatures can be distinguished in the N±S oriented section. The continued lines represent the measured
homogenization temperatures, whereas the dashed lines give the in situ measured values.

silica, quartz, kaolinite, and illite are also present
(Izquierdo et al., 1995). This mineral paragenesis
may be found from ground level to 500 m depth, at
temperatures lower than 1708C and pressure up to
50 bar.
Zone II: This zone is characterized by the presence
of chlorite, calcite, quartz, zeolites (heulandite and
wairakite), anhydrite, albite, sphene, pyrite, hematite
and illite. Quartz, chlorite and calcite reach here their
maximum abundance. Depth ranges between 500 and
1500 m, where 2508C and 150 bar may be reached.
Zone III: The deepest zone in the ®eld is distin-
guished by the presence of epidote, amphibole (tremo-
lite), prehnite and garnet. As well as for other zones,
chlorite, quartz, calcite, pyrite and hematite are also
present. This mineral paragenesis may be found at
depths .1500 m, where temperatures higher than
2508C and pressures between 150 and 200 bar are
normally reached.
5. Samples and methodology
Microthermometric determinations were made on
well cuttings and core samples from wells Az-9,
Az-16, Az-18, Az-23, Az-25, Az-26, Az-27A, Az-
35, Az-44 and Az-50 (Figs. 5 and 6), containing
veins which are ®lled with secondary minerals
(epidote, quartz, wairakite, anhydrite and calcite).
Core slices and cuttings were double polished. The
microthermometric measurements were performed
on a Chaix-Meca heating±cooling stage, calibrated
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 283

Fig. 6. The W±E oriented section of the Tejamaniles production zone illustrates the microthermometric zonation of the geothermal reservoir.
The continued lines represent the measured homogenization temperatures, whereas the dashed line gives the in situ measured values.
Decreasing homogenization temperatures can be observed towards the well Az-50.

using the melting points of several analytical reagents 6. Results

as standards. From the observation of each ¯uid inclu-
sion, two parameters were determined: (1) ice melting
temperatures to estimate ¯uid salinity in terms of
equivalent weight percent of NaCl (using Potter's
equation; Potter et al., 1978); and (2) the homogeniza-
tion temperatures to estimate minimum formation
temperature of the studied minerals. Further
details on the analytical procedures and techniques
followed are described by GonzaÂlez Partida et al.
(1997).
6.1. FI studies
FI in hydrothermal quartz, calcite, wairakite, and
epidote were studied. Table 1 summarizes the infor-
mation obtained from the ¯uid inclusion analyses. The
results are shown in Figs. 5 and 6, with an orientation
of the cross-sections identical to the geological
pro®les of Figs. 3 and 4. Most measured FI consisted
of liquid 1 vapor at room temperature, with
284 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Table 1
Results of the microthermometric studies of ¯uid inclusion in hydrothermal minerals from Los Azufres geothermal ®eld. Th ˆ homogenization
temperature (8C); Tmi ˆ ice melting temperature (8C); n ˆ number of inclusions measured; depth in meters; salinity in wt% NaCl eq; Qz ˆ
quartz; Ep ˆ epidote; Cc ˆ calcite; Pre ˆ prhenite

Depth Host min. Th range Th av. n Tmi range Tmi av. n Salinity

Az-9
2450 Qz 317 347 334 23 20.1 20.3 20.2 23 0.3
2450 Ep 312 351 335 3 20.6 20.6 20.6 3 1.0
2300 Qz 303 346 340 28 20.1 20.6 20.3 28 0.5
2300 Ep 340 348 345 7 20.5 20.6 20.5 7 0.8
2127 Qz 324 340 329 26 20.3 20.5 20.4 26 0.7
2127 Ep 324 326 325 3 20.5 20.5 20.5 3 0.8
1900 Qz 307 311 310 25 20.1 20.3 20.2 25 0.3
1900 Ep 302 307 309 4 20.5 20.3 20.4 4 0.7
1700 Qz 282 305 296 11 20.8 20.7 20.7 11 1.2
1700 Ep 286 305 297 12 21.3 21.3 21.3 12 2.2
1500 Ep 285 287 286 5 20.3 20.3 20.3 5 0.5
1300 Qz 320 327 322 22 20.9 20.8 20.9 22 1.4
1000 Wai 248 272 173 21 20.4 20.8 20.5 21 0.8
1000 Qz 234 295 285 11 20.4 20.8 20.5 11 0.8
800 Qz 223 273 243 10 21.5 21.5 21.5 10 2.4
500 Qz 210 255 240 10 0.4 0.6 0.5 10 ±
400 Wai 203 208 205 6 0.3 0.6 0.5 6 ±
400 Qz 215 229 220 91 0.3 0.4 0.4 91 ±
300 Wai 195 203 200 10 20.2 20.5 20.4 10 0.7
300 Qz 199 215 205 7 0.3 0.5 0.4 7 ±
200 Qz 180 188 185 12 0.5 0.5 0.5 12 ±

Az-16
2450 Qz 328 346 335 8 20.3 20.7 20.4 8 0.7
2100 Ep 299 319 310 16 20.6 22.0 21.5 16 2.5
2100 Qz 284 330 305 42 21.0 21.8 21.3 42 2.2
1950 Wai 290 309 301 25 21.1 21.5 21.2 25 2.0
1950 Ep 302 318 310 6 20.4 20.4 20.4 6 0.7
1550 Qz 268 288 286 11 20.6 22.2 21.0 11 1.7
1550 Wai 285 291 288 23 20.6 20.6 20.6 23 1.0
1400 Wai 260 272 264 21 20.5 20.7 20.6 21 1.0
1250 Wai 252 268 262 37 20.6 20.6 20.6 37 1.0
1250 Qz 241 265 256 80 20.6 20.6 20.6 80 1.0
950 Wai 241 265 260 32 20.4 21.1 20.8 32 1.4
800 Wai 206 257 240 35 20.6 21.3 21.1 35 1.9
550 Qz 220 225 223 5 21.2 21.2 21.2 5 2.0
400 Qz 204 210 208 10 21.1 21.1 21.1 10 1.9
Az-18
1320 Ep 230 233 231 15 20.6 20.6 20.6 15 1.0
1220 Wk 324 324 324 20 20.4 20.4 20.4 20 0.7
1160 Qz 252 286 272 49 21.2 20.5 20.7 49 1.2
1000 Qz 236 274 257 60 20.2 21.0 20.6 60 1.0
900 Qz 213 262 232 50 21.0 21.0 21.0 50 1.7
800 Cc 190 237 212 18 20.5 20.5 20.5 18 0.8

Az-23
1700 Qz 285 315 310 11 20.1 20.2 20.2 11 0.3
1275 Qz 251 292 276 8 20.1 20.6 20.3 8 0.5
1100 Qz 210 282 264 14 20.5 21.6 21.1 14 1.9
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 285

Table 1 (continued)

Depth Host min. Th range Th av. n Tmi range Tmi av. n Salinity

1000 Qz 229 261 250 32 20.2 21.1 20.6 32 1.0

900 Qz 220 265 254 10 20.6 21.3 20.9 10 1.5
800 Qz 202 264 253 31 20.3 21.2 20.8 31 1.4
600 Qz 237 261 257 9 20.3 20.7 20.5 9 0.8
500 Wk 210 227 223 12 20.3 21.7 21.2 12 2.0
500 Qz 221 224 221 5 20.3 21.6 21.1 5 1.9
400 Qz 209 233 220 9 21.2 21.6 21.5 9 2.5
200 Qz 136 203 160 8 20.1 2.1 ± ± ±
100 Qz 110 177 159 5 20.1 2.0 ± ± ±
Az-25
2060 Ep 267 337 307 13 0.0 20.1 20.1 13 0.1
2000 Qz 260 317 292 38 21.2 21.7 21.3 38 2.2
1900 Ep 265 265 265 10 21.0 21.0 21.0 10 1.7
1800 Qz 265 301 289 66 20.7 20.9 20.8 66 1.4
1700 Ep 296 315 305 9 21.6 21.7 21.6 9 2.7
1600 Ep 275 319 309 11 20.9 20.9 20.9 11 1.5
1520 Qz 288 388 306 38 20.7 20.9 20.8 38 1.4
1400 Ep 280 337 298 14 21.5 21.9 21.6 14 2.7
1300 Qz 248 343 306 26 21.2 21.4 21.4 26 2.4
1220 Qz 246 261 253 28 21.2 21.2 21.2 28 2.0
800 Qz 222 232 228 20 20.7 20.7 20.7 20 1.2
700 Qz 199 224 209 31 20.7 20.7 20.7 31 1.2
600 Qz 163 172 168 33 21.9 22.1 22.0 33 3.3
500 Qz 138 158 145 30 20.9 20.9 20.9 30 1.5
400 Qz 125 125 125 28 4.6 2.2 4.0 28 ±
Az-26
1200 Qz 250 276 260 35 20.1 21.5 20.7 35 1.2
1100 Qz 245 302 266 20 20.4 20.4 20.4 20 0.7
1000 Qz 206 242 212 28 23.6 26.1 24.0 28 6.4
900 Qz 196 260 219 40 21.2 24.4 23.5 40 5.7
800 Cc 191 247 218 10 21.0 21.0 21.0 10 1.7
700 Qz 175 263 198 25 21.5 21.5 21.5 25 2.5
600 Qz 140 152 143 7 1.0 3.1 2.5 7 ±
Az-27A
2000 Qz 283 327 309 58 20.5 0.9 20.8 58 1.4
1700 Qz 291 328 321 20 20.8 20.8 20.8 20 1.4
1700 Ep 295 335 318 7 20.8 20.8 20.8 7 1.4
1600 Qz 339 394 320 16 20.8 20.8 20.8 16 1.4
1500 Qz 311 341 320 24 20.9 21.1 21.0 24 1.7
1300 Ep 267 268 267 6 20.8 20.8 20.8 6 1.4
1200 Ep 269 286 275 9 20.9 20.9 20.9 9 1.5
1100 Qz 274 281 278 15 20.1 20.9 20.7 15 1.2
900 Ep 262 279 271 11 20.6 20.8 20.7 11 1.2
800 Qz 228 295 275 44 20.1 21.7 20.7 44 1.2
600 Ep 244 275 260 10 20.1 20.8 20.3 10 0.5
400 Qz 196 215 212 10 21.2 21.4 21.3 10 2.2
200 Qz 224 230 225 61 20.6 20.6 20.6 61 1.0
Az-29
2900 Ep 321 334 325 9 20.4 20.4 20.4 9 0.7
2800 Qz 287 345 314 32 21.5 20.8 20.9 32 1.5
286 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Table 1 (continued)

Depth Host min. Th range Th av. n Tmi range Tmi av. n Salinity

2680 Ep 287 310 301 10 21.0 21.0 21.0 10 1.7

2580 Ep 289 334 303 18 20.4 20.4 20.4 18 0.7
2380 Qz 287 308 300 22 20.8 20.8 20.8 22 1.4
2320 Ep 227 359 308 18 22.1 21.0 21.2 18 2.0
2080 Ep 273 283 280 10 21.0 21.0 21.0 10 1.7
1980 Qz 254 312 277 25 22.4 20.8 21.5 25 2.5
1820 Qz 261 298 272 40 21.7 21.7 21.5 40 2.5
1600 Qz 212 360 292 60 23.6 21.0 22.0 60 3.3
1400 Qz 223 350 295 29 21.0 21.0 21.0 29 1.7
1200 Qz 247 288 275 30 21.4 21.4 21.4 30 2.4
1000 Qz 202 290 236 41 21.5 21.5 21.5 41 2.5
800 Qz 203 231 219 38 20.7 20.7 20.7 38 1.2
700 Qz 158 198 172 20 20.7 20.7 20.7 20 1.2
500 Qz 106 134 115 15 20.4 0.9 0.5 15 ±
400 Qz 104 139 126 18 0.6 0.6 0.6 18 ±
Az-35
1050 Qz 252 274 264 36 21.3 21.3 21.3 36 2.2
1000 Qz 232 261 243 50 20.4 22.4 21.5 50 2.5
900 Qz 205 277 220 40 20.4 21.2 20.7 40 1.2
780 Qz 177 212 190 35 23.4 24.0 23.2 35 5.2
700 Qz 169 244 204 20 21.7 23.9 22.0 20 3.3
600 Qz 148 149 148 18 20.9 21.0 20.9 18 1.5
Az-40
2080 Ep 230 326 242 5 20.7 20.7 20.7 5 1.2
2000 Ep 226 267 243 10 20.8 20.8 20.8 10 1.4
1900 Qz 232 292 263 32 20.5 20.5 20.5 32 0.8
1800 Ep 206 260 228 11 21.0 20.7 20.5 11 0.8
1700 Ep 216 304 252 6 21.2 20.6 20.6 6 1.0
1600 Cc 226 334 230 26 20.8 20.8 20.8 26 1.4
1500 Qz 222 340 229 40 20.8 20.8 20.8 40 1.4
1400 Ep 222 231 227 13 21.2 20.6 20.7 13 1.2
1300 Ep 221 221 221 10 21.9 20.7 21.0 10 1.7
1200 Ep 218 287 274 7 21.1 20.7 21.0 7 1.7
1100 Qz 217 273 228 26 21.7 21.7 21.7 26 2.9
1000 Ep 217 290 232 8 20.6 20.6 20.6 8 1.0
900 Cc 221 277 243 36 21.1 21.6 21.5 36 2.5
800 Qz 166 242 212 26 20.3 20.8 20.6 26 1.0
700 Qz 136 205 199 28 20.4 20.8 20.6 28 1.0
120 Qz 132 149 141 10 6.0 8.1 7.0 10 ±
Az-44
4200 Qz 250 276 260 35 20.1 21.5 20.7 35 1.2
3300 Qz 302 327 313 23 20.4 21.2 20.6 23 1.0
3200 Qz 300 310 302 14 20.9 22.1 21.0 14 1.7
3100 Qz 297 303 288 19 20.9 21.6 21.2 19 2.0
2880 Qz 293 321 303 6 21.1 21.1 21.1 6 1.9
2880 Ep 307 332 300 29 20.9 20.9 20.9 29 1.5
2600 Ep 298 325 310 20 20.7 20.7 20.7 20 1.2
2400 Anh 290 337 307 43 20.7 21.4 20.8 43 1.4
2400 Qz 301 335 320 17 20.6 21.3 20.8 17 1.4
2400 Ep 305 322 314 2 20.6 20.6 20.6 2 1.0
2200 Ep 289 353 309 20 21.1 21.1 21.1 20 1.9
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 287

Table 1 (continued)

Depth Host min. Th range Th av. n Tmi range Tmi av. n Salinity

1900 Ep 285 339 305 10 20.7 21.2 20.9 10 1.5

1660 Ep 275 288 284 33 22.6 23.5 23.0 33 4.9
1400 Qz 231 284 278 46 21.4 21.4 21.4 46 2.4
1100 Ep 238 277 255 32 20.9 25.3 22.0 32 3.3
900 Qz 204 270 250 49 21.2 21.2 21.2 49 2.0
900 Wai 208 243 237 28 21.1 21.1 21.1 28 1.9
600 Wai 196 248 220 61 20.9 20.9 20.9 61 1.5
400 Wai 211 223 210 22 21.0 22.0 21.0 22 1.7
400 Qz 226 235 227 64
200 Cc 177 207 205 9
200 Wai 175 222 208 26 21.0 21.0 21.0 25 1.7
200 Qz 163 223 195 22
80 Cc 110 164 140 17 20.8 20.8 20.8 17 1.4
80 Qz 131 142 137 50 1.0 12.0 7.5 50 ±

Az-49
2494 Qz 290 359 303 40 20.9 20.9 20.9 40 1.5
2400 Qz 286 318 296 50 20.4 20.4 20.4 50 0.7
2300 Qz 242 359 298 31 20.8 20.8 20.8 31 1.4
2200 Ep 278 285 281 5 21.2 21.2 21.2 5 2
2100 Ep 270 332 288 3 21.4 21.1 21.4 3 2
2000 Qz 268 336 304 48 20.2 20.2 20.2 48 2.0
1900 Ep 279 304 286 7 20.6 20.6 20.6 7 1.0
1800 Ep 201 281 273 10 20.6 20.6 20.6 10 1.0
1700 Ep 263 304 382 11 20.6 20.6 20.6 11 1.0
1600 Qz 263 277 268 26 21.0 21.0 21.0 26 1.7
1500 Qz 254 278 260 58 20.8 20.8 20.8 58 1.4
1400 Ep 241 275 260 12 21.4 21.4 21.4 12 3.2
1200 Cc 236 264 252 31 22.4 22.4 22.4 31 4.0
1100 Qz 235 250 241 42 21.0 21.0 21.0 42 1.7
1000 Qz 220 245 239 28 21.1 21.1 21.1 28 1.9
700 Qz 143 172 165 33 20.4 20.4 20.4 33 0.7
600 Qz 143 144 144 20 20.2 20.2 20.2 20 0.3
Az-50
1400 Qz 186 220 195 49 21.2 21.2 21.2 49 2.0
1280 Qz 181 197 186 38 20.3 20.8 20.6 38 1.0
1100 Cc 150 159 152 26 20.5 20.5 20.5 26 0.8
800 Cc 114 140 122 18 0.3 21.0 ± ± ±
Az-52
1900 Qz 263 291 262 42 20.5 20.5 20.5 42 0.8
1700 Qz 247 303 262 40 20.5 20.3 20.4 40 0.7
1500 Ep 246 292 267 32 22.4 21.9 22.0 32 3.3
1400 Ep 250 299 276 10 21.4 21.4 21.4 10 2.4
1300 Ep 243 280 253 5 21.9 21.4 21.6 5 2.7
1212 Pre 227 262 248 50 20.5 20.5 20.5 50 0.8
1200 Ep 251 287 273 10 20.7 20.3 20.5 10 0.8
1100 Pre 237 296 259 24 20.6 21.1 20.8 24 1.4
1000 Ep 237 283 255 10 20.8 20.8 20.8 10 1.4
900 Qz 221 261 253 20 20.1 20.2 20.1 20 0.2
800 Qz 218 236 225 34 20.1 20.1 20.1 34 0.1
700 Cc 211 229 222 26 20.8 20.4 20.6 26 1.0
600 Cc 181 236 213 31 0.1 0.1 0.1 31 ±
288 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Table 1 (continued)

Depth Host min. Th range Th av. n Tmi range Tmi av. n Salinity

500 Cc 144 246 168 20 0.3 0.3 0.3 20 ±

400 Cc 144 246 168 10 0.1 0.1 0.1 10 ±
300 Qz 140 257 155 8 0.1 0.1 0.1 8 ±

Az-53
2000 Ep 307 380 324 10 20.8 20.8 20.8 10 1.4
1900 Ep 298 358 335 8 20.8 20.8 20.8 8 1.4
1820 Ep 311 335 326 11 20.6 20.6 20.6 11 1.0
1700 Qz 289 334 315 28 20.6 20.6 20.6 28 1.0
1600 Qz 289 333 305 37 20.4 20.4 20.4 37 0.7
1500 Qz 268 333 285 40 20.6 20.6 20.6 40 1.0
1400 Qz 256 375 265 46 21.0 21.0 21.0 46 1.7
1300 Qz 206 300 261 50 20.6 20.6 20.6 50 1.0
1200 Cc 198 355 272 28 20.1 20.8 20.1 28 0.8
1100 Qz 231 348 267 26 20.6 20.6 20.6 26 1.0
1000 Cc 184 255 221 60 20.1 20.3 20.1 60 0.3
900 Qz 221 247 241 50 20.2 20.2 20.2 50 0.3
800 Cc 149 249 213 20 20.3 20.3 20.3 20 0.5
720 Cc 190 232 215 28 20.6 20.6 20.6 28 1.0
600 Cc 104 202 176 31 20.2 20.2 20.2 31 0.3
500 Qz 118 184 357 12 0.3 0.3 0.3 12 ±
400 Cc 127 163 150 10 0.2 0.2 0.2 10 ±

predominance of the liquid phase. The sizes of FI
ranged from 3 to 10 mm.
6.1.1. Ice melting temperatures
The microthermometric analyses indicated a
geothermal ¯uid of relatively low concentration,
since ice melting temperatures (Tmi) vary from 20.1
to 23.08C (0.2 to 4.9 wt% NaCl eq.). This concentra-
tion is compatible with the composition of geothermal
¯uids in the present system (Moreno Ochoa, 1989).
The ice melting temperatures in Los Azufres show
consistent changes in the ¯uid concentration with
increasing depth (Figs. 5 and 6). A ®rst zone, observed
in the deepest areas of the geothermal wells, shows
very diluted ¯uids as the Tmi from this area ranged
from 20.1 to 20.58C (0.2±0.9 wt% NaCl eq.). A
second zone was identi®ed overlying the ®rst one.
Due to its higher salinity, Tmi ranges between 20.5
to 20.78C (0.9±1.2 wt% NaCl eq.). The highest ¯uid
concentrations were measured in FI in hydrothermal
minerals, sampled between 1200 and 1500 m depth.
Their Tmi yielded values between 20.7 and 238C,
reaching salinities as high as 6.4 wt% NaCl eq. It is
important to note that some samples presented FI with
only one liquid phase (vapor) in them, and that some
inclusions homogenize into the vapor phase (and not
into the liquid phase, as normally seen in the ®eld).
These observations may indicate the in¯uence of a
vapor rich zone in this area, e.g. the zone where the
geothermal brine is supposed to boil. The important
gain in ¯uid salinity may as well re¯ect the boiling
process, as gas loss from the system changes the ¯uid
composition signi®cantly.
The shallowest areas in the ®eld presented system-
atically positive ice melting temperatures (Tmi from
10.4 to 17.58C). This has been observed in other
®elds and hydrothermal systems (Bodnar et al.,
1985; Hedenquist and Henley, 1985; Sasada, 1985)
and have attributed positive Tmi to the presence of
CO2 in the ¯uids. Moore et al. (1992) emphasized
the existence of a CO2-rich liquid phase in the shal-
lowest zones in Los Azufres, estimating a CO2
concentration up to 5.7 wt%. However, these observa-
tions have not been con®rmed by any analytical studies
(e.g. Raman spectroscopy). Consequently, further studies
are necessary in Los Azufres to corroborate the presence
of CO2 in the gas phase of the FI and to explain the
positive melting temperatures at shallow depths.
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 289

Temperature [ºC]

0 50 100 150 200 250 300 350

0

0 % NaCl
5 % NaCl
10 % NaCl
250 Measured
Quarz
Calcite

500
Depth [m]

750

1000

1250

Fig. 7. Depth distribution of the homogenization temperatures (Th) and in situ measured temperatures of the well Az-26 from the southern part
of the geothermal ®eld. The positions of the mineral symbols show the Th mean values.

6.1.2. Homogenization temperatures
Measured homogenization temperatures (Th) of the
FI range from 122 to 3458C (Table 1). Using these
results, isotherms were drawn for two cross sections
through the entire ®eld (Figs. 5 and 6). For compar-
ison, in situ temperatures were also plotted on these
®gures. In Los Azufres, in situ temperatures are
systematically measured using geophysical methods
directly in the drilled well (shut-in), after reaching
thermal recuperation (up to 24 h). Figs. 5 and 6
show that homogenization temperatures are consis-
tently higher than the present in situ temperatures.
This may indicate a retrograde cooling of the Los
Azufres geothermal ®eld of about 50±708C, since
the time of widespread hydrothermal mineral
formation.
Figs. 7 and 8 present the range of Th measured and
in situ temperatures versus depth for the wells Az-26
and Az-44 from the southern and northern part of the
®eld, respectively. Boiling curves for ¯uids with a
concentration (NaCl-equivalent) similar to that in
Los Azufres are also shown in the ®gures. Figs. 7
and 8 show that most of the observed Th ranges at
different depths do not reach the boiling curves of
waters with composition similar to that of Los
Azufres. Since boiling is an important process in the
Los Azufres system (Iglesias et al., 1985; Nieva et al.,
1986, 1987a), we conclude, that important physico-
chemical parameters (in particular pressure) have
changed since the time of mineral formation and/or
start of ®eld exploitation.
The cross section presented in Fig. 6 reveals a
290 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Temperature [ºC]
0 50 100 150 200 250 300 350
0

500

1000

1500
Depth [m]

2000

0 % NaCl
5 % NaCl
2500
10 % NaCl
Measured
Quartz
3000 Wairakite
Epidote

3500

Fig. 8. Depth distribution of the homogenization temperatures (Th) and in situ measured temperatures of the well Az-44 from the northern part
of the geothermal ®eld. The positions of the mineral symbols show the Th mean values.

decrement in the homogenization temperatures in the
deepest parts of well Az-50. In order to corroborate
this lower temperature gradient, two plan sections at
an altitude of 1000 and 2000 m were drawn in Fig. 9.
These ®gures show a group of isotherms distributed
almost concentrically, with the highest temperatures
in the vicinities of well Az-9. A region of lower
temperatures is observed to the SW, where Az-50 is
located. This may indicate the presence of cold ¯uids
recharging the geothermal reservoir from the SW
during formation of the hydrothermal minerals.
6.2. Isotopic indications
6.2.1. Global hydrothermal systems
A variety of theories exist on the origin of ¯uids in
hydrothermal systems. Craig (1963) indicated that
geothermal waters were composed mostly of local
meteoric origin with minor contributions from other
sources. Deviations of the primary meteoric compo-
sition in form of a positive 18O-shift are explained by
secondary water/rock-interaction processes. On the
other hand, studies of Sakai and Matsubaya (1977),
Taran et al. (1989) and Giggenbach (1992) indicate
the in¯uence of a magmatic component in hydrother-
mal systems hosted at some relatively young volca-
noes. The most probable composition of primary
magmatic waters (PMW) is intermediate between
that of degassed magma and subduction related vol-
canic vapor with an estimated d D of 260 ^ 10½
(Giggenbach, 1992) (Fig. 10). Primary magmatic
water is considered to be identical to ªresidualº
magmatic water, i.e. water left after crystallization
of the magma (Taylor, 1992). In subduction related
tectonic systems, such as the Paci®c Convergent Plate
Boundaries, seawater is transported together with
marine clay sediments by the subducting slab to
depth beneath the continental crust. The d D values
of this subducted sedimentary water, also called
ªconvergent margin degassed magmatic watersº
(D'Amore and Bolognesi, 1994) or ªandesitic
watersº, is assumed to be 230 ^ 10½ (Giggenbach,
1992). Most of the largely neutral, high Cl waters
from the Paci®c Convergent Plate Boundaries are
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296 291

Fig. 9. Isotherms of the homogenization temperatures of the geothermal reservoir at 1000 m.a.s.l. (above) and 2000 m.a.s.l. (below).

characterized by a large positive isotope shift in both,
d 18O and d D (Giggenbach, 1992), indicating other
processes than water/rock interaction.
The formation of hydrothermal ore deposits causes
modi®cations in the isotopic composition of the
hydrothermal ¯uids: Lower temperature sericitic
alteration is characterized by various mixtures
between late-stage magmatic water and meteoric
water with a range of isotopic composition depending
on the palaeolatitude and altitude (Sheppard et al.,
1971; Hedenquist and Lowenstern, 1994).
6.2.2. The hydrothermal system of Los Azufres
Isotopic data from springs (Birkle, 1998) and from
production wells during the initial (1980±1981) and
intermediate (1985±1987) period of geothermal
production (Nieva et al., 1983; Nieva et al., 1987b,
respectively) are illustrated in Fig. 10. Most of the
surface samples are located close to the global meteo-
ric water line, but two samples with elevated d D and
d 18O ratios are affected by evaporation processes.
The positive isotopic trend of the initial geothermal
¯uids, especially the increase in d D in comparison to
292 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296

Fig. 10. d D and d 18O composition of primary magmatic and andesitic waters (Giggenbach, 1992), as well as secondary alteration processes,
such as epithermal ore deposits (low sulphidation, high sulphidation) (O'Neil and Silberman, 1974; Taylor, 1979; Rye, 1993) or hydrothermal
systems (sericitation) (Hedenquist and Lowenstern, 1994). The Los Azufres brines show an intermediate isotopic position between meteoric
water and subduction-related andesitic water. Secondary sericitation processes caused probably a further shift from the meteoric water line
towards more positive isotopic values.

recent meteoric water, indicates the in¯uence of both,
water±rock interaction and/or mixing processes
between local meteoric water and magmatic ¯uids
within the geothermal reservoir. Similar mixing
processes were described for hydrothermal ¯uids
from Mount St. Helens, USA (Shevenell and Goff,
1993), and Larderello, Italy (D'Amore and Bolognesi,
1994). Because of the very small fractionation factors
governing mineral-water isotope exchange at
magmatic temperatures (Friedman and O'Neil,
1977), the d 18O values of magmatic waters are likely
to be close to those of local parent magmas (D'Amore
and Bolognesi, 1994).
Therefore, a measured d 18O value of 18½ for
ma®c rocks (Torres-Alvarado, 1996) from the Los
Azufres reservoir and surface meteoric water with
dD ˆ 275½ and d18 O ˆ 210:7½ were used as
magmatic and meteoric end members, respectively.
A mixing portion between 25:75 and 35:65 between
magmatic waters and meteoric water was achieved for
the Los Azufres ¯uids. The low d D-values of the
geothermal ¯uids can not be deduced exclusively to
the subducted sedimentary slab, but to a primary
magmatic water component. On the other hand, the
lack of 14C in the geothermal ¯uids indicates a major
in¯uence of magmatic CO2 gas and minor in¯uence of
recent meteoric water within the geothermal reservoir
(Birkle, 1998). In addition, the existence of hydrother-
mal alteration, related to the formation of a variety of
secondary minerals (see Petrology Chapter) supports
 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296
the hypothesis of further isotopic modi®cations by
posterior water±rock interaction. The geothermal
liquids from Los Azufres could also be related to
high sulphidation or low temperature sericitic alter-
ation processes (Fig. 10). Due to the abundance of
sericitic mineral paragenesis, the latter case is
favored. Thus, the positive 18O- and D-shift of the
geothermal ¯uids can be explained by: (a) fossil
meteoric water, that subducted partially as part of
the sedimentary slab (ªandesitic watersº), or in®l-
trated during glacial period; and (b) was mixed with
primary magmatic water and c) modi®ed by second-
ary sericitation processes. Especially the latter process
camou¯ages the real proportion of the meteoric water
component.
The Broadlands geothermal system, New Zealand,
is an isotopic similar case to the Los Azufres reser-
voir: the H-shift indicates a 20% component of low-
salinity magmatic vapor mixed with local meteoric
water. Both systems are characterized by elevated
gas contents (2.0 and 1.1 wt%, respectively)
(Brown, 1986).
7. Discussion
Small differences in the chemical composition of
the FI (differences in Tmi) indicate a distinctive zona-
tion of the geothermal ¯uids with depth. Two zones
are important to distinguish: a deeper zone with low
concentrated ¯uids and the overlying zone with a
higher salinity (Figs. 5 and 6). These chemical differ-
ences may be interpreted as the effect of boiling
processes, since the loss of the gas phase changes
the ¯uid composition. In fact, boiling is a frequent
process in low pressure environments (such as
geothermal systems; Hedenquist and Henley, 1985).
Its presence in Los Azufres is supported by some
evidences such as: (a) the occurrence of some gas
inclusions together with liquid ones; and (b) homoge-
nization into the gas phase, as well as into the liquid
phase in the same mineral sample; (c) elevated ¯uid
concentration; (d) lower pressure than the hydrostatic
one (Figs. 7 and 8). In this sense, the FI results support
the model of the physical state of the Los Azufres
¯uids presented by Iglesias et al. (1985), who inter-
preted three distinguishable zones in the ®eld: (1) a
compressed-liquid zone under hydrostatic pressure
293
regime at increased depths (,1600 m); (2) a zone
with two ¯uid phases (where boiling occur); and, (3)
a shallow, vapor pressure-dominated zone. This
observation may have important implications for
®eld exploitation.
On the other hand, ¯uid inclusion results seem to
support the hypothesis related to the origin of the
geothermal ¯uids, based on their isotopic characteris-
tics (see above). Very little variation of the salinity
was observed at constant Th (see Table 1), indicating a
probable mixing process between diluted and slightly
saline ¯uids during hydrothermal mineral formation.
Furthermore, samples with constant salinities and
changing Th (see Table 1) re¯ect the general cooling
(50±708C) taking place in the ®eld.
Unfortunately, few studies of FI in hydrothermal
minerals have been accomplished on active geother-
mal systems (Cathelineau and Marignac, 1994). Two
case studies of two hydrothermal systems (Los
Humeros, Mexico, and Larderello, Italy) will be
discussed in the following section and compared to
the Los Azufres system.
The Los Humeros geothermal ®eld resembles Los
Azufres in several aspects. Both systems are present in
the Mexican Volcanic Belt and related to young, felsic
volcanism. However, in Los Humeros, the volcanic
sequence rests upon a calcareous basement of Cretac-
eous age. These older rocks provide special chemical
conditions to the occurring water±rock interaction
processes, resulting in abundance of hydrothermal
calc-silicate minerals (especially garnet, wairakite,
and wollastonite), besides the common propylitic
alteration of the volcanic rocks. FI in secondary quartz
and calcite from volcanic and calcareous cores,
obtained from wells in Los Humeros, were studied
by Prol-Ledesma and Browne (1989). They observed
mainly liquid-rich FI and no clatharates or daughter
minerals were detected. Freezing temperatures indi-
cated the presence of a diluted ¯uid during mineral
formation (0.2±2.7 wt% NaCl eq., slightly less
concentrated than in Los Azufres) with some contri-
bution to freezing point depression by a relatively
high CO2 concentration. Most Th-values match with
present bore temperatures (contrasting the observa-
tions made in Los Azufres). FI results in Los Humeros
pointed out the importance of geological structures for
the ¯uid circulation regime with a zonation of the
temperature pattern related to the central collapse
294 E. GonzaÂlez-Partida et al. / Journal of Volcanology and Geothermal Research 104 (2000) 277±296
structures and some cooling effect due to the intersec-
tion of the geothermal wells with major faults. This
kind of correlation has not been encountered in Los
Azufres due to its complex structural characteristics.
The Larderello geothermal ®eld is one of the best-
studied active geothermal systems in the world. It is
characterized by productive horizons in permeable
layers of Triassic dolomite. Fluid inclusion studies
from Cathelineau et al. (1994) demonstrated the
presence of magmatic ¯uids in the very early stages
of the hydrothermal system. They observed several
generations of high temperature, high concentrated
¯uids trapped in several ¯uid inclusion planes, record-
ing several hydrothermal circulation regimes. They
differentiated: (1) aqueous-carbonic ¯uids, interpreted
as the result of reheating of the ¯uids in the meta-
morphic basement series during contact metamorph-
ism; and (2) Li-rich ¯uids considered to be expelled
from an underlying Li-rich leucogranite and to have
migrated through the metamorphic series, having as a
consequence the mixing of both ¯uids. The character-
ization of Li-rich ¯uids in different proportions of the
observed FI was possible by the identi®cation of salt
hydrate (LiCl´5H2O) using Raman spectroscopy at
very low temperature. This study showed the impor-
tance of precise geochemical analyses of ¯uids
trapped in FI and the necessity of following a similar
attempt at Los Azufres, in order to prove the hypoth-
esis of mixing as the origin of the geothermal ¯uids in
the ®eld.
8. Conclusions
The Los Azufres geothermal ®eld is one of several
hydrothermal systems related to young silicic volcan-
ism in Mexico. Hydrothermal alteration has affected
most rocks in the ®eld to varying extent. Argillitiza-
tion, zeolite and calcite formation and propillitization
are the most important alteration processes occurring
in the ®eld. Studies of FI in hydrothermal minerals
show that the geothermal ¯uid at the time of mineral
formation presented low concentrations (up to
,7 wt% NaCl eq.), very similar to present ¯uids
composition. Homogenization temperatures show,
however, that retrograde cooling and probably
changes in the pressure of the system have been taking
place since mineral formation. Lower homogenization
temperatures to the SW re¯ect a former recharge zone
near well Az-50 during the formation of the hydro-
thermal system.
The high temperature conditions of the Los Azufres
reservoir can be explained by conductive heat produc-
tion of a shallow magma chamber, and additionally by
the rise of heated meteoric water mixed with
magmatic ¯uids. Mixing of the primary magmatic
¯uids with in®ltrating meteoric water causes changes
in the d 18O and d D ratios of the original meteoric
¯uids. Besides, more recent in®ltration of consider-
able components of meteoric water under low
temperature conditions causes sericitic alteration
processes within the more shallow part of the reser-
voir.
Acknowledgements
CFE provided valuable information for this study.
CONACyT (grant I-25814-T) and DGAPA-UNAM
(IN-119798) partially supported this work. We thank
two anonymous reviewers for their helpful comments.
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