Applied

Geochemistry
Applied Geochemistry 20 (2005) 23–39
www.elsevier.com/locate/apgeochem

Hydro-geochemical and isotopic fluid evolution of the Los

Azufres geothermal field, Central Mexico
E. González-Partida a,*, A. Carrillo-Chávez a, G. Levresse a, E. Tello-Hinojosa b,
S. Venegas-Salgado b, G. Ramirez-Silva b, M. Pal-Verma c,
J. Tritlla a, A. Camprubi a
a
Centro de Geociencias, UNAM, Campus Juriquilla, A.P. 15, Juriquilla, Qro., México 76230
b
Comisión Federal de Electricidad, A.P. 31-7, C.P. 58090 Morelia, Mich., México
c
Instituto de Investigaciones Electricas, A.P. 1-475, C.P. 62001 Cuernavaca, Morelos, México

Received 30 August 2002; accepted 19 July 2004

Editorial handling by H. Ármansson

Abstract

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with
depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity
of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant
fluid type and ice melting temperatures (Tmi) near zero (0
C), and salinities of 0.8 wt% NaCl equivalent. The homoge-
nization temperature (Th) = 325 ± 5
C. The boiling zone shows Th = ±300
C and apparent salinities between 1 and 4.9
wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases
(NCGs), mostly CO2. Positive clathrate melting temperatures (fusion) with Th = 150
C are observed in the upper part
of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The
current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host
rock at temperatures between T = 300 and 340
C. The hot spring waters are acid-sulfate, indicating that they are derived
from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of
CO2 (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.
The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures
connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within
the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone,
and mixes with meteoric water in perched aquifers. Stable isotope compositions (d18O–dD) of the geothermal brine indi-
cate mixing between meteoric water and a minor magmatic component. The enrichment in d18O is due to the rock–wa-
ter interaction at relatively high temperatures. d13C stable isotope data show a magmatic source with a minor meteoric
contribution for CO2. The initial isotopic value d34SRES =
2.3&, which implies a magmatic source. More negative val-
ues are observed for shallow pyrite and range from d34S (FeS2) =
4& to
4.9&, indicating boiling. The same fracti-
onation tendencies are observed for fluids in the reservoir from results for d18O.
 2004 Elsevier Ltd. All rights reserved.

*
Corresponding author. Fax: +442 238 1105.
E-mail address: egp@geociencias.unam.mx (E. González-Partida).

0883-2927/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2004.07.006
24 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
1. Introduction
The geothermal reservoir of Los Azufres, situated in
the Trans-Mexican Volcanic belt (Fig. 1) was first dis-
covered in 1972. It is located in the eastern central por-
tion of the Michoacan state, central Mexico. Currently,
the geothermal field has an installed capacity of 88 MW
within an area of 35 km2. There are 67 drilled wells (37
are producers) with an average production of 39 t/h of
steam. The depth of the production wells ranges from
627 to 3544 m. The 88 MW are generated with 7 units
of 5 MW each, a condensation unit of 50 MW and
two units of binary cycle of 1.5 MW each. There are
plans to expand the capacity of the geothermal field to
128 MW with the installation of two more units of 20
MW each.
Los Azufres is the first geothermal field producing
electricity from saturated fluids in volcanic rocks in
Mexico, and the second in importance after Cerro Pri-
eto, Baja California. Los Azufres field is a typical
high-enthalpy hydrothermal system related to a volcanic
caldera and intense fracturing (Ferrari et al., 1991; Pra-
dal and Robin, 1994). The Los Azufres geothermal field
is classified as a ‘‘low sulfidation’’ system (González,
1999) based on its geochemical and petrologic character-
istics, the hydrothermal mineral alteration and the fluid
composition, where S is mostly in the form of H2S.
2. Geological setting
2.1. Surface geology
Fig. 1 shows the regional and local geologic and tec-
tonic framework and a local geologic map of the Los
Azufres region. Fig. 2(a) shows a W–E cross-section
indicated in Fig. 1, based on data from 6 geothermal
wells in the northern sector of Los Azufres area. The lo-
cal basement constitutes a group of andesitic rocks with
some paleo-soil layers, basaltic rocks and volcanic
agglomerates interstratified with the andesites. Overly-
ing this sequence (unconformably) is a sequence of silicic
volcanic rocks (Agua Frı́a rhyolite), lake sediments, the
San Andres dacite, and ignimbrite deposits (Yerbabuena
rhyolite), the last one forming dome structures. Mafic
volcanic rocks (basalts) represent the last volcanic stage
at Los Azufres, with outcrops and some cinder cones in
the east and west of the geothermal field. The whole rock
geochemistry from the different units shows a calc-alka-
line trend (Cathelineau et al., 1987). Structural geology
studies by Garduño (1988) and Ferrari et al. (1991) indi-
cate the existence of three, sub-vertical, main fault sys-
tems. The main one trends E–W and cross-cuts the
other two (minors) with a NE 22–44 SW trend. These
faults are the major cause of the secondary porosity in
the geothermal reservoir. The E–W fault system has a
lateral displacement, with regional relation to the Acam-
bay fault, affecting mostly the south of the Los Azufres
Caldera. The main surface hydrothermal activity in the
caldera is associated with this E–W faulting. These faults
allow fluids to ascend and form an alteration zone, sili-
ceous and clay-rich sinters, ‘‘hot’’ soils, hot springs, mud
volcanoes and fumaroles at the surface.
2.2. Recent mineralogy (hydrothermal alteration)
The deepest well in the Los Azufres reservoir reaches
3,600 m depth (Well Az-44). The host rock is mostly
andesites and minor rhyolites. Hydrothermal alteration
is evidenced by calc-silicates, which define paragenetic
propylitic zones. Fig. 2(a) shows the boundaries of these
alteration zones. The paragenetic mineral assemblages
have been divided into three zones based on the thermal
ranges defined by the fluid inclusion analyses within the
newly formed minerals (González, 2000). From bottom
to surface, these zones are named zone III, zone II and
zone I. Zone III (deepest) is situated in the 300–325
C
range, it is characterized by the assemblage epi-
dote + clinozoisite + actinolite + tremolite ± garnet and
smectite + illite + chlorite in the clay fraction (more chl-
orite than illite and smectite). Zone II is situated in the
220–300
C range, with the following mineral assem-
blage, epidote + laumontite + wairakite, and within the
clay fraction illite + smectite + chlorite. Zone I is situ-
ated in the 150–220
C range and is defined by the pre-
dominance of laumontite. Clay minerals dominate the
zone characterized by a temperature between 100 and
150
C. The assemblage chlorite + quartz + calcite is
present in all the three zones in variable quantities, with
significantly abundant calcite in well Az-40. In surface
sinters, there are elemental S + alunite + kaolinite +
quartz + pyrite.
A generalized zoning of the calc-silicate assemblage
can be observed in the alteration zones, with zeolites
in the upper part and epidote–clinozoisite in the deepest
levels. An argillic alteration zone overlies the calc-silicate
zone and is the dominant surface manifestation of the
hydrothermal alteration. In some parts, there is a min-
eral assemblage composed of kaolinite–alunite–S–quartz
(advanced argillic zone) formed by the interaction of
steam and shallow groundwater.
Chalcopyrite, bornite, covellite, digenite and idaite
(in order of abundance) represent Cu sulfides at Los
Azufres. Other metal sulfides present are pyrite, pyr-
rhotite and marcasite. Hematite is the only metal oxide
present in the opaque mineral assemblages. A redox
process at depth controls mostly the paragenetic assem-
blage succession of the opaque minerals. Boiling of
ascending fluids seems to control the precipitation of
hematite and pyrite in an oxidizing medium, associated
with a considerable rate of generation of steam. Marca-
site is associated with low permeability zones and acid
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39 25

110˚ 100˚
(a) (b) 100˚70'W 100˚50'W 100˚30'W

North America Plate

ACAMBARO
N
20˚00'N

Cuitzeo
Lac
Paci

Sierra
19˚50'N los azufres
La Primavera
fic

Los Humeros
C
Plat

20˚
Los Azufres
e

MORELIA volcanic
Los Azufres
Acoculo complex
Coco HIDALGO
0 km 500 10 km
Plate

100˚42' 30'' 100˚41' 30'' 100˚40' 30'' 100˚39'

(c)
Rio

to
ali
A

19˚50' p
No
gri

W Az-52 Az-27A
o

Az-40

Maritaro Az-53
30'' E
Zone North

Az-44 Az-29
Az-49

Lagu
19˚49' La Cumbre

na V
Az-9

erde
El Chino
30''

Laguna larga
Zone South

Laguna
Larga San Alejo
19˚48'

Az-23
Az-25
Quaternary Alluvium &
Pleistocene Pyroclastics Az-35
Yerbabuena
Rhyolite Az-18
Pleistocene Tejamaniles Az-26
Dacite
Agua Fria
Rhyolite Los Azufres
Pliocene Az-16
Andesite
U. Miocene Complex
Well Fault Az-50 0 1km

Fig. 1. (a) Regional tectonic framework of Mexico and distribution map of the main geothermal zones. (b) General structural map of
the Los Azufres caldera and geothermal field. (c) Detailed geologic map of Los Azufres, location of the geothermal wells and location
of the cross-section W–E (wells Az-40, Az-52, Az-27A, Az-53 and Az-29).
26 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

Fig. 2. (a) W–E geologic cross-section (see Fig. 1(c) for location), showing the depth of the wells from which fluid was analyzed in the
northern sector of Los Azufres geothermal field. The paragenetic zones I, II and III were determined with regard to petrologic
considerations (see text for detailed discussion). Geologic symbols are the same as for Fig. 1(c). (b) W–E cross-section indicating iso-
concentration zones of the paleo-brine (fluid inclusions) and isotherms obtained from microthermometric analyses of fluid inclusions.
Continued lines correspond to average homogenization temperatures zones, where (1) clathrate positive fusion temperatures; (2) fusion
temperatures from
0.7 to
2.4
C; (3) fusion temperatures from
0.5 to
0.7
C; (4) microthermometric analysis of quartz (d); (5)
microthermometric analysis of epidote (m); (6) microthermometric analysis of calcite (j); (7) microthermometric analysis of prehenite
( ).
*
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
pH, related to rhyolite domes (González et al., 2000;
González, 2001).
3. Fluid in fluid inclusions
At Los Azufres, fluid trapped in inclusions during the
growth of hydrothermal minerals in veins (calcite, preh-
nite, wairakite, anhydrite, quartz and epidote) give a re-
cord of the earliest known fluids in this active
hydrothermal system. Fluid inclusions are common in
mineral veins occurring in samples from drill cuttings
and core slices (Lemieux et al., 1989; Moore et al.,
1992 and González, 2000). Complete data for samples
from 15 wells are presented by González (2000), who
presents and discusses the microthermometric behavior
of fluid inclusions from the southern and central por-
tions of the Los Azufres field. Data from González
(2000) were used to plot the microthermometric results
from the northern and NW portion of the Los Azufres
area (Fig. 2(b)).
The iso-concentrations of the proto-fluid and the
average Th are indicated in Fig. 2(b), which is a cross-
section based on 6 geothermal wells. The fluid inclusions
have a first ice melting temperature (eutectic tempera-
ture, Te), Te =
21.5 ± 0.5
C, which implies a NaCl-
rich brine. The final ice melting temperatures (Tmi)
reveals a zoning distribution: (a) deepest zone, close to
the base line 0, zone 3 in Fig. 2(b), where Tf =
0.5 to

0.7
C, with salinities between 0.88 and 1.23 wt%
equivalent NaCl; (b) intermediate zone, located between
1000 and 2500 m. a.s.l. (zone 2 in Fig. 2(b)), with a mix-
ture of L + V and V fluid inclusions, and Tmi =
0.7 to

2.4
C, which corresponds to apparent salinities of
ap.1.2–4.9 wt% NaCl; and (c) shallowest zone located
between the surface and the steam-rich zone (steam
cap or ‘‘clathrate cap’’ zone 1 in Fig. 2(b)), with positive
values for the fusion temperature, indicating a strong
chemical change in the paleo-brine (proto-fluid). The fu-
sion temperatures in this zone are Tmi = +0.1 to +7
C,
which implies an invasion of CO2 with some CH4, N2,
CO, H2 and H2S. A high concentration of CO2 in this
sector of Los Azufres (Suárez et al., 1997) could affect
the cryometric behavior of the fluid inclusions.
The measured homogenization temperatures, plotted
as isotherms (Fig. 2(b)), show an ascending zone be-
tween wells Az-29 and Az-27A, and a descending zone
in well Az-40 (this well has a thermal inversion at depth).
Boiling processes start at the Th = ±300
C isotherm,
which coincides with an increase in the apparent salinity
determined, and an increase of gas concentrations in the
fluid (Suárez et al., 1997).
Fig. 3 shows a depth vs. temperature diagram, in
which the boiling curve for a fluid with 2 wt% NaCl
equivalent has been plotted (considering the water table
to be at the surface since the Agria River discharges
27
water to the local aquifer). The same plot (Fig. 3) shows
the data for the end member wells (Az-29, the hottest,
and Az-40, the coolest), data for S stable isotope S from
the geothermal fluids, data on the distribution of wt% of
non condensable gases NCGs and alteration types for
the different zones. The deepest location from which
data were obtained are in the liquid field and the data
show small dispersion. At a depth of 2300 m, where boil-
ing has been estimated to occur, the data show a wider
dispersion and the liquid steam field is entered. At 700
m depth, where the geothermal fluid is interpreted to
mix with meteoric water, the data suggest liquid phase,
but with positive fusion temperatures, indicating the
presence of NCGs. The average data for the two end
member wells show that the fluids in well Az-40 are cool-
er than those in well Az-29.
In order to understand the vertical evolution of the
geothermal system of Los Azufres, data from Potter
(1977), Haas (1971) and the average homogenization
temperatures (Th), corrected for pressure effects, have
been taken into consideration to plot 3 points (a, b
and c), where important thermodynamic processes have
affected the paleo-fluids (proto-fluid). At a depth of 2900
m in well Az-29 (point a), the characteristics of the pa-
leo-fluid were: homogenization temperature, Th = 325

C; salinity, S = 0.7 wt% NaCl equivalent, pressure,
P = 128 bar; fluid density = 0.640 g/cm3; corrected
homogenization temperature (trapping temperature,
TA), TA = 334
C (TA = Th + 8
C); enthalpy, E = 1499
kJ/mol. Boiling would then occur at 2300 m depth (point
b) with Th = 300
C; apparent salinity S = 1.4 wt%
NaCl; density = 0.734 g/cm3; pressure, P = 85 bar; enth-
alpy, E = 2749 kJ/mol; and +8
C for pressure correction
(TA = 308
C). At 700 m depth (point c) the conditions
would be: Th = 172
C; apparent salinity, S = 1.2 wt%
NaCl equivalent; density = 0.913 g/cm3; pressure, P = 8
bars; and Th = TA.
Currently, the Los Azufres reservoir is composed of
two sectors with different thermodynamic characteristics
(Suárez et al., 1997). The northern sector is a single-
phase liquid reservoir. It is characterized by a hydro-
static vertical profile at an average pressure of 90 bar
and average temperature of 300
C. On the other hand,
the southern sector constitutes three zones (Fig. 3): (1) a
shallow 2-phase steam dominated (2FSD) zone, at initial
average conditions of 55 bar and 270
C; (2) an interme-
diate 2-phase liquid dominated zone (2FLD), at 100 bar
and 300
C; (3) and a deep compressed liquid zone
(CLS), at 180 bar and 350
C. Noncondensable gases
(NCGs in Fig. 3) that accompany steam extraction from
this geothermal field are typically composed of a mixture
of CO2 ± 90 wt% of total NCGs. In the same way, the
distribution of the NCGs constitutes a vertical zonation.
At the deepest levels (CLS zone in Fig. 3), the NGCs
wt% varies from 0.1 to 0.3; in the intermediate zone
(2FLD) the wt% varies from 2.8 to ±0.3; and in the
28 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

Fig. 3. Temperature vs. depth diagram showing the boiling curve for water with 2 wt% NaCl equivalent salinity (BPC). The water
table level is considered to coincide with the surface. Temperature data for well Az-29 is in whole lines. Temperature data for well Az-
40 are shown as dashed lines; where FI, fluid inclusions; (1) positive fusion temperature; (2) fusion temperatures from
0.7 to
2.4
C;
(3) fusion temperatures from
0.5 to
0.7
C; (a)–(c) are points (samples), where the thermodynamic data were calculated.
NGC = distribution in wt% of the non condensable gases. Isotopic behavior of 34S&, 18O& and D&. Types of hydrothermal
alteration with respect to depth.

uppermost zone (2FSD) the wt% varies between 6 and 8.
Since boiling is an important process in the Los Azufres
system (González, 2000), it is concluded that important
physical–chemical parameters (in particular pressure)
have changed since the time of mineral formation and/
or starting of field exploitation. According to Moore
et al. (1992), boiling and segregation of steam is the most
likely mechanism for concentrating vertically transferred
CO2. The transfer of steam and gas to the upper parts of
the Los Azufres geothermal system is demonstrated by
the existence of an advanced argillic alteration zone
formed by the interaction of steam and shallow ground-
water (González, 2000), and by the current distribution
of the NCGs.
The original fluid (proto-fluid) phase starts boiling
during its ascent through the fractured host rock. The
deepest fluid has relatively low salinity (0.7 eq. wt%
NaCl). The salinity recorded in the boiling zone is 2–5
times higher than the original salinity (from 1.0 to 4.9
ap. eq. wt% NaCl). The salinity increase implies an
important vaporization process. It is also known that
the high content of some gases (mostly CO2) can exten-
sively contribute to lower the melting temperature of ice
within fluid inclusions. Boiling causes separation of CO2
and other volatiles, initially dissolved in the liquid phase,
causing the residual fluid to be more oxidizing than that
in the deepest reservoir.
Boiling is a common process in geothermal systems
(Browne, 1984), as well as in epithermal systems during
one or more stages of mineral deposition (Bodnar et al.,
1985). This is due to the fact that, in both systems the
hydrothermal fluids circulate at relatively high tempera-
tures and low pressures. Boiling phenomena are charac-
terized by a significant steam phase increase, during
which there is considerable release of gases (H2, CO2,
CH4, N2, CO, H2S). The gas release leads to a concen-
tration of the brine (higher apparent salinity). The vola-
tile components in geothermal fields and most
epithermal systems are probably similar. The important
role played by these gases in the geochemical control of
the solubility of the fluids has been demonstrated. More
important for the present discussion is the significant
way in which gases affect pressure in the reservoir, and
their direct control of boiling depth. In most active geo-
thermal fields pressure and depth of formation can be
calculated directly from fluid inclusion data. The results
of these calculations can then be compared with direct
field measurements, in order to test the accuracy of the
data interpretation. This is not the case for ‘‘fossil’’
hydrothermal systems, for which there is a need for pres-
sure corrections to calculate the depth of boiling. Boiling
is the key process controlling of the precipitation of
metallic and non-metallic minerals in an ore deposit
system.
The interpretation of the microthermometric data al-
lows the understanding the general thermodynamic evo-
lution of the Los Azufres geothermal field and the
vertical evolution of its geothermal fluids. The concep-
tual model of Nieva et al. (1987) shows that in the deep-
est zone (3500 m), the system is controlled by a
pressurized hot fluid (330
C). According to these
authors, boiling is accompanied by a pressure drop,
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
which in turns favors an increase in steam phase as the
brine ascends towards the surface. During this ascent,
the fluid changes to two phase in the shallowest zone
with steam-dominated and then steam phases, where
steam mixes with water in perched aquifers and with
meteoric water. This model proposed by Nieva et al.
(1987), suggests the existence of ascent and partial con-
densation of steam in the reservoir, during the ascent,
non-volatile species (Cl) concentrate in the liquid in
the deepest portion of the reservoir. According to Moore
et al. (1992), liquid-rich fluid inclusions with CO2 con-
tents between 4 and 6 wt% are characterized by a CO2
clathrate dissociation temperature greater than 0.0
C.
Collins (1979), and Hedenquist and Henley (1985), have
shown that dissolved CO2 within the Na–Cl brine could
lower the ice melting temperature within an inclusion 2

C below the normal range. Thus, variations in ice melt-
ing temperature of inclusions in Los Azufres reservoir
could be explained in terms of the variation in concen-
tration of trapped brine within the fluid inclusions.
4. Geochemistry of present day fluids
4.1. Hydrogeochemistry
Rodriguez (1984), Quijano (1987) and Tello (1991,
1996) have studied the hydrogeochemistry of the Los
Azufres geothermal field. Table 1 shows the chemical
composition of water produced from the different geo-
thermal wells. Table 2 shows the chemical composition
of water from hot springs. The geothermal brine from
Los Azufres is dominated by Cl and Na. The Cl concen-
tration ranges between 1485 and 7297 mg/L, and Na
concentration varies between 914 and 4442 mg/L. The
next highest dissolved species are SiO2 and K. Boron
concentration is relatively high but the Ca and Mg con-
centrations are relatively low (Table 1). Fig. 4 shows a
triangular diagram (SO4–Cl–HCO3, Giggenbach, 1989)
for groundwater from geothermal wells and hot-springs
water. In this diagram, the water can be classified into 4
types: (a) mature type or geothermal water (Cl-rich); (b)
steam heated water (SO4-rich); (c) peripheral water
(HCO3-rich); and (d) volcanic water (Cl–SO4-rich).
Fig. 4 shows that the water from all the geothermal wells
is ‘‘mature’’ water type (Cl-rich), which is characteristic
of deep geothermal water. Water from a third of the hot
springs (Table 2), is heated by geothermal steam (SO4-
rich), another third is peripheral water (meteoric water
with little or no geothermal influence). Samples from a
couple of hot springs fall in the Cl-rich corner, indicat-
ing that this geothermal water reaches the surface
through faults and fractures. The rest of the samples
are scattered in the diagram between steam heated
water–meteoric water– and geothermal water, likely
reflecting water mixing processes.
29
The acid SO4-rich water is meteoric water that inter-
acts with geothermal steam. The SO4-rich waters are
present in geothermal and volcanic systems where steam
condensate interacts with shallow meteoric water caus-
ing oxidation of H2S to SO4 (Ellis and Mahon, 1977).
The high concentrations of B in this type of water
(B = 0.08 and 7.97 mg/L; Table 2) and the relatively
low concentrations of Mg (Mg = 0.03 and 112.5 mg/L;
Table 2), suggest a deep circulation. Furthermore, the
water/rock interaction must have taken place at rela-
tively high temperature because chlorite solubility de-
creases with increase in temperature, thus lowering the
concentration of Mg. All other waters from the springs
fit a HCO3-Cl and HCO3 Cl-poor trend (<12 mg/L),
with a low B concentration (<1 mg/L). However, the
Ca and Mg concentrations of these intermediate waters
are high, suggesting that they are meteoric waters with
shallow circulation through volcanic rocks.
4.2. Water–rock equilibrium state
Solute geothermometers are a powerful tool for
evaluating the conditions at depth in geothermal sys-
tems. However, this method should be applied to sam-
ples with the following basic assumptions: (1) the
system should be in equilibrium; and (2) water–rock
interaction should take place at depth and at a high
temperature. The equilibrium state and the tempera-
tures of the Los Azufres geothermal system can be de-
duced from Fig. 5, where all the samples from the
geothermal wells plot closely indicating an equilibrium
between water and rock. The temperature of this equi-
librium state is from 300 to 340
C. Some water sam-
ples from surface springs are close to this equilibrium
state. Fig. 5 shows a ternary diagram for Na–K–Mg.
The samples at equilibrium (geothermal wells) plot
along the Na–K lines. The bicarbonate-Na springs
are displaced towards the Mg corner and indicate a
temperature <100
C from the K/Mg geothermometer.
This confirms that the bicarbonate-Na springs dis-
charge shallow waters equilibrated with the host rock
at a relatively low temperature. On the other hand,
the acid-sulfate springs also fall in the region of shal-
low waters, but the K/Mg geothemometer yields tem-
peratures >100
C. These are waters of relatively
recent infiltration heated by geothermal steam.
The calculation of hydrological balance resulted in a
potential, average annual infiltration rate of 446 mm/m2
for the Los Azufres geothermal area, which corresponds
to a total of 82 · 106 m3/a. Due to the highly fractured
and faulted structure of the volcanic formations, a con-
siderable potential for the infiltration of recent meteoric
water into deeper sections of the volcanic formations
can be assumed. Isotopic data indicate the minor impor-
tance of recent meteoric water for the recharge of the
geothermal reservoir (Birkle et al., 2001).
 30
Table 1
Chemical composition of the water produced from the geothermal wells from Los Azufres
Well Ho (kJ/kg) Pc (Bars) pH CE (mhos/cm) Cl B HCO3 SiO2 SO4 Na K Li Rb Cs Ca Mg As
Concentrations are in mg/L
AZ-001 7.11 11,600 4029.8 320.3 0.00 1023.7 9.50 2318.2 638.90 31.90 6.800 4.30 7.40 0.000 32.20
AZ-002 1308 26.00 6.58 16,200 6284.6 521.5 2.51 986.3 23.62 3722.4 510.10 30.10 6.370 16.28 302.90 0.045 12.90
AZ-004 1360 10.55 6.64 8950 3190.0 287.0 0.00 1360.0 29.98 1672.0 381.00 24.95 4.680 7.24 5.23 0.035 20.99
AZ-005 2474 26.00 3.83 1600 434.1 60.2 283.0 73.95 234.7 61.42 1.45 0. 950 1.11 4.18 0.040 5.06
AZ-009 1575 16.50 6.81 11,340 4023.0 327.0 1.49 1541.4 15.92 2112.0 544.22 30.37 5.150 7.55 6.77 0.033 15.51

E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

AZ-013 2690 14.64 4.66 139 10.2 33.7 9.89 48.6 15.30 27.4 2.60 0.10 0.340 0.05 0.03 0.007 1.60
AZ-014 1909 10.90 6.02 4500 1485.6 133.7 92.43 583.5 71.80 914.0 180.00 13.00 0.000 0.00 4.00 0.020 20.00
AZ-016 1184 10.00 6.89 20,400 7927.6 600.4 11.78 841.5 48.38 4442.0 746.00 32.40 6.500 11.20 201.00 0.120 7.14
AZ-018 2618 15.98 6.90 10,000 3121.2 467.6 6.78 642.5 55.82 1697.1 379.80 16.78 9.550 18.36 64.61 0.054 20.60
AZ-019 2531 12.71 7.01 8000 4152.3 361.2 0.30 783.4 59.00 2247.0 573.00 31.30 7.400 11.20 15.50 0.040 33.00
AZ-021 7.20 15,000 6451.6 917.9 0.00 431.5 20.50 2730.0 460.00 46.50 5.500 3.60 70.00 6.600 21.00
AZ-022 1860 13.70 7.00 10,790 3743.0 335.0 16.73 1292.0 16.15 1970.0 497.00 27.90 4.220 5.95 10.92 0.020 45.70
AZ-023 7.80 9500 3081.6 243.9 0.00 667.5 16.00 1686.0 420.00 26.70 3.900 2.90 9.00 0.110 25.00
AZ-025 1327 29.40 7.67 8900 3074.3 244.3 24.12 1456.5 40.20 1716.5 403.00 23.54 5.800 9.93 13.44 0.016 22.64
AZ-026 1685 11.62 7.07 8800 2858.9 255.9 44.92 926.0 24.95 1712.7 368.50 19.60 5.010 12.95 47.77 0.019 23.80
AZ-028 1822 33.00 6.63 9650 3292.3 266.9 1.43 1193.7 26.15 1753.2 387.00 22.10 5.400 5.80 12.10 0.012 23.30
AZ-030 6.50 11,600 4212.8 372.5 0.42 1354.2 32.39 2119.4 517.30 36.14 10.420 17.77 26.18 0.048 27.80
AZ-031 7.66 4220 686.4 96.1 1406.50 771.8 364.40 800.0 209.40 6.90 1.600 2.30 9.20 15.800 50.00
AZ-032 2694 34.85 4.80 300 54.4 27.8 18.64 120.4 32.70 59.3 5.90 0.53 0.570 0.07 0.06 0.002 0.40
AZ-033 1900 12.70 6.42 18,700 6636.8 477.4 17.17 1229.5 19.85 3605.8 651.00 20.30 4.520 6.62 240.00 0.023 9.00
AZ-035 44.60 7.50 5900 1866.6 268.6 0.00 240.0 17.00 1035.0 224.70 14.60 1.300 0.90 10.60 0.010 15.10
AZ-036 2490 11.70 6.68 16,000 5716.5 481.5 13.13 847.7 24.42 3195.0 521.24 31.02 6.390 7.52 152.80 0.054 21.09
AZ-042 1242 23.60 6.89 8600 2917.1 228.5 0.53 1232.0 23.40 1636.0 363.00 21.60 3.400 5.90 2.30 0.000 15.00
AZ-043 1974 12.70 7.33 8450 2790.8 232.1 11.96 1240.3 24.51 1539.8 330.60 16.81 3.890 3.58 13.23 0.002 18.00
AZ-045 2563 44.60 6.74 5000 1895.3 301.7 81.42 0.0 27.53 1000.0 277.00 13.60 0.000 0.00 6.50 0.010 24.30
AZ-046 2300 16.87 6.53 17,600 6584.9 497.6 9.12 831.7 26.83 3494.7 542.78 34.76 6.420 7.83 194.20 0.088 13.81
AZ-047 2300 3.54 6.90 25,400 7861.8 66.6 0.00 1046.1 60.00 4426.2 1162.50 65.80 9.500 6.80 27.80 0.500 58.00
AZ-048 1875 39.00 5.43 9050 2966.7 216.7 0.51 1359.7 32.48 1583.1 365.50 19.40 5.100 5.40 9.50 0.014 20.80
AZ-049 8.35 9500 2980.5 222.6 0.00 167.0 66.00 2197.3 522.90 25.40 3.600 3.90 14.00 3.600 16.70
AZ-051 1344 37.12 7.50 7500 2476.1 195.2 0.00 981.1 24.40 1402.7 345.10 19.70 2.800 2.40 3.50 0.010 17.20
AZ-053 7.18 6500 2990.8 205.8 44.97 1109.2 41.11 1570.0 439.00 23.10 0.000 0.00 4.80 0.070 23.90
AZ-055 7.50 11,200 3776.5 365.0 0.00 1025.4 15.80 2111.6 505.00 29.00 3.600 3.60 16.10 0.030 35.00
AZ-056 1739 10.50 7.05 7800 4071.5 0.0 40.24 0.0 19.23 2085.0 618.00 32.00 0.000 0.00 10.30 0.030 31.80
AZ-059 1963 26.41 7.22 4700 2141.0 153.6 2.67 0.0 37.60 1237.0 230.00 15.60 2.800 6.00 31.70 0.030 16.10
AZ-062 1868 39.20 7.03 10,360 3505.5 318.0 20.44 1257.0 14.01 1865.0 431.00 29.69 3.990 5.63 8.97 0.050 27.27
Data refers to atmospheric conditions. R indicates that the well is currently used for injection.
Table 2
Chemical composition of hot spring water located in and around the Los Azufres geothermal field
Locality No Temp. pH EC Cl B HCO3 SiO2 SO4 Na K Li Rb Cs Ca Mg As Fe Al
sup. (mhos
Concentrations are in mg/L
/cm)
Agua Fria II M-47 83 6.6 890 2.80 0.59 0.40 172.30 373.00 27.60 53.40 0.018 0.85 0.00 4.40 0.30 0.10 4.60 0.00

E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

Agua Fria III M-48 70 2.9 1335 4.20 1.87 0.00 323.40 732.80 26.80 29.60 0.037 0.52 0.00 18.60 2.20 0.00 12.30 0.00
AGUA FRIA IV M-49 90 2.2 3300 9.80 0.59 0.00 464.60 866.50 34.30 29.50 0.034 0.55 0.00 2.10 0.00 0.55 9.90 0.00
AZUFRES I M-34 29 2.5 1760 13.70 1.42 0.00 365.20 498.40 72.80 30.30 0.180 1.56 0.00 12.90 1.10 0.00 4.20 0.00
CASA LAZARO M-43 44 8.4 705 7.30 0.94 324.70 455.00 45.20 68.00 16.50 0.107 0.28 0.00 26.40 25.40 0.10 0.00 0.00
CARDENAS
CUMBRES I M-28 85 1.95 6580 10.00 47.28 0.00 456.00 4472.00 20.28 5.66 0.051 0.24 0.00 3.57 0.59 0.10 84.32 139.20
CUMBRES II M-29 90 2.0 5650 52.70 39.20 0.00 377.00 843.30 8.10 5.30 0.000 0.10 0.00 4.40 1.70 0.10 39.90 0.00
CURRUTACO M-37 50 2.0 6800 30.10 8.30 0.00 496.70 2598.30 8.30 6.60 0.026 0.21 0.00 0.90 0.30 0.10 44.10 0.00
CHIFLADOR M-38 91 2.2 7500 19.60 70.40 0.00 489.80 1140.30 27.30 34.80 0.016 0.27 0.00 8.20 0.30 0.00 32.10 0.00
EL BOSQUE M-56 23 8.0 380 6.30 0.10 228.00 187.60 9.70 23.70 4.40 0.050 0.50 0.00 25.10 22.50 0.00 0.10 0.00
STA. ROSA
EL CARCAMO M-7 25 6.12 398 2.43 0.09 234.00 134.00 7.80 11.27 6.07 0.049 0.05 0.00 13.78 30.53 0.00 0.03 0.40
FABRICA LA M-6 18 8.3 370 17.20 0.08 124.60 118.50 25.70 19.50 6.70 0.000 0.48 0.00 30.00 15.40 0.10 0.00 0.00
VIRGEN
JARIPEO M-10 25 8.4 960 7.40 0.31 600.20 180.70 10.40 60.30 9.30 0.100 0.65 0.00 7.30 74.70 0.00 0.00 0.00
LAS ADJUNTAS M-16 40 6.92 338 2.07 0.34 165.00 190.00 27.53 39.05 12.36 0.074 0.10 0.00 8.93 6.24 0.01 0.03 0.49
LA HERRADURA M-20 26 8.4 350 18.60 0.31 147.70 93.20 28.70 65.90 2.80 0.000 0.98 0.00 21.00 4.00 0.10 0.00 0.00
LA TRASQUILA M-65 20 6.92 178 2.31 0.34 45.96 95.34 23.22 9.13 4.31 0.000 0.16 0.00 8.89 5.92 0.00 0.08 0.61
LAGUNA VERDE M-32 22 2.4 2950 491.40 46.40 0.00 223.80 444.80 247.50 60.70 3.440 2.12 0.00 22.40 2.60 0.50 39.70 0.00
LOS HERVIDEROS M-18 80 7.06 3850 1058.10 65.80 152.00 342.00 150.00 721.50 10.66 6.940 0.88 1.58 21.60 0.33 3.00 0.13 0.54
MARITARO M-25 91 3.9 1205 23.20 2.96 0.00 606.70 708.70 32.80 10.80 0.047 1.21 0.00 82.80 29.00 0.00 112.50 0.00
NOPALITO I M-27 78 2.31 3770 3.22 3.19 0.00 327.30 1363.00 23.22 16.00 0.090 0.20 0.00 53.33 49.29 0.00 11.97 42.10
POZO AZ-24 M-0 90 7.4 1185 55.40 9.27 16.20 554.50 602.00 208.50 31.90 0.679 0.96 0.00 3.30 0.20 0.00 0.30 0.00
PUENTECILLAS M-39 63 6.64 947 33.84 4.91 91.55 266.95 324.59 173.15 20.80 0.220 0.26 0.00 11.00 0.13 0.00 0.07 0.40
SANTA ROSA I M-8 18 8.0 1380 9.80 0.38 886.90 189.20 11.40 78.40 11.60 0.180 0.60 0.00 4.90 112.50 0.00 0.00 0.00
TEJAMANILES II M-42 68 8.3 790 2.60 4.60 136.50 310.80 161.50 144.80 36.30 0.278 0.42 0.00 3.40 0.10 0.00 0.00 0.00
ZIMIRAO M-17 40 8.0 3600 1067.00 76.97 109.30 386.40 147.40 689.90 45.50 6.200 3.00 0.52 54.80 0.40 3.00 0.20 0.00
TEMP SUP indicates surface temperature in
C.

31
32 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

C1 Na/1000
100 0 100 0
Well Well
Hot spring Hot spring

80 20 80 20

Mature waters

60 40 60 tK Full equilibrium 40
/N
a
180˚ 160˚ 140˚ 120˚
200˚
rs
te

220˚ 100˚
wa

C1 240˚
60
nic

40 60 40
ca

260˚

Per
Vol

iph
era
Partial equilibrium
lw
SO4 HCO3 ate
80 20 80
20 rs
Immature

t K/Mg
waters
Steam Heat Waters
100 0 100
0
SO4 HCO3 K/100 100 60 40 20 0 Mg
100 80 60 40 20 0 80

Fig. 4. Ternary diagram showing the relative Cl–SO4–HCO3
content in the Los Azufres thermal waters. The digram shows
the fields of the different types of water: mature water, volcanic
water, steam-heated water and peripheral water. See text for
discussion (Giggenbach, 1989).
Fig. 5. Ternary diagram Na–K–Mg showing the evolution of
the Los Azufres thermal waters from wells and srpings. The
diagram shows the fields for the different equilibrium states
(inmature-partial equilibrium-full equilibrium), and isotherms
(Giggenbach, 1989).

of gases from smokers are shown in Fig. 6. Two groups

5. Geochemistry of gases
5.1. Noncondensable gases in the steam
The results of the chemical analyses of gases pro-
duced from the geothermal wells are presented in Table
3. The gases in the steam dominant zone are mostly
composed of CO2 (80–98% of all the gases). Other gases
present are: H2S (1.16%), H2 (0.026%), N2 (0.77%), and
CH4 (0.01%). The average concentration of the gases is
between 2 and 9 wt% of the total mass of the fluid in
the reservoir (Suárez et al., 1997). Giggenbach (1980)
proposed a ternary diagram for He–Ar–N2 to identify
the relative proportion of the 3 components: (1) atmos-
pheric, (2) crustal and (3) magmatic, in the geothermal
fluids. Fig. 6 is a ternary diagram for N2, He and Ar.
Samples from geothermal wells (Az-9, Az-46, Az-17)
plot on the mixing line between crustal and meteoric sat-
urated water. The high He content detected in some of
the geothermal well fluids suggests a relatively slow cir-
culation of the geothermal fluids through the host rock.
It is important to mention the two trends shown by the
gases of deep circulation (geothermal samples) and the
atmospheric-rich gases (fumaroles and smokers). Some
geothermal wells are used for deep injection, and this
process produces an equilibration of N2/Ar with atmos-
pheric conditions.
5.2. Noncondensable gases in the smokers
In order to understand the genesis of the gases in the
surface geothermal manifestations (fumaroles), several
samples were collected. The results of chemical analyses
of samples are indicated, the northern and southern
groups. The smokers from the north are derived from
saturated water and gases of magmatic genesis. The
samples from the Agua Frı́a site are most representative
for this group. However, fumarole samples from the
southern zone plot in the region of deep circulation in
the crust. This suggests a longer residence time of the flu-
ids in the host rock, or relatively lower permeability in
the southern zone. Based on the local geology of this
geothermal field, there are rhyolites with low permeabil-
ity in the southern zone. These rhyolites act as seal rock,
which causes a longer time for the fluids to reach the sur-
face through the smokers. This process causes the for-
mation of He by radioactive decay of 3H.
The Cl analyses show that boiling has been more in-
tense in the southern than in the northern sector. Initial
studies of the composition of phases in the reservoir
(Nieva et al., 1987) showed that concentration of fluid
volatile components such as CO2 and 2H will decrease
with depth, while concentration of non-volatile compo-
nents such as 18O and Cl will increase (Nieva et al.,
1987; Suárez et al., 1997).
5.3. Water–gas equilibrium
The chemical composition of the gases produced by
the geothermal wells and smokers can be used to calcu-
late the equilibrium state between water and gases and
the equilibrium temperature as well. Fig. 7 is a plot of
log H2/Ar vs. log CO2/Ar. The maximum temperature
for the geothermal wells is close to 350
C, which is con-
sistent with estimations by liquid geothermometers
(González, 2000). The water–gas equilibrium conditions
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39 33

Table 3
Chemical composition of the gases produced by geothermal wells at Los Azufres
Well Ho kJ/kg Pc Bars Ps Bars Xg wt% He H2 Ar N2 O2 CH4 CO2 H2S NH3
Data in wt% (dry)
AZ-002 1308 26.00 9.30 1.171 0.00000 0.0410 0.4460 25.4000 0.0000 0.0000 71.94 2.191 0.008
AZ-004 1360 10.55 6.64 0.128 0.02800 0.0790 0.0070 3.3100 0.0000 0.0550 86.09 7.214 3.222
AZ-005 2474 26.00 8.50 3.113 0.00011 0.0100 0.0316 0.3620 0.0000 0.0317 98.17 1.367 0.025
AZ-006* 10.50 8.10 4.209 0.00065 0.0187 0.0432 3.1360 0.0000 0.0164 96.32 0.462 0.000
AZ-009 1575 16.50 8.50 0.842 0.00000 0.3850 1.5300 40.4000 0.0000 0.0000 53.32 3.075 1.291
AZ-013 2690 14.64 12.67 2.086 0.00028 0.0675 0.0107 0.4399 0.0000 0.0593 97.15 2.200 0.126
AZ-014 1909 10.90 0.00 0.577 0.00000 0.0618 0.0506 2.5320 0.0000 0.0780 95.91 1.370 0.000
AZ-015 17.13 7.69 1.655 0.00000 0.0208 0.0188 0.9299 0.0000 0.0229 97.78 1.130 0.000
AZ-016 1184 10.00 9.10 4.008 0.00000 0.0181 0.0171 0.7361 0.0000 0.0000 98.65 0.577 0.000
AZ-016D 2567 11.62 11.40 4.063 0.00000 0.0318 0.5069 31.9303 0.0000 0.0000 66.10 1.427 0.000
AZ-017* 9.70 8.80 2.870 0.00000 0.0432 0.1818 12.8170 0.0000 0.0074 86.06 0.890 0.000
AZ-018 2618 15.98 9.15 8.016 0.00043 0.0040 0.0025 0.3213 0.0000 0.0384 99.18 0.454 0.000
AZ-019 2531 12.71 5.87 0.207 0.00000 0.1504 0.1298 5.5350 0.0000 0.1018 85.11 8.973 0.000
Az-022 1860 13.70 8.30 1.250 0.00110 0.0300 0.0054 1.0600 0.0000 0.0250 95.80 2.240 0.874
AZ-025 1327 29.40 9.50 0.590 0.00400 0.0300 0.0086 0.8800 0.0000 0.0720 95.60 2.620 0.755
AZ-026 1685 11.62 10.07 12.930 0.00060 0.0027 0.0023 0.2743 0.0000 0.0638 99.32 0.284 0.044
AZ-028 1822 33.00 10.40 0.312 0.00000 0.0640 1.3500 1.5700 0.0000 0.0189 90.11 5.365 1.528
AZ-030 0.195 0.00000 0.0330 2.3760 11.5800 0.0000 0.0000 85.77 0.061 0.169
AZ-032 2694 34.85 12.30 1.271 0.00024 0.0105 0.0115 0.5863 0.0000 0.0800 96.57 2.588 0.145
AZ-033 1900 12.70 9.80 3.163 0.00059 0.0096 0.0226 1.6393 0.0000 0.0232 97.53 0.697 0.078
AZ-034* 38.00 9.80 7.010 0.00057 0.0370 0.0028 1.6210 0.0000 0.0510 97.80 0.354 0.138
AZ-035 44.60 10.40 1.593 0.00006 0.0185 0.0185 0.6571 0.0000 0.0278 97.31 1.787 0.176
AZ-036 2490 11.70 10.40 3.920 0.00019 0.0149 0.0187 1.1000 0.0000 0.0145 97.95 0.859 0.045
AZ-038* 13.80 8.40 5.920 0.00033 0.0160 0.0030 0.8382 0.0000 0.0470 98.40 0.646 0.071
AZ-041* 10.60 9.30 2.670 0.00016 0.0557 0.0534 2.5980 0.0000 0.0253 95.24 1.742 0.329
AZ-042 1242 23.60 21.20 0.490 0.00000 0.0000 0.0000 0.0000 0.0000 0.0000 94.84 5.159 0.000
AZ-043 1974 12.70 9.80 2.080 0.00009 0.0094 0.0040 0.3382 0.0000 0.0352 98.00 1.595 0.026
AZ-045 2563 44.60 10.30 0.491 0.00000 0.8076 1.3900 42.1100 0.0000 0.0000 49.01 4.330 2.350
AZ-046 2300 16.87 9.70 2.050 0.00030 0.0400 0.0160 3.1300 0.0000 0.0031 94.81 1.320 0.684
AZ-047 2300 3.54 3.54 1.600 0.00000 0.0146 0.1761 0.3063 0.0000 0.0255 97.45 1.887 0.137
AZ-048 1875 39.00 9.50 0.214 0.01400 0.0500 0.0200 1.6600 0.0000 0.0900 84.81 9.300 4.070
AZ-051 1344 37.12 1.51 0.600 0.00081 0.0418 0.0544 1.8499 0.0000 0.1221 93.89 4.042 0.000
AZ-053 0.796 0.00000 0.0293 0.0218 1.1380 0.0000 0.0896 95.94 2.779 0.000
AZ-055 0.850 0.00010 0.0217 0.0134 0.8420 0.0000 0.0251 97.04 2.054 0.000
AZ-056 1739 10.5 10.5 0.518 0.00000 0.0539 0.0459 1.9810 0.0000 0.0855 90.85 6.988 0.000
AZ-059 1963 26.41 9.95 1.592 0.00007 0.0735 0.1626 2.4318 0.0000 0.0519 93.31 3.478 0.000
AZ-062 1868 39.20 10.20 1.782 0.00320 0.0220 0.0033 0.8270 0.0000 0.0530 97.50 1.350 0.263
Data is in wt% (dry), Xg indicates total content of the gas Ho, enthalpy of the mixture; Pc, pressure at the head of the well; Ps, pressure
at the separation.
Note: the wells* indicate dry steam.

are determined from Fig. 7. It can be said that there is
equilibrium with the liquid phase in water dominated
geothermal wells, whereas in vapor dominated wells
there is equilibrium with the steam phase. This also indi-
cates a water-steam mixing process at relatively high
temperatures, and/or Ar loss.
5.4. Steam excess
Two phases are considered to exist in the system if
the enthalpy of the production wells exceeds that of
the saturated liquid at the reservoir temperature. The
production enthalpy of the wells at Los Azufres varies
between 1235 and 2716 kJ/kg. A high discharge enthalpy
reflects two phases in the reservoir (water and steam).
The discharge enthalpy for well Az-2 corresponds to a
saturated liquid at a steam temperature of 280
C, hence
the steam excess at reservoir conditions is small. For the
rest of the wells the enthalpy is higher, but they produce
from a liquid-rich zone. Some wells produce dry steam
with an enthalpy of 2700 kJ/kg, these are mostly located
within the southern sector of the reservoir.
One of the factors that causes steam excess or enth-
alpy excess in wells is different mechanisms of steam
and liquid phase movement within the rock formations
(different relative viscosities). On the other hand, is it
34 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39

N2/100 in explaining the chemical evolution of the water in

100 0 Well the geothermal reservoir with regard to steam excess
Fumerole data. If the reservoir contains water only, it would be
easy to relate the water chemistry to the reservoir phys-
80 20 ico-chemical conditions (Arnorsson, 1982). On the other
Magmatic hand, if there is excess steam, it is not possible to relate
the chemistry of the fluid at the surface with reservoir
60 40
conditions. Thus, it is only possible to apply this method
to wells with enthalpy below 2400 kJ/kg, which is the
40 60 case for most of the wells at Los Azufres. This method
is not applicable to dry-steam wells.
Meteoric
20 80
6. Stable isotopes
Crustal
0 100
10He Ar Stable isotopes have proven to be a very helpful tool
100 80 60 40 20 0 for understanding the complexity of hydrothermal sys-
Fig. 6. Relative N2–He–Ar content in Los Azufres geothermal
tems (recent-geothermal, or fossil-ore deposits; Valley
gas discharges. The diagram shows the field for the differnet et al., 1986). The use of stable isotopes for solutions of
sources of gases (magmatic, crustal, meteoric, – Giggenbach, geologic problems depends on the assumption of some
1980). basic physico-chemical conditions. The most basic
assumption is chemical and isotopic equilibrium be-
also possible that the steam excess is due to vaporization tween the different species considered (Henley et al.,
during contact of steam with conductively heated host 1984). The definition of the original isotopic source for
rocks, and a drop in pressure during extraction of fluid the different species and their later evolution has been
by the wells. The combined processes cool the fluids a major research topic in earth sciences. Among the
(by boiling). There are, however, some complications different environments, the modern-day hydrothermal

4
Equilibrium steam 100˚ 200˚ 300˚

3 Well

350˚
2
300˚
Log (XH / XAr)

1
2

0 200˚
id CO2 / Ar -temp
liqu
i um
br
-1 uili
Eq
100˚

H2 / Ar -temp
-2

-3
0 1 2 3 4 5 6
Log (XCO / XAr)
2

Fig. 7. Evolution of H2/Ar vs. CO2/Ar at equilibrium conditions in the Los Azufres reservoir. See text for further discussion.
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39 35

Table 4
Stable isotope data for geothermal brine and spring water
Reservoir/Brine Springs
18
Well dD& d O& Locality dD& d18O&
AZ-5
63.2
4.1 AGUA FRIA
71.4
10.3
AZ-6
61.0
4.8 ARARO
58.6
5.8
AZ-9
60.8
3.2 AZUFRES
65.6
8.5
AZ-13
60.8
2.8 AZUFRES
70.4
10.5
AZ-16AD
59.7
4.6 CURRUTACO
25.2 0.4
AZ-17
58.5
4.9 CHIFLADOR
27.9 1.2
AZ-18
61.8
3.0 CHINO 1
70.1
10.2
AZ-22
64.4
3.0 ESPINAZO DEL DIABLO
34.9 1.9
AZ-28
60.1
3.2 LAGO CUITZEO
20.7 2.6
AZ-31
64.2
3.7 LAGUNA AZUFRES
51.1
5.6
AZ-33
64.1
5.3 LAGUNA LARGA
65.4
9.3
AZ-34
56.5
4.7 LAGUNA LLANO GRANDE
79.9
4.9
AZ-35
60.0
4.7 LAGUNA SECA
60.7
6.7
AZ-36
63.0
5.4 LAGUNA VERDE
51.5
5.5
AZ-37
62.3
4.8 MARITARO
17.7 6.9
AZ-38
62.5
5.3 NOPALITO 1
53.3
0.6
AZ-46
56.0
2.6 NOPALITO 3
41.5 2.4
POZO HEDIONDO
59.8
4.4
TEJAMANILES
64.5
8.9

systems provide a great deal of information on physico-
chemical processes that are not observable in ‘‘fossil’’
hydrothermal systems, especially those related to the
chemical controls of the hydrothermal brines.
6.1. Isotopic characteristics of the liquid phase
Table 4 and Fig. 8 show the corrected d18O&–dD&
data for discharge water from the wells and hot springs
at Los Azufres. In Fig. 8 well samples show a positive
d18O& compared to the meteoric line, which is a charac-
teristic of geothermal fluids. This enrichment in d 18O is
due to water–rock interaction at relatively high temper-
atures. Most of the spring samples plot close to the glo-
bal meteoric water line. However, other spring samples,
especially those with SO4-rich chemistry, indicate a
modified isotopic composition and plot along a vapori-
zation line at temperatures above 100
C. The isotopic
composition of surface water samples (lakes) present
an isotopic composition characteristic of highly evapo-
rated water at surface temperature. The regression line
for boiling is shown in Fig. 8 and is: D& = 3.11d18O

39.3. The isotopic composition of the meteoric precip-
itation in the zone can be obtained from this expression
and is
10.7 for d18O&, and
75 for dD&. On other
hand, a value of d18O = +8 & as been recorded for mafic
rocks from the Los Azufres reservoir (Torres, 1996).
6.2. d34S&, and d13C&
Values for d13C in CO2 from the reservoir at Los
Azufres range between 13C =
5& and
11& (Tabaco
et al., 1991). According to Hoefs (1980) CO2of mag-
matic origin ranges between
5& and
8&. The d13C
of the CO2 in meteoric waters varies from d
13
C =
7& to
30&, and the d13C in carbonate rocks
is between
2& to +2&. The influence of an atmos-
pheric component in Los Azufres is reflected by the
abundance of negative d13C values, which indicate some
organic input into the reservoir by meteoric water. An-
other process taking place in the reservoir is the dilution
of paleo-meteoric water with ascending magmatic CO2
(Birkle et al., 2001).
The isotopic composition of the dissolved CO2-
(d 13C &) in water is representative of its ultimate
source (magmatic, carbonate rocks, organic matter
or meteoric water–atmospheric). Thus, the composi-
tion of d 13C& in water can indicate the fractionation
processes like boiling or condensation of the hydro-
thermal fluid (Henley and Ellis, 1983; Panichi and
Tongiorgi, 1976). The isotopic composition of hydro-
thermal fluids depends on: (1) geochemistry of the
source; (2) physico-chemical processes within the reser-
voir; and (3) water–rock equilibrium temperature (Ma-
hon et al., 1980). The detailed studies on d13C& in
Los Azufres by Tabaco et al. (1991) show a range
between
5& and
11&, in which the isotopic fracti-
onation observed is explained by a boiling–condensa-
tion process of the hydrothermal fluid within the
productive zone of the reservoir. Fig. 9 shows the re-
sults for d34S& in pyrites, and H2S and SO4 from the
hydrothermal fluid (see Fig. 3 for special distribution
within the reservoir). The isotopic composition of
the pyrite falls into two distinctive groups, the first
36 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
0
-24
ate
cW
ori
ete
M
al
-48
ob
Gl
δD ˚/˚˚
-72
-96
-120
-13 -11 -9 -7
Fig. 8. Stable isotopes (dD& vs. d18O&) plot for samples of the geothermal brine and surface manifestations (hot springs) of Los
Azufres. (SMOW, standard mean oceanic water). Aditional plotted data from Tello (1996).
group (deepest zones without boiling) with values
from d34 SFeS2 ¼
1:57‰ to
2:97‰, and the second
group (shallowest zones with dominant steam) with
values between d34 SFeS2 ¼
4‰ to
4:83‰. The aver-
age value for FeS2 ðd34 SFeS2 ¼
2:5‰Þ is very similar
to the average value for H2S ðd34 SH2 S ¼
2‰Þ. The
aqueous SO4 has d34 SSO4 ¼ þ21:47‰.
The sulfide–sulfate system in aqueous and crystal-
line media plays a very important role in geochemical
cycles. It is widely known that sulfides oxidize easily,
and that sulfates are difficult to reduce at relatively
low temperatures (<200
C, or near-surface environ-
ments). Sulfate is reduced at temperatures >200
C
only when the pH is low (acidic conditions) and the
S concentration is high. At Los Azufres, the pH is near
neutral at depth and the total concentration of S is
low, but the temperature is ±340
C. González (1985)
shows that the isotopic composition for the source in
the reservoir is d34SRES. =
2.3& (average). The results
of a calculation by Arnold and Gonzales-Partida
(1985) indicate that there is equilibrium between sul-
fates and sulfides at 300
C at the Los Azufres geother-
mal field. It is accepted that the chemical and isotopic
equilibrium between sulfate and sulfides is reached
when the difference d34 SSO4
d34 SH2 S ¼ 103 LnaSO4
H2 S
is obtained (Truesdell, 1984). At the reservoir tempera-
SMOW
ine
r L
.32
-39
δ 18O n
atio
3.11 or
δ D= vap
E
Magmatic
Component
Geothermals fluids
Cold Springs
-5 -3 -1 1 3 5 7 9
δ18O ˚/˚˚
ture of Los Azufres (T = 330 +
10
C), the numeric
value of 103 LnaSO4
H2 S ¼ 23:5‰ (Truesdell, 1984),
which is very similar to measured the ratio
d34 SSO4
d34 SH2 S ¼ 23:47‰ for the reservoir. These
data confirm the chemical and isotopic equilibrium
state at Los Azufres. The initial isotopic value for S
in the reservoir is d34SRES. =
2.3&, which implies a
magmatic source. Values that are more negative have
been observed in pyrites from shallower zones
ðd34 SFeS2 ¼
4‰ to
4:9‰Þ. On the other hand, the
liquid phase from the reservoir has the following iso-
topic values (see Fig. 3): (a) deepest zone,
d18O =
2.4&; (b) shallowest zone d18O =
5.54&,
with an average of dD =
69& from both zones (Nie-
va et al., 1987). Boiling (extensively documented for the
reservoir) seems to control the sulfide precipitation.
González (2000), indicates that these processes promote
a massive separation of sulfide from CO2, H2, and
other volatiles initially dissolved in the liquid phase.
The ascending meteoric water is more oxidizing than
the deepest water from the reservoir, and more oxidiz-
ing than the volcanic rock environment which hosts the
fluid. This situation is responsible for the evolution of
paragenetic assemblages of Fe sulfides and Fe oxides,
from pyrrhotite to pyrite to marcasite and pyrite–hem-
atite in the Los Azufres reservoir (González, 2000).
 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
15
number of measurments
H2S
10
SO4
FeS2
5
0
-15
34
Fig. 9. Isotopic behavior of S from pyrites (shallow zone) and H2S and SO4 from the current geothermal brines in the Los Azufres
geothermal field. See text for further discussion.
The higher concentration of S coincides with the
highest concentrations of calcite in the reservoir and
with the more negative values for the ice melting temper-
atures within fluid inclusions (González, 1999). Accord-
ing to Reed (1998), the constraints of heat transfer in
boiling, near neutral-pH, control the precipitating min-
eral assemblages through the relationship of gas fraction
to CO2 partitioning into the gas phase (and the pH of
the aqueous phase). At higher boiling rates, the residual
fluid is depleted in H2CO3, whereas the CO2 in the steam
phase increases its concentration. These processes pro-
duce the precipitation of calcite by way of:
H2 CO3 ¼ Hþ þ HCO3
HCO3 ðaqÞ þ Hþ ðaqÞ ¼ H2 OðaqÞ þ CO2 ðgÞ
2HCO3 þ Ca ¼ CaCO3 þ CO2 þ H2 O
Birkle et al. (1998) and Tabaco et al. (1991), show
that the lack of 14C in the geothermal fluids indicates a
major influence of magmatic CO2 gas and a minor influ-
ence of recent meteoric water within the geothermal res-
ervoir. According to Suárez et al. (1997), an inverse
relationship seems to exist between bottom hole temper-
ature and pressure on the one hand and gas content on
the other. Non-condensable gas concentrations decline
when pressure and temperature increase.
7. Conclusions
Hydrothermal alteration at the Los Azufres geother-
mal field is mostly composed of calc-silicate minerals
that defines a propylitic type alteration zone (see Fig.
2), which shows progressive dehydration with depth
and temperature increase. A generalized zoning of the
calc-silicate can be observed, with zeolites in the upper
part and epidote–clinozoisite at the deepest levels. An
argillic alteration zone overlies the calc-silicate zone
and is the dominant surface manifestation of the hydro-
thermal alteration. In some parts, there is a mineral
37
at T = 330˚C
3
10 Ln aSO -H S = 23.5 ˚/ (Truesdell, 1984)
4 2 ˚˚
34 34
Reservoir δ SSO - δ SH S = 23.47 ˚/˚˚
4 2
SO4 and H2S from the same fluid
δ34S ˚/˚˚
-10 -5 0 5 10 15 20 25
assemblage composed of kaolinite–alunite–sulfur–
quartz (advanced argillic zone) formed by the interac-
tion of steam and shallow groundwater. The proto-fluid
(fluid inclusions) at the Los Azufres geothermal system
is related to near-neutral NaCl brine, which favors deep
propylitic alteration (productive zone). This zone in
characterized by secondary permeability due to fractur-
ing. At depth, the geothermal field is dominated by a
pressurized liquid, yielding steam in more shallow zones.
The gradual change from liquid to steam phase takes
place through boiling, and is accompanied by changes
in the hydrothermal alteration mineralogy. The type of
alteration passes from propylitic to argillic by means
ð1Þ of an oxidation-acidification process, which includes
NCG particularly CO2.
ð2Þ The zoning of fluids (Tmi) observed within the fluid
inclusions is in acord with the distribution of the
ð3Þ
NCG, the increases in apparent salinity in the boiling
zone and the formation of clathrate in the advanced arg-
illic zone (clatherate cap). The isotopic behavior of the
species analyzed suggests the same general trend.
The deepest fluids in the northern sector of the Los
Azufres geothermal field (Maritano zone) are liquid-
dominated with a dominant NaCl composition, general
low salinity and temperatures ranging from 150 to
325
C. The salinity of the deepest brine as determined
by fluid inclusion analyses is 0.8 wt% NaCl equivalent
(near zero fusion temperatures). The salinity recorded
in the boiling zone at a temperature of Th = 300
C is
2–5 times higher (1–4.9 wt% NaCl equivalent), implying
vaporization and a strong influence of the dissolved
gases (mostly CO2). The fluid inclusions from the top
of the reservoir (from 0 to 700 m depth) have positive fu-
sion temperatures, indicating a high concentration of
gases and fluid temperatures of 150
C. The vertical
cooling down of the reservoir is the result of boiling
(sudden drop of pressure and temperature), which also
causes a sudden increase of apparent salinity, density
and enthalpy of the fluid. The deep water, initially only
a liquid phase, starts boiling during its ascent through
the faulted and fractured host rock. The current fluids
38 E. González-Partida et al. / Applied Geochemistry 20 (2005) 23–39
are NaCl-rich and are in chemical and isotopic equilib-
rium with the rock. The isotopic composition (d18O&-
d D&) of the spring waters shows that it is mostly mete-
oric water since the samples plot near to the global mete-
oric water line. Stable isotopes of the geothermal brine
indicate mixing processes between meteoric water and
a minor magmatic component. The enrichment in d18O
is due to water–rock interaction at a relatively high tem-
perature. The d13C data shows a range between
5&
and
11&, in which the isotopic fractionation observed
is explained by a boiling–condensation process in the
hydrothermal fluid within the production zone of the
reservoir, and a mostly magmatic, with minor meteoric,
source for CO2. The initial isotopic value for S in the res-
ervoir d34SRES. =
2.3& implies a magmatic source.
Values more negative observed in pyrites from the shal-
lowest zones ðd34 SFeS2 ¼
4‰ to
4:9‰Þ are produced
by fractionation during boiling of hydrothermal fluids.
Acknowledgement
This research has been made possible thanks to
Grants UNAM-PAPIIT # IN107203 and # UNAM-
PAPIIT # IN114102.
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