Arab J Geosci (2016) 9: 517
DOI 10.1007/s12517-016-2529-0
ORIGINAL PAPER
Solute geothermometry of Cerro Prieto and Los Humeros
geothermal fields, Mexico: considerations on chemical
characteristics of thermal water
America Yosiris Garca-Soto 1 & Kailasa Pandarinath 2 & Jos Enrique Marrero-Ochoa 3 &
Carlos Daz-Gmez 3
Received: 26 January 2016 / Accepted: 26 May 2016 / Published online: 15 June 2016
# Saudi Society for Geosciences 2016
Abstract A comprehensive study on the chemical consider-
ations of thermal waters (springs and geothermal wells) on the
performance of solute geothermometers in predicting the
reservoir temperatures of Cerro Prieto and los Humeros geo-
thermal fields of Mexico has been carried out. The reservoir
temperatures from these thermal waters were calculated by
applying all the available 28 solute geothermometers and the
obtained temperatures were compared with the bottom hole
temperatures (BHT) of the geothermal wells. Thermal waters
of springs and geothermal wells of Cerro Prieto geothermal
field (CPGF) are Cl type and majority of them are partially
equilibrated. In the case of Los Humeros geothermal field
(LHGF), spring waters are HCO3 type and all of them have
indicated non-equilibrium conditions. Majority of the pre-
dicted reservoir temperatures by Na/K geothermometers
America Yosiris Garca-Soto and Jos Enrique Marrero-Ochoa were on
an academic stay at IER-UNAM, during 20132014, for realizing the
undergraduate thesis work.
Electronic supplementary material The online version of this article
(doi:10.1007/s12517-016-2529-0) contains supplementary material,
which is available to authorized users.
* Kailasa Pandarinath
pk@ier.unam.mx
1
Posgrado en Ingeniera, Instituto de Energas Renovables,
Universidad Nacional Autnoma de Mxico, Priv. Xochicalco s/no.,
62580 Temixco, Mor., Mexico
2
Departamento de Sistemas Energticos, Instituto de Energas
Renovables, Universidad Nacional Autnoma de Mxico, Priv.
Xochicalco s/no., Col. Centro, Apartado Postal 34,
62580 Temixco, Mor., Mexico
3
Universidad Politcnica del Estado de Morelos, Bvld. Cuauhnhuac
#566 Col. Lomas del Texcal, Jiutepec, Morelos, Mexico
from spring waters of CPGF and LHGF are within 20 %
differences compared to average BHTs, whereas estimated
temperatures by all other solute geothermometers (non-Na/K)
from spring waters of both the geothermal fields have shown
wide differences (> 20 %). In the case of geothermal well
waters, majority of the reservoir temperatures estimated by
only Na/K geothermometers from well waters of CPGF are
within 20 % differences and in the case of wells of LHGF,
majority of the reservoir temperatures estimates by all solute
geothermometers are having differences > 20 %. The present
study indicates the following: (1) only 3 geothermometers
(out of 28) from spring waters of CPGF have predicted
reservoir temperatures similar (statistically no significant
differences) to the average of BHTs, although all springs
are of Cl type; (2) different chemical characteristics of
spring and well waters of CPGF and LHGF may be the
result of the wide differences in the lithology of their
reservoirs; (3) more number of solute geothermometers
from non-equilibrated spring waters of CPGF and LHGF
have predicted reliable reservoir temperatures than partially
equilibrated waters; (4) In general, Na/K geothermometers
have predicted more reliable reservoir temperatures from
spring and well waters of both geothermal fields, when
compared to other solute geothermometers; (5) the predic-
tion of non-reliable reservoir temperatures by other than
Na/K geothermometers may be the result of dilution/
mixing of deep thermal waters with the meteoric surface
waters; and (6) more number of geothermometers have
predicted reliable reservoir temperatures from well waters
in comparison to spring waters of both the studied geo-
thermal fields.
Keywords Solute geothermometers . Thermal springs .
Geothermal wells . Reservoir temperature
517 Page 2 of 11
Introduction
Several geothermometers (solute, gas, isotope, mineral, and
fluid inclusions) are widely being used to predict deep equi-
librium temperatures of geothermal systems. They are low-
cost tools based on specific chemical equilibrium reactions
and are very useful during the exploration and exploitation
stages of the production of geothermal energy. Among them,
solute geothermometers are widely applied in estimating the
reservoir temperatures as their application is relatively easier
and economical. Chemical composition of fluids from thermal
springs, fumaroles, and geothermal wells reflect the prevailing
deep reservoir conditions, and subsurface volcanic activity.
Verma et al. (2008) have compiled the available 35 solute
geothermometers in the literature and developed computer
software (SolGeo) for their application. The literature reveals
that there are several studies on the application of these solute
geothermometers for thermal springs (for example, Gile
1994; Simmons et al. 1994; Verma et al. 2006; Pandarinath
2011; etc.) and for geothermal well waters (for example,
Gile 1994; Portugal et al. 2000; Verma 2002; Gonzlez-
Partida et al. 2003, Pandarinath 2011; Garca-Lpez et al.
2014; etc.). It is suggested to apply as many geothermometers
as possible and compare the indicated temperatures by con-
sidering the lithology of the region and other hydrological
processes, as not all thermal waters (springs, fumaroles, geo-
thermal wells) nor all geothermometers provide reliable esti-
mation of the reservoir temperature (Pandarinath 2011;
Garca-Lpez et al. 2014). In several applications, significant
differences among the estimated and the measured tempera-
tures (bottom hole temperatures (BHT)) have been reported.
Mexico, with a total installed capacity of 958 MWe
(Gutirrez-Negrn et al. 2010), occupies fourth place among
the countries producing geothermal electricity. In Mexico,
there are four geothermal fields (Cerro Prieto, Las Tres
Vrgenes, Los Azufres, and Los Humeros) in production of
electricity (Fig. 1) and some in exploration stage (for example,
Fig. 1 Locations of four important and electricity-producing geothermal
fields of Mexico
Arab J Geosci (2016) 9: 517
Cerritos Colorados, Acoculco, etc.). Recently, there are some
studies on the application and evaluation of the reliability
(exactitude) of solute geothermometers from thermal wa-
ters (springs and wells) of Los Azufres geothermal field
(LAGF) and Las Tres Virgenes geothermal field (LTVGF)
(Pandarinath 2011) and Cerritos Colorados (also known as
La Primavera; Pandarinath and Domnguez-Domnguez
2015). In this article, we have evaluated the accuracy of the
estimated reservoir temperatures based on geochemometric
methods in thermal waters of two important electricity-
producing geothermal fields, Cerro Prieto and Los Humeros,
of Mexico.
Geology of the study area
Cerro Prieto geothermal field (CPGF; Fig. 1) is a liquid-
dominated high-temperature geothermal field (>300 C), lo-
cated in Quaternary sediments of Cucapah Range and deltaic
sediments of Colorado River. These Quaternary deposits over-
lay metamorphosed Cenozoic sediments, which are discor-
dant on the granitic and meta-sedimentary Upper Cretaceous
basement (Puente and De la Pea 1979). The producing
reservoirs are located in sandstone and sandy shale units.
The fluids of the CPGF are a mixture of Colorado River
waters and marine brines along with a minor magmatic
component (Truesdell et al. 2003).
Los Humeros geothermal field (LHGF; Fig. 1) is a vapor-
dominated geothermal system located in the eastern part of the
MVB about 200 km east of Mexico City (Verma 1983; Tello
2005). The basement of this geothermal system consists of
limestone sequences of Late Cretaceous age (e.g., Viniegra
1965; Yaez 1980) and is overlined by andesites, dacites,
rhyodacites, rhyolitic tuffs, rhyolites, and basaltic rocks.
Surface lithology towards the east of LHGF consist andesites,
basalts, rhyolites along with Pliocene-Holocene clastic sedi-
ments near the coast. Geology of the eastern part is recently
synthesized by Armstrong-Altrin (2015).
Methodology
A geochemical database consisting of chemical compositions
of fluids from thermal springs and geothermal wells and bot-
tom hole temperature (BHT) measurements has been created.
The main criteria for the selection of the springs and wells for
this study is the availability of concentration data of cations
and anions as well as measured well bottom temperatures.
With this requirement, we could compile the chemical data
for 59 thermal springs and 51 drilled geothermal wells of
CPGF and 65 thermal springs and 20 drilled geothermal wells
of LHGF (Molina and Banwell 1970; Manon et al. 1977;
Valette-Silver et al. 1981; Giggenbach 1988; Barragn et al.
Arab J Geosci (2016) 9: 517
1991; Tello 1992; Martinez et al. 1996; Tello et al. 2000;
Bernard et al. 2011).
Water samples of the springs and geothermal wells are
chemically classified and equilibrium conditions were
obtained based on the ternary diagrams of Giggenbach
(1988) by employing the computer program CCWater
(Pandarinath et al. 2011; Prez-Espinosa 2011). With this
method, the geothermal water is classified into three chemical
types (bicarbonate, sulfate, and chloride) and also equilibrium
conditions (completely, partially, and non-equilibrated water
types; Figs. 2 and 3). A computer program, SolGeo (Verma
et al. 2008) was applied for estimating the reservoir tempera-
tures. We have employed a geochemometrical (geochemical
and statistical) methodology to understand the effectiveness of
the geothermometers in estimating the reservoir temperatures
by considering the type of water, equilibrium conditions, and
statistical analysis. The estimated reservoir temperatures for
the spring water and fluids of geothermal wells were com-
pared with the actually measured BHT of the wells of the
respective geothermal system. We have employed the follow-
ing formula to find out the difference percentage between the
measured and estimated reservoir temperatures:
Difference % T Geotherm T BHT =T BHT   100:
Based on the total propagated errors quantified by Verma
and Santoyo (1997) and Daz-Gonzlez et al. (2008) for some
solute geothermometers, an upper limit difference of 20 %
(positive or negative) was assumed as acceptable difference
for the comparison purpose. If the predicted reservoir temper-
atures by the geothermometers are higher (positive difference)
or lower (negative difference) than the respective BHTs of
the wells, it is interpreted as over- or underestimation,
respectively. These difference percentages were used to
find out whether the estimated reservoir temperatures are
equal (no differences; considering the differences are with-
in 0.5 %; rounding the temperature data to integers),
acceptable (when the differences are, either positive or
negative, within the range of 0.5 % and 20 %), and
unacceptable (when the differences are, either positive or
negative, greater than 20 %; referred in tables as > 20 %).
The difference percentage of a 20 % when compared to the
BHTs was assumed as acceptable (based on the total propa-
gated errors quantified in some solute geothermometers; e.g.,
Verma and Santoyo 1997; Daz-Gonzlez et al. 2008).
Results
The reservoir temperatures calculated by using SolGeo software
(Verma et al. 2008) for thermal waters of CPGF and LHGF are
presented in Supplementary Tables S1S4 and performance of
Page 3 of 11 517
the geothermometers in predicting the reservoir temperatures
are presented in Supplementary Tables S5S6. To restrict the
length of the manuscript, the compiled raw chemical data of the
springs and wells are not included but the data source references
are referred in the Methodology section. Analytical errors, and
methods followed for water sampling and chemical analysis are
reported in the articles (referred to in the Methodology section)
from which the present data is compiled (for example, Table 1 of
Molina and Banwell 1970 shows the estimated analytical errors
for the chemical parameters). The acceptability percentages of
the estimated reservoir temperatures by each solute
geothermometer for different chemical types of water (dominat-
ed by HCO3, SO4, or Cl) and for different chemical equilibrium
conditions of the springs and wells were calculated and are pre-
sented in the Tables S5 and S6. Finally, the results on Students t
test and F test to understand the accuracy of each
geothermometer in predicting the reservoir temperatures com-
paring to BHT are presented in Table 1 for CPGF and in Table 2
for LHGF.
Chemical characteristics of thermal springs of Cerro Prieto
(CPGF) and Los Humeros geothermal fields (LHGF) are very
different (Figs. 2 and 3). Spring waters of CPGF are of chlo-
ride type (Cl), whereas those of LHGF are bicarbonate
(HCO3) type. Majority of spring waters (41 out of 59) of
CPGF have attained partial equilibrium conditions and the
remaining (18 out of 59) are non-equilibrated water (immature
water). However, all spring waters of LHGF have exhibited
non-equilibrium conditions (Fig. 2b). In the case of geother-
mal well waters, CPGF are of Cl type (matured water), where-
as LHGF are spread over into three types (9, 6, and 5 are
HCO3, SO4, and Cl, respectively). Majority (26 out of
39) of well water samples of CPGF are partially equil-
ibrated followed by completely equilibrated (12 out of
39) and non-equilibrated (1 out of 39). In the case of
LHGF, 9 samples are partially equilibrated and 11 sam-
ples are non-equilibrated. Statistical results on the effec-
tiveness of the solute geothermometers in predicting the
reservoir temperatures in relation to the chemical char-
acteristics of waters of the thermal springs and geother-
mal well are presented in the following section.
Spring waters from CPGFsolute geothermometry
Among the studied 59 spring water samples from CPGF, 58
are Cl type and the one is HCO3 type (Fig. 2a). Hence, the
spring water samples of CPGF are generally considered as Cl
type and statistical results are presented to only these 58
samples.
Majority of the temperatures (636 out of 655; 97 %) esti-
mated by Na/K geothermometers (TNa/K) from these spring
waters are within the acceptable differences (< 20 %;
Table S5). However, the temperature prediction performance
by other geothermometers (non-Na/K) is very poor. Out of the
517 Page 4 of 11
Fig. 2 Triangular diagrams
(Giggenbach 1988) showing
water types a and equilibrium
conditions b of springs of Cerro
Prieto and Los Humeros
geothermal fields
total 561 temperatures estimated by other (non-Na/K and non-
quartz) geothermometers, only 116 (21 %) are within the ac-
ceptable differences (< 20 %). Similarly, the temperature
prediction performance of quartz geothermometers is also
very poor (only 6 out of 341 estimated temperatures; <2 %
are within the acceptable difference).
Statistical comparison of the estimated reservoir tempera-
ture from spring waters indicates only 3 out of the 28 applied
Arab J Geosci (2016) 9: 517
geothermometers for CPGF (TNK2A83 Y TNKG88,
TNKCF73M; Table 1) have indicated reservoir tempera-
tures similar/comparable to the average BHT of their re-
spective geothermal fields. Among these 59 spring waters,
41 are partially equilibrated and the remaining 18 are non-
equilibrated. Statistical similarity tests indicate only three
solute geothermometers (TNK2A83, TNKG88,
TNKCF73M) from partially equilibrated spring waters and
Arab J Geosci (2016) 9: 517 Page 5 of 11 517

Fig. 3 Triangular diagrams

(Giggenbach 1988) showing
water types a and equilibrium
conditions b of geothermal wells
of Cerro Prieto and Los Humeros
geothermal fields

10 geothermometers (TNKFT73, TNKF79, TNKT80, out of the total 28 applied geothermometers, have predicted the
TNK2A83, TNKG88, TNKVS87, TNKDSR08, TNL2FM81, reservoir temperatures similar/comparable to the average BHT
TNL2VS97, and TSV00) from non-equilibrated spring waters, of their respective geothermal fields.
517 Page 6 of 11 Arab J Geosci (2016) 9: 517

Table 1 Performance of geothermometers for different water types based on Students t test and F test from geothermal waters of Cerro Prieto
geothermal field

Water type Group 1 Group 2 Group 1 Group 2

Spring waters Geothermal well waters

HCO3
SO4
Cl TNK2A83, TNKG88 TNKCF73M TNKF79, TNKVS97, TNKA00, TNK2A83, TSA00
TNKC02, TNKDSR08, TNK2DS08,
TSFP82, TS2VS97
Full equilibrium TNK2A83, TNKA00, TNKC02, TKMF91, TLMKM89
TNKCF73M, TNKMNN87,
TCCGNN87
Partial equilibrium TNK2A83, TNKG88 TNKCF73M TNKA00, TNKC02, TNKDSR08, TNLFM81, TCCGNN87
TNK2DS08, TKMG88, TSF77,
TSFP82, TS2VS97, TSA00
No equilibrium TNKF79, TNK2A83, TNKFT73, TNKT80,
TNKG88, TNKVS97, TNL2FM81, TNL2VS97,
TNKDSR08 TSV00

The expansion to the geothermometer is as follows: For example, in TNKFT73, the first three letters TNK refer to the temperature predicted by the Na/
K geothermometer, successive letters refer to authors of the geothermometer and finally the numbers refer to the year of publication. So, TNKFT73
represents temperature predicted by Na/K geothermometer of Fournier and Truesdell (1973). This expansion procedure applies to all the
geothermometers. Please see Tables 1 and 2 of Verma et al. (2008) for the equations of the geothermometers and for the expansions to the abbreviated
codes of the geothermometers, respectively
The geothermometers listed in Group 1 and Group 2 have predicted the reservoir temperatures similar to BHTs of the wells (statistically there are no
significant differences between the estimated temperatures by geothermometers and measured BHTs of the wells)
Group 1 No statistically significant difference in the means and variances
Group 2 Statistically significant differences in the variances only (the variance estimates include both field and laboratory variances)

Geothermal well waters from CPGFsolute
geothermometry
Geothermal well waters of CPGF are of Cl type (matured water;
Fig. 3a). Among the total 39 well water samples, 26 (67 %) are
partially equilibrated, 12 (31 %) are completely equilibrated, and
1 (2 %) is non-equilibrated (Fig. 3b).
Majority of the temperatures (445 out of 526; 85 %) esti-
mated by Na/K geothermometers (TNa/K) from these well wa-
ters are within the acceptable differences (< 20 %; Table S5).
However, the temperature prediction performance by other
geothermometers (non-Na/K) is very poor. Out of the total
439 temperatures estimated by other (non-Na/K and non-
quartz) geothermometers, only 187 (43 %) are within the ac-
ceptable differences (< 20 %). Similarly, the temperature
prediction performance of quartz geothermometers is also
poor (only 100 out of 154 estimated temperatures; 65 % are
within the acceptable difference).
Statistical comparison of the estimated reservoir temperature
from geothermal well waters indicates only 10 out of the total 28
applied geothermometers for CPGF (TNKF79, TNKVS97,
TNKA00, TNKC02, TNKDSR08, TNK2DS08, TSFP82,
TS2VS97, TNK2A83, and TSV00; Table 1) have indicated the
reservoir temperatures similar/comparable to the average BHTof
their respective geothermal fields. En relation to the conditions of
equilibrium of the well waters, 8 out of total 28 applied
geothermometers (TNK2A83. TNKA00, TNKC02,
TNKCF73M, TNKMNN87, TCCGNN87, TKMF91, and
TLMKM89) from fully equilibrated and 11 out of 28 applied
solute geothermometers (TNKA00, TNKC02, TNKDSR08,
TNK2DS08, TKMG88, TSF77, TSFP82, TS2VS97, TSV00,
TNLFM81, and TCCGNN87) from partially equilibrated geo-
thermal well waters have predicted the reservoir temperatures
similar/comparable to the average bottom hole temperatures
(BHT) of their respective geothermal fields.
Spring waters from LHGFsolute geothermometry
All the studied spring waters of LHGF are of HCO3 (Fig. 2a)
type and all of them have indicated non-equilibrated condi-
tions (Fig. 2b).
Majority of the reservoir temperatures estimated by Na/K
(388 out of 447; 86.8 %) geothermometers are within the
acceptable differences (< 20 %; Table S6), whereas almost none
of the reservoir temperatures estimated by other
geothermometers (non-Na/K) from these spring waters are
within the acceptable differences. Regarding quartz
geothermometers, only four out of the total seven
geothermometers were able to be applied for these spring waters
and none of the temperatures estimated by these SiO 2
geothermometers are within the acceptable differences
(Table S6).
Statistical comparison of the estimated reservoir tempera-
ture from these spring waters indicates only 3 out of the 28
Arab J Geosci (2016) 9: 517 Page 7 of 11 517

Table 2 Performance of geothermometers for different water types based on Students t test and F test from geothermal waters of Los Humeros
geothermal field

Water type Group 1 Group 2 Group 1 Group 2

Spring waters Geothermal well waters

HCO3 TNKF79, TNKG88, TNKT80, TNKG88, TSFP82, TNKF79, TNK2A83, TNKVS97,

TNKVS97 TS2VS97 TKMF91, TNKCF73M, TSV00
SO4 TNKCFT73, TNKT76, TNKF79, TNK2A83, TNKCF73M
TNKT80, TNKG88, TNKVS97,
TNKA00, TNKC02, TNKDSR08,
TNK2DS08, TKMF91, TSFP82,
TS2VS97, TSA00, TSV00
Cl TKMF91, TS2VS97 TNKCF73M, TSFP82, TSA00,
TSV00
Full-equilibrium
Partial equilibrium TNK2A83, TKMF91, TNKFT73,
TS2VS97, TSV00
No-equilibrium TNKF79, TNKG88, TNKFT73, TNKT80, TNKDSR08, TNKF79, TNK2A83, TNKG88,
TNKVS97 TS2F77, TSFP82, TS2VS97, TNKVS97, TNKC02, TNK2DS08
TSA00, TSV00

For expansions to the abbreviations of the geothermometers and explanation to the Group 1 and Group 2, please see the footnote of Table 1

applied geothermometers for LHGF (TNKF79, TNKG88,
TNKVS97; Table 2) have indicated the reservoir temperatures
similar/comparable to the average BHT of their respective
geothermal fields.
Geothermal well waters from LHGFsolute
geothermometry
Geothermal well waters from LHGF are spread over into three
types (9, 6, and 5 are HCO3 type, SO4 type, and Cl type,
respectively; Fig. 3a) and out of the total 20 well waters, 9
samples are partially equilibrated and 11 samples are non-
equilibrated (Fig. 3b).
The performance in estimation of reservoir temperature, in
general, by solute geothermometers from these well waters is
very poor. The success rates (acceptable differences; < 20 %)
in predicting the reservoir temperatures by Na/K, other (non-
Na/K and non-quartz) and quartz geothermometers are, re-
spectively, 53 % (115 out of 216), 15 % (26 out of the total
174), and 61 % (33 out of the total 54; Table S6).
The performance of Na/K geothermometers in accordance
to the chemical types of waters are as follows: (1) HCO3 type
(46 out of total 95 estimated reservoir temperatures; 48 %); (2)
SO4 type (47 out of 65; 72 %); and (3) Cl type (21 out of 38;
55 %). Performances of other geothermometers (non-Na/K
and non-quartz) are as follows: (1) HCO3 type (17 out of total
76 estimated reservoir temperatures; 22 %); (2) SO4 type (5 out
of 18; 28 %); and (3) Cl type (4 out of 8; 50 %). Performances of
quartz geothermometers are as follows: (1) HCO3 type (11 out
of total 17 estimated reservoir temperatures; 65 %); (2) SO4 type
(11 out of 15; 73 %); and (3) Cl type (11 out of 15; 73 %).
Statistical comparison of the estimated reservoir tempera-
ture from geothermal well waters (ungrouped into different
equilibrium conditions) indicates only 5 out of the 28 applied
geothermometers for LHGF (TKMF91, TNKCF73M,
TS2VS97, TSA00, TSV00) have indicated the reservoir tem-
peratures similar/comparable to the BHT of their respective
geothermal wells (Table 2).
Statistical comparison of the estimated reservoir temperature
from geothermal well waters (completely non-equilibrated) of
LHGF indicated 14 out of the 27 applied geothermometers
(TNKFT73, TNKF79, TNKT80, TNK2A83, TNKG88,
TNKVS97, TNKC02, TNKDSR08, TNK2DS08, TS2F77,
TSFP82, TS2VS97, TSA00, and TSV00; Table 2) have indi-
cated reservoir temperatures similar/comparable to the BHT of
their respective geothermal fields.
Statistical comparison of the estimated reservoir temper-
ature from geothermal well waters (partially equilibrated)
of LHGF indicated only 5 out of the 27 applied
geothermometers (TNK2A83, TKMF91, TNKCF73M,
TS2VS97, and TSV00) have indicated the reservoir tem-
peratures similar/comparable to the BHT of their respective
geothermal fields (Table 2).
Discussion
Chemical composition of geothermal waters depends on sev-
eral factors and the final composition depends on temperature-
dependent reactions between host rock and thermal water;
mineral components of reservoir rocks; and processes of
mixing, boiling, and cooling. Meteoritic water infiltrates to
517 Page 8 of 11
deeper parts through faults and form geothermal reservoirs.
Various chemical reactions occur between the water and the
rock formations of the reservoir. Bicarbonate (HCO3)-rich
waters originate through dissolution of CO2-bearing gases or
condensation of geothermal steam in relatively deep, oxygen
poor ground waters (Gupta and Roy 2006). These HCO3 wa-
ters form when circulating meteoric water encounters and
mixes with CO2-rich steam or water that has condensed from
such steam. HCO3 water is a mixture of a major portion of
meteoric water with little or no geothermal fluids. Hence,
these waters may not indicate the reliable reservoir tempera-
tures. Sulfate (SO4) water type is the mixture of geothermal
steam with groundwater. SO4-rich water is the result of inter-
action of shallow meteoric water with steam condensate which
gives the oxidation of H2S to H2SO4 (Ellis and Mahon
1977). A small amount of geothermal water may be
derived from gases which were originally dissolved in
magmas. Cl type water is generally considered as mature
or characteristic of deep geothermal fluid and therefore,
this water is expected to provide more reliable reservoir
temperatures. The triangular diagrams of Giggenbach (1988)
are widely used for chemical classification of geothermal wa-
ters into HCO3, SO4, and Cl types, and for classification of
different chemical equilibrium conditions (full, partial, and
non-equilibrium). Generally, the neutral, low-sulfate, high-
chloride geothermal waters (along the ClHCO3 axis, close
to the Cl corner; triangular diagram of Giggenbach 1988;
Figs. 2a and 3a) are considered as mature waters and are best
suited for geothermometry.
The deep reservoir temperatures estimated by the solute
geothermometers from different chemical types of geothermal
waters of the springs and geothermal wells are compared,
respectively, with average BHTs of the wells and with the
BHT of the corresponding geothermal wells. In the present
study, all springs at CPGF are of Cl type and those at LHGF
are of HCO3 type. Interestingly, Na/K geothermometers were
highly successful in predicting reliable reservoir temperatures
from the springs of both these geothermal fields and perfor-
mances of all other geothermometers (non-Na/K) from these
waters are very poor (Tables S5 and S6). Nearly 97 and 87 %
of total estimated temperatures by Na/K geothermometers from
waters of springs of CPGF and LHGF, respectively, are within
the acceptable differences (< 20 %). Similarly, the majority of
the temperatures estimated by Na/K geothermometers from
waters of wells from CPGF (85 %) and LHGF (53 %) are
within the acceptable differences (Tables S5 and S6).
Generally, more reliable prediction of the reservoir tempera-
tures are expected from Cl-type waters because they are con-
sidered as mature or characteristic of deep geothermal fluids.
Similarly, an unreliable estimated reservoir temperature from
HCO3-type water is generally expected as it comes mainly
from shallow meteoric water that did not undergo significant
chemical and thermal equilibration with host rocks. Contrary to
Arab J Geosci (2016) 9: 517
this general observation, Na/K geothermometers were highly
successful in predicting the reservoir temperatures from the
springs of HCO3-type water at LHGF. Pandarinath (2014) has
also reported that Na/K geothermometry of HCO3-rich water
from Los Azufres geothermal field (LAGF) has provided tem-
peratures closer to the BHT, but fully mature geothermal water
(Cl-rich) of springs have indicated reservoir temperatures hav-
ing large differences when compared with average BHTs.
Burgos (1999) have reported that this type of behavior by
HCO 3 type is typical for water associated with high-
temperature systems, probably of volcanic origin, but consid-
erably diluted due to mixing with meteoric water during its rise
to the surface. Similarly, in the present study, LHGF is a high-
temperature system. Deep spring water at LHGF may have
contained a part of volcanic component but as these waters
ascend to the surface might have diluted by mixing with
shallower water and finally enriched with HCO3. This may
be the reason for better temperature prediction performance of
Na/K geothermometers from spring waters of LHGF, even
though water is of HCO 3 type. Apart from this, Na/K
geothermometers are less affected by dilution or steam loss
because they are based on a ratio of cationic concentrations.
HCO3/Cl ratio varies between 0.00 and 0.43 for spring waters
and between 0.00 and 0.03 for well waters of CPGF. Whereas,
HCO3/Cl ratio varies between 1.76 and 109.05 for spring wa-
ters and between 0.01 and 52.68 for well waters of LHGF.
Comparatively higher HCO3/Cl ratio for spring water compar-
ing to the deep geothermal well waters in LHGF indicates
addition of HCO3 from fluid-rock interaction processes (CO2-
rock reaction) at shallower depths. The difference in chemical
characteristics of spring and well waters of CPGF and LHGF
may reflect the differences in the lithology of their reservoirs. In
the present study, the basement of CPGF consists of granitic
and meta-sedimentary rocks (Puente and De la Pea 1979),
whereas the basement of LHGF consists of limestone se-
quences (e.g. Viniegra 1965; Yaez 1980). The interaction
processes between the fluids and the limestone rocks
(CaCO3 composition) in LHGF might be contributing
HCO3 component to these spring and well waters. This
may be the reason for higher HCO3/Cl ratios for spring
and well waters in LHGF comparing to those of CPGF.
In general, solute geothermometry of well waters is more
successful in predicting the reservoir temperatures than that of
spring waters for both the geothermal fields (Tables S5 and S6).
Spring waters of CPGF and LHGF have underestimated the
reservoir temperatures (Fig. 4) in comparison with equilibrium
temperatures of Giggenbach (1988).
Student t and F tests were carried out to understand the
accuracy of the estimated reservoir temperatures in compari-
son to the BHTs. These tests have revealed that 10 out of 28
solute geothermometers from non-equilibrium spring waters
of CPGF have presented statistically similar to average BHTs
in comparison to only 3 out of 28 solute geothermometers
Arab J Geosci (2016) 9: 517
Fig. 4 Chemical equilibrium temperatures versus temperatures estimated
by different solute geothermometers for spring waters of a Cerro Prieto
geothermal field and b Los Humeros geothermal field. Bottom hole
from partially equilibrated waters (Table 1). All the studied
spring waters of LHGF have indicated non-equilibrated con-
ditions and only 3 out of 28 solute geothermometers from
these spring waters have presented comparatively better per-
formance in predicting the reservoir temperatures (Table 2). In
the case of geothermal well waters of CPGF, 11 and 8 solute
geothermometers (out of total 28), respectively, from partially
Page 9 of 11 517
temperatures versus temperatures estimated by different solute
geothermometers for well waters of c Cerro Prieto geothermal field and
d Los Humeros geothermal field
and fully equilibrated waters have predicted reliable reservoir
temperatures (Table 1). Whereas, 14 and 5 geothermometers
(out of total 28), respectively, non-equilibrated and partially
equilibrated geothermal well waters of LHGF have predicted
reliable reservoir temperatures (Table 2). This is in contrary to
the generally expected better performance by more equilibrat-
ed waters. However, similar contrary behavior is also
517 Page 10 of 11
observed in spring waters of LAGF and Cerritos Colorados
(La Primavera) geothermal fields (CCGF), Mexico. In
LAGF, non-equilibrated spring waters have indicated the
reservoir temperatures closer to average BHT (Pandarinath
2014) whereas, non-equilibrated and partially equilibrated
spring waters of CCGF (Pandarinath and Domnguez-
Domnguez 2015) have indicated more reliable reservoir
temperatures than those of partially and fully equilibrated
waters, respectively. This type of performance of the sol-
ute geothermometers by spring waters, in relation to the
existing equilibrium conditions, may be due to the prevail-
ing mixing process at the shallower depths. Mixing of
ascending thermal fluids with colder groundwater in
shallower aquifers is reported in Cerro Prieto geothermal
field (Lippmann et al. 1991). The spring waters from
CPGF and LHGF appear to be mixed with shallow mete-
oric water which resulted in to inconsistent reservoir tem-
peratures obtained by all the solute geothermometers, ex-
cept Na/K geothermometers. When the spring water rises
to the surface, probably is being diluted by mixing of
shallower meteoric water (Burgos 1999). Spring water dur-
ing rise to the surface may cool by conduction, boiling,
mixing with colder water, or a combination of these pro-
cesses. Fournier (1979) has reported that the temperature
of the resulting mixed spring water may be above or
below the boiling temperature (at atmospheric pressure),
and after mixing, chemical re-equilibrium (fully or partial)
may or may not occur. Attaining of chemical re-equilibrium
by the mixed spring water may be possible if the temperature
after mixing is greater than 100 C. Thermal waters of
chloride type from high-temperature reservoirs (>180 C)
are generally considered suitable for Na/K geothermometers
(for example, Karingithi 2009). The better performance of
Na/K geothermometry and very poor performance by
quartz geothermometry in predicting the reservoir temper-
atures, in the present study, may also suggest the prevailed
mixing processes at shallower depths. Apart from this, the
quartz geothermometry of the spring waters of both CPGF
(Tables S1 and S5) and LHGF (Tables S3 and S6) has
provided very low reservoir temperatures. These results
indicate the possible mixing of shallower meteoritic water
at both CPGF and LHGF. These mixing processes may
not be or less affecting the Na/K geothermometry as these
geothermometers are based on Na and K ratios (not directly
the individual concentrations) unlike quartz geothermometry
which is based directly on concentration of silica. The
chemical composition and equilibrium conditions of ther-
mal waters from springs and wells at CPGF and LHGF
are influenced by water-rock interaction processes, and
mixing of deeper thermal water with shallower meteoric
water. The observed contrary performance in predicting the
reservoir temperatures by solute geothermometers in relation
to chemical type of water and equilibrium conditions may be
Arab J Geosci (2016) 9: 517
the result of existing water mixing process at shallower
depths. These processes have to be considered in the studies
relating to the evaluation on the performance of solute
geothermometers in predicting reservoir temperatures from
springs and well waters of different chemical composition
and equilibrium conditions.
Conclusions
Springs and well waters of CPGF are chemically different to
those of LHGF. Irrespective of the chemical types of these
waters, Na/K geothermometers have predicted more reliable
reservoir temperatures than other solute geothermometers in
both fields. More number of solute geothermometers from
non-equilibrium spring waters and partially equilibrated well
waters have presented reliable reservoir temperatures than,
respectively, partially equilibrated spring waters and fully
equilibrated well waters of CPGF. Similarly, in the case of
LHGF, more numbers of solute geothermometers from non-
equilibrated well waters have predicted reliable reservoir tem-
peratures than from partially equilibrated well waters. The
obtained solute geothermometry from springs and well waters
of different chemical composition and equilibrium conditions
suggests that the thermal water composition reflect the lithol-
ogy of the reservoirs and dilution of deep thermal waters, as
they ascend to the surface, by shallow meteoritic waters.
Acknowledgment America Yosiris Garca-Soto and Jos Enrique
Marrero would like to thank Mirna Guevara Garca of IER-UNAM for
the help during the course of this work. We convey our sincere thanks to
two anonymous reviewers and Associate Editor of the journal Dr. John S.
Armstrong-Altrin for reviewing and providing their valuable comments
on the earlier version of the manuscript.
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