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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- from spring waters of CPGF and LHGF are within 20 %
ations of thermal waters (springs and geothermal wells) on the differences compared to average BHTs, whereas estimated
performance of solute geothermometers in predicting the temperatures by all other solute geothermometers (non-Na/K)
reservoir temperatures of Cerro Prieto and los Humeros geo- from spring waters of both the geothermal fields have shown
thermal fields of Mexico has been carried out. The reservoir wide differences (> 20 %). In the case of geothermal well
temperatures from these thermal waters were calculated by waters, majority of the reservoir temperatures estimated by
applying all the available 28 solute geothermometers and the only Na/K geothermometers from well waters of CPGF are
obtained temperatures were compared with the bottom hole within 20 % differences and in the case of wells of LHGF,
temperatures (BHT) of the geothermal wells. Thermal waters majority of the reservoir temperatures estimates by all solute
of springs and geothermal wells of Cerro Prieto geothermal geothermometers are having differences > 20 %. The present
field (CPGF) are Cl type and majority of them are partially study indicates the following: (1) only 3 geothermometers
equilibrated. In the case of Los Humeros geothermal field (out of 28) from spring waters of CPGF have predicted
(LHGF), spring waters are HCO3 type and all of them have reservoir temperatures similar (statistically no significant
indicated non-equilibrium conditions. Majority of the pre- differences) to the average of BHTs, although all springs
dicted reservoir temperatures by Na/K geothermometers 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
America Yosiris Garca-Soto and Jos Enrique Marrero-Ochoa were on reservoirs; (3) more number of solute geothermometers
an academic stay at IER-UNAM, during 20132014, for realizing the from non-equilibrated spring waters of CPGF and LHGF
undergraduate thesis work. have predicted reliable reservoir temperatures than partially
Electronic supplementary material The online version of this article equilibrated waters; (4) In general, Na/K geothermometers
(doi:10.1007/s12517-016-2529-0) contains supplementary material, have predicted more reliable reservoir temperatures from
which is available to authorized users.
spring and well waters of both geothermal fields, when
compared to other solute geothermometers; (5) the predic-
* Kailasa Pandarinath
pk@ier.unam.mx 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
1
Posgrado en Ingeniera, Instituto de Energas Renovables, waters; and (6) more number of geothermometers have
Universidad Nacional Autnoma de Mxico, Priv. Xochicalco s/no.,
62580 Temixco, Mor., Mexico
predicted reliable reservoir temperatures from well waters
2
in comparison to spring waters of both the studied geo-
Departamento de Sistemas Energticos, Instituto de Energas
Renovables, Universidad Nacional Autnoma de Mxico, Priv.
thermal fields.
Xochicalco s/no., Col. Centro, Apartado Postal 34,
62580 Temixco, Mor., Mexico
3
Universidad Politcnica del Estado de Morelos, Bvld. Cuauhnhuac Keywords Solute geothermometers . Thermal springs .
#566 Col. Lomas del Texcal, Jiutepec, Morelos, Mexico Geothermal wells . Reservoir temperature
517 Page 2 of 11 Arab J Geosci (2016) 9: 517

Introduction Cerritos Colorados, Acoculco, etc.). Recently, there are some


studies on the application and evaluation of the reliability
Several geothermometers (solute, gas, isotope, mineral, and (exactitude) of solute geothermometers from thermal wa-
fluid inclusions) are widely being used to predict deep equi- ters (springs and wells) of Los Azufres geothermal field
librium temperatures of geothermal systems. They are low- (LAGF) and Las Tres Virgenes geothermal field (LTVGF)
cost tools based on specific chemical equilibrium reactions (Pandarinath 2011) and Cerritos Colorados (also known as
and are very useful during the exploration and exploitation La Primavera; Pandarinath and Domnguez-Domnguez
stages of the production of geothermal energy. Among them, 2015). In this article, we have evaluated the accuracy of the
solute geothermometers are widely applied in estimating the estimated reservoir temperatures based on geochemometric
reservoir temperatures as their application is relatively easier methods in thermal waters of two important electricity-
and economical. Chemical composition of fluids from thermal producing geothermal fields, Cerro Prieto and Los Humeros,
springs, fumaroles, and geothermal wells reflect the prevailing of Mexico.
deep reservoir conditions, and subsurface volcanic activity.
Verma et al. (2008) have compiled the available 35 solute
geothermometers in the literature and developed computer Geology of the study area
software (SolGeo) for their application. The literature reveals
that there are several studies on the application of these solute Cerro Prieto geothermal field (CPGF; Fig. 1) is a liquid-
geothermometers for thermal springs (for example, Gile dominated high-temperature geothermal field (>300 C), lo-
1994; Simmons et al. 1994; Verma et al. 2006; Pandarinath cated in Quaternary sediments of Cucapah Range and deltaic
2011; etc.) and for geothermal well waters (for example, sediments of Colorado River. These Quaternary deposits over-
Gile 1994; Portugal et al. 2000; Verma 2002; Gonzlez- lay metamorphosed Cenozoic sediments, which are discor-
Partida et al. 2003, Pandarinath 2011; Garca-Lpez et al. dant on the granitic and meta-sedimentary Upper Cretaceous
2014; etc.). It is suggested to apply as many geothermometers basement (Puente and De la Pea 1979). The producing
as possible and compare the indicated temperatures by con- reservoirs are located in sandstone and sandy shale units.
sidering the lithology of the region and other hydrological The fluids of the CPGF are a mixture of Colorado River
processes, as not all thermal waters (springs, fumaroles, geo- waters and marine brines along with a minor magmatic
thermal wells) nor all geothermometers provide reliable esti- component (Truesdell et al. 2003).
mation of the reservoir temperature (Pandarinath 2011; Los Humeros geothermal field (LHGF; Fig. 1) is a vapor-
Garca-Lpez et al. 2014). In several applications, significant dominated geothermal system located in the eastern part of the
differences among the estimated and the measured tempera- MVB about 200 km east of Mexico City (Verma 1983; Tello
tures (bottom hole temperatures (BHT)) have been reported. 2005). The basement of this geothermal system consists of
Mexico, with a total installed capacity of 958 MWe limestone sequences of Late Cretaceous age (e.g., Viniegra
(Gutirrez-Negrn et al. 2010), occupies fourth place among 1965; Yaez 1980) and is overlined by andesites, dacites,
the countries producing geothermal electricity. In Mexico, rhyodacites, rhyolitic tuffs, rhyolites, and basaltic rocks.
there are four geothermal fields (Cerro Prieto, Las Tres Surface lithology towards the east of LHGF consist andesites,
Vrgenes, Los Azufres, and Los Humeros) in production of basalts, rhyolites along with Pliocene-Holocene clastic sedi-
electricity (Fig. 1) and some in exploration stage (for example, 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
Fig. 1 Locations of four important and electricity-producing geothermal of LHGF (Molina and Banwell 1970; Manon et al. 1977;
fields of Mexico Valette-Silver et al. 1981; Giggenbach 1988; Barragn et al.
Arab J Geosci (2016) 9: 517 Page 3 of 11 517

1991; Tello 1992; Martinez et al. 1996; Tello et al. 2000; the geothermometers in predicting the reservoir temperatures
Bernard et al. 2011). are presented in Supplementary Tables S5S6. To restrict the
Water samples of the springs and geothermal wells are length of the manuscript, the compiled raw chemical data of the
chemically classified and equilibrium conditions were springs and wells are not included but the data source references
obtained based on the ternary diagrams of Giggenbach are referred in the Methodology section. Analytical errors, and
(1988) by employing the computer program CCWater methods followed for water sampling and chemical analysis are
(Pandarinath et al. 2011; Prez-Espinosa 2011). With this reported in the articles (referred to in the Methodology section)
method, the geothermal water is classified into three chemical from which the present data is compiled (for example, Table 1 of
types (bicarbonate, sulfate, and chloride) and also equilibrium Molina and Banwell 1970 shows the estimated analytical errors
conditions (completely, partially, and non-equilibrated water for the chemical parameters). The acceptability percentages of
types; Figs. 2 and 3). A computer program, SolGeo (Verma the estimated reservoir temperatures by each solute
et al. 2008) was applied for estimating the reservoir tempera- geothermometer for different chemical types of water (dominat-
tures. We have employed a geochemometrical (geochemical ed by HCO3, SO4, or Cl) and for different chemical equilibrium
and statistical) methodology to understand the effectiveness of conditions of the springs and wells were calculated and are pre-
the geothermometers in estimating the reservoir temperatures sented in the Tables S5 and S6. Finally, the results on Students t
by considering the type of water, equilibrium conditions, and test and F test to understand the accuracy of each
statistical analysis. The estimated reservoir temperatures for geothermometer in predicting the reservoir temperatures com-
the spring water and fluids of geothermal wells were com- paring to BHT are presented in Table 1 for CPGF and in Table 2
pared with the actually measured BHT of the wells of the for LHGF.
respective geothermal system. We have employed the follow- Chemical characteristics of thermal springs of Cerro Prieto
ing formula to find out the difference percentage between the (CPGF) and Los Humeros geothermal fields (LHGF) are very
measured and estimated reservoir temperatures: different (Figs. 2 and 3). Spring waters of CPGF are of chlo-
ride type (Cl), whereas those of LHGF are bicarbonate
Difference % T Geotherm T BHT =T BHT   100:
(HCO3) type. Majority of spring waters (41 out of 59) of
CPGF have attained partial equilibrium conditions and the
Based on the total propagated errors quantified by Verma remaining (18 out of 59) are non-equilibrated water (immature
and Santoyo (1997) and Daz-Gonzlez et al. (2008) for some water). However, all spring waters of LHGF have exhibited
solute geothermometers, an upper limit difference of 20 % non-equilibrium conditions (Fig. 2b). In the case of geother-
(positive or negative) was assumed as acceptable difference mal well waters, CPGF are of Cl type (matured water), where-
for the comparison purpose. If the predicted reservoir temper- as LHGF are spread over into three types (9, 6, and 5 are
atures by the geothermometers are higher (positive difference) HCO3, SO4, and Cl, respectively). Majority (26 out of
or lower (negative difference) than the respective BHTs of 39) of well water samples of CPGF are partially equil-
the wells, it is interpreted as over- or underestimation, ibrated followed by completely equilibrated (12 out of
respectively. These difference percentages were used to 39) and non-equilibrated (1 out of 39). In the case of
find out whether the estimated reservoir temperatures are LHGF, 9 samples are partially equilibrated and 11 sam-
equal (no differences; considering the differences are with- ples are non-equilibrated. Statistical results on the effec-
in 0.5 %; rounding the temperature data to integers), tiveness of the solute geothermometers in predicting the
acceptable (when the differences are, either positive or reservoir temperatures in relation to the chemical char-
negative, within the range of 0.5 % and 20 %), and acteristics of waters of the thermal springs and geother-
unacceptable (when the differences are, either positive or mal well are presented in the following section.
negative, greater than 20 %; referred in tables as > 20 %).
The difference percentage of a 20 % when compared to the Spring waters from CPGFsolute geothermometry
BHTs was assumed as acceptable (based on the total propa-
gated errors quantified in some solute geothermometers; e.g., Among the studied 59 spring water samples from CPGF, 58
Verma and Santoyo 1997; Daz-Gonzlez et al. 2008). 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.
Results Majority of the temperatures (636 out of 655; 97 %) esti-
mated by Na/K geothermometers (TNa/K) from these spring
The reservoir temperatures calculated by using SolGeo software waters are within the acceptable differences (< 20 %;
(Verma et al. 2008) for thermal waters of CPGF and LHGF are Table S5). However, the temperature prediction performance
presented in Supplementary Tables S1S4 and performance of by other geothermometers (non-Na/K) is very poor. Out of the
517 Page 4 of 11 Arab J Geosci (2016) 9: 517

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- geothermometers for CPGF (TNK2A83 Y TNKG88,
quartz) geothermometers, only 116 (21 %) are within the ac- TNKCF73M; Table 1) have indicated reservoir tempera-
ceptable differences (< 20 %). Similarly, the temperature tures similar/comparable to the average BHT of their re-
prediction performance of quartz geothermometers is also spective geothermal fields. Among these 59 spring waters,
very poor (only 6 out of 341 estimated temperatures; <2 % 41 are partially equilibrated and the remaining 18 are non-
are within the acceptable difference). equilibrated. Statistical similarity tests indicate only three
Statistical comparison of the estimated reservoir tempera- solute geothermometers (TNK2A83, TNKG88,
ture from spring waters indicates only 3 out of the 28 applied 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.
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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 TNKCF73M, TNKMNN87, TCCGNN87, TKMF91, and
geothermometry TLMKM89) from fully equilibrated and 11 out of 28 applied
solute geothermometers (TNKA00, TNKC02, TNKDSR08,
Geothermal well waters of CPGF are of Cl type (matured water; TNK2DS08, TKMG88, TSF77, TSFP82, TS2VS97, TSV00,
Fig. 3a). Among the total 39 well water samples, 26 (67 %) are TNLFM81, and TCCGNN87) from partially equilibrated geo-
partially equilibrated, 12 (31 %) are completely equilibrated, and thermal well waters have predicted the reservoir temperatures
1 (2 %) is non-equilibrated (Fig. 3b). similar/comparable to the average bottom hole temperatures
Majority of the temperatures (445 out of 526; 85 %) esti- (BHT) of their respective geothermal fields.
mated by Na/K geothermometers (TNa/K) from these well wa-
ters are within the acceptable differences (< 20 %; Table S5). Spring waters from LHGFsolute geothermometry
However, the temperature prediction performance by other
geothermometers (non-Na/K) is very poor. Out of the total All the studied spring waters of LHGF are of HCO3 (Fig. 2a)
439 temperatures estimated by other (non-Na/K and non- type and all of them have indicated non-equilibrated condi-
quartz) geothermometers, only 187 (43 %) are within the ac- tions (Fig. 2b).
ceptable differences (< 20 %). Similarly, the temperature Majority of the reservoir temperatures estimated by Na/K
prediction performance of quartz geothermometers is also (388 out of 447; 86.8 %) geothermometers are within the
poor (only 100 out of 154 estimated temperatures; 65 % are acceptable differences (< 20 %; Table S6), whereas almost none
within the acceptable difference). of the reservoir temperatures estimated by other
Statistical comparison of the estimated reservoir temperature geothermometers (non-Na/K) from these spring waters are
from geothermal well waters indicates only 10 out of the total 28 within the acceptable differences. Regarding quartz
applied geothermometers for CPGF (TNKF79, TNKVS97, geothermometers, only four out of the total seven
TNKA00, TNKC02, TNKDSR08, TNK2DS08, TSFP82, geothermometers were able to be applied for these spring waters
TS2VS97, TNK2A83, and TSV00; Table 1) have indicated the and none of the temperatures estimated by these SiO 2
reservoir temperatures similar/comparable to the average BHTof geothermometers are within the acceptable differences
their respective geothermal fields. En relation to the conditions of (Table S6).
equilibrium of the well waters, 8 out of total 28 applied Statistical comparison of the estimated reservoir tempera-
geothermometers (TNK2A83. TNKA00, TNKC02, 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, Statistical comparison of the estimated reservoir tempera-
TNKVS97; Table 2) have indicated the reservoir temperatures ture from geothermal well waters (ungrouped into different
similar/comparable to the average BHT of their respective equilibrium conditions) indicates only 5 out of the 28 applied
geothermal fields. geothermometers for LHGF (TKMF91, TNKCF73M,
TS2VS97, TSA00, TSV00) have indicated the reservoir tem-
Geothermal well waters from LHGFsolute peratures similar/comparable to the BHT of their respective
geothermometry geothermal wells (Table 2).
Statistical comparison of the estimated reservoir temperature
Geothermal well waters from LHGF are spread over into three from geothermal well waters (completely non-equilibrated) of
types (9, 6, and 5 are HCO3 type, SO4 type, and Cl type, LHGF indicated 14 out of the 27 applied geothermometers
respectively; Fig. 3a) and out of the total 20 well waters, 9 (TNKFT73, TNKF79, TNKT80, TNK2A83, TNKG88,
samples are partially equilibrated and 11 samples are non- TNKVS97, TNKC02, TNKDSR08, TNK2DS08, TS2F77,
equilibrated (Fig. 3b). TSFP82, TS2VS97, TSA00, and TSV00; Table 2) have indi-
The performance in estimation of reservoir temperature, in cated reservoir temperatures similar/comparable to the BHT of
general, by solute geothermometers from these well waters is their respective geothermal fields.
very poor. The success rates (acceptable differences; < 20 %) Statistical comparison of the estimated reservoir temper-
in predicting the reservoir temperatures by Na/K, other (non- ature from geothermal well waters (partially equilibrated)
Na/K and non-quartz) and quartz geothermometers are, re- of LHGF indicated only 5 out of the 27 applied
spectively, 53 % (115 out of 216), 15 % (26 out of the total geothermometers (TNK2A83, TKMF91, TNKCF73M,
174), and 61 % (33 out of the total 54; Table S6). TS2VS97, and TSV00) have indicated the reservoir tem-
The performance of Na/K geothermometers in accordance peratures similar/comparable to the BHT of their respective
to the chemical types of waters are as follows: (1) HCO3 type geothermal fields (Table 2).
(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 Discussion
and non-quartz) are as follows: (1) HCO3 type (17 out of total
76 estimated reservoir temperatures; 22 %); (2) SO4 type (5 out Chemical composition of geothermal waters depends on sev-
of 18; 28 %); and (3) Cl type (4 out of 8; 50 %). Performances of eral factors and the final composition depends on temperature-
quartz geothermometers are as follows: (1) HCO3 type (11 out dependent reactions between host rock and thermal water;
of total 17 estimated reservoir temperatures; 65 %); (2) SO4 type mineral components of reservoir rocks; and processes of
(11 out of 15; 73 %); and (3) Cl type (11 out of 15; 73 %). mixing, boiling, and cooling. Meteoritic water infiltrates to
517 Page 8 of 11 Arab J Geosci (2016) 9: 517

deeper parts through faults and form geothermal reservoirs. this general observation, Na/K geothermometers were highly
Various chemical reactions occur between the water and the successful in predicting the reservoir temperatures from the
rock formations of the reservoir. Bicarbonate (HCO3)-rich springs of HCO3-type water at LHGF. Pandarinath (2014) has
waters originate through dissolution of CO2-bearing gases or also reported that Na/K geothermometry of HCO3-rich water
condensation of geothermal steam in relatively deep, oxygen from Los Azufres geothermal field (LAGF) has provided tem-
poor ground waters (Gupta and Roy 2006). These HCO3 wa- peratures closer to the BHT, but fully mature geothermal water
ters form when circulating meteoric water encounters and (Cl-rich) of springs have indicated reservoir temperatures hav-
mixes with CO2-rich steam or water that has condensed from ing large differences when compared with average BHTs.
such steam. HCO3 water is a mixture of a major portion of Burgos (1999) have reported that this type of behavior by
meteoric water with little or no geothermal fluids. Hence, HCO 3 type is typical for water associated with high-
these waters may not indicate the reliable reservoir tempera- temperature systems, probably of volcanic origin, but consid-
tures. Sulfate (SO4) water type is the mixture of geothermal erably diluted due to mixing with meteoric water during its rise
steam with groundwater. SO4-rich water is the result of inter- to the surface. Similarly, in the present study, LHGF is a high-
action of shallow meteoric water with steam condensate which temperature system. Deep spring water at LHGF may have
gives the oxidation of H2S to H2SO4 (Ellis and Mahon contained a part of volcanic component but as these waters
1977). A small amount of geothermal water may be ascend to the surface might have diluted by mixing with
derived from gases which were originally dissolved in shallower water and finally enriched with HCO3. This may
magmas. Cl type water is generally considered as mature be the reason for better temperature prediction performance of
or characteristic of deep geothermal fluid and therefore, Na/K geothermometers from spring waters of LHGF, even
this water is expected to provide more reliable reservoir though water is of HCO 3 type. Apart from this, Na/K
temperatures. The triangular diagrams of Giggenbach (1988) geothermometers are less affected by dilution or steam loss
are widely used for chemical classification of geothermal wa- because they are based on a ratio of cationic concentrations.
ters into HCO3, SO4, and Cl types, and for classification of HCO3/Cl ratio varies between 0.00 and 0.43 for spring waters
different chemical equilibrium conditions (full, partial, and and between 0.00 and 0.03 for well waters of CPGF. Whereas,
non-equilibrium). Generally, the neutral, low-sulfate, high- HCO3/Cl ratio varies between 1.76 and 109.05 for spring wa-
chloride geothermal waters (along the ClHCO3 axis, close ters and between 0.01 and 52.68 for well waters of LHGF.
to the Cl corner; triangular diagram of Giggenbach 1988; Comparatively higher HCO3/Cl ratio for spring water compar-
Figs. 2a and 3a) are considered as mature waters and are best ing to the deep geothermal well waters in LHGF indicates
suited for geothermometry. addition of HCO3 from fluid-rock interaction processes (CO2-
The deep reservoir temperatures estimated by the solute rock reaction) at shallower depths. The difference in chemical
geothermometers from different chemical types of geothermal characteristics of spring and well waters of CPGF and LHGF
waters of the springs and geothermal wells are compared, may reflect the differences in the lithology of their reservoirs. In
respectively, with average BHTs of the wells and with the the present study, the basement of CPGF consists of granitic
BHT of the corresponding geothermal wells. In the present and meta-sedimentary rocks (Puente and De la Pea 1979),
study, all springs at CPGF are of Cl type and those at LHGF whereas the basement of LHGF consists of limestone se-
are of HCO3 type. Interestingly, Na/K geothermometers were quences (e.g. Viniegra 1965; Yaez 1980). The interaction
highly successful in predicting reliable reservoir temperatures processes between the fluids and the limestone rocks
from the springs of both these geothermal fields and perfor- (CaCO3 composition) in LHGF might be contributing
mances of all other geothermometers (non-Na/K) from these HCO3 component to these spring and well waters. This
waters are very poor (Tables S5 and S6). Nearly 97 and 87 % may be the reason for higher HCO3/Cl ratios for spring
of total estimated temperatures by Na/K geothermometers from and well waters in LHGF comparing to those of CPGF.
waters of springs of CPGF and LHGF, respectively, are within In general, solute geothermometry of well waters is more
the acceptable differences (< 20 %). Similarly, the majority of successful in predicting the reservoir temperatures than that of
the temperatures estimated by Na/K geothermometers from spring waters for both the geothermal fields (Tables S5 and S6).
waters of wells from CPGF (85 %) and LHGF (53 %) are Spring waters of CPGF and LHGF have underestimated the
within the acceptable differences (Tables S5 and S6). reservoir temperatures (Fig. 4) in comparison with equilibrium
Generally, more reliable prediction of the reservoir tempera- temperatures of Giggenbach (1988).
tures are expected from Cl-type waters because they are con- Student t and F tests were carried out to understand the
sidered as mature or characteristic of deep geothermal fluids. accuracy of the estimated reservoir temperatures in compari-
Similarly, an unreliable estimated reservoir temperature from son to the BHTs. These tests have revealed that 10 out of 28
HCO3-type water is generally expected as it comes mainly solute geothermometers from non-equilibrium spring waters
from shallow meteoric water that did not undergo significant of CPGF have presented statistically similar to average BHTs
chemical and thermal equilibration with host rocks. Contrary to in comparison to only 3 out of 28 solute geothermometers
Arab J Geosci (2016) 9: 517 Page 9 of 11 517

Fig. 4 Chemical equilibrium temperatures versus temperatures estimated temperatures versus temperatures estimated by different solute
by different solute geothermometers for spring waters of a Cerro Prieto geothermometers for well waters of c Cerro Prieto geothermal field and
geothermal field and b Los Humeros geothermal field. Bottom hole d Los Humeros geothermal field

from partially equilibrated waters (Table 1). All the studied and fully equilibrated waters have predicted reliable reservoir
spring waters of LHGF have indicated non-equilibrated con- temperatures (Table 1). Whereas, 14 and 5 geothermometers
ditions and only 3 out of 28 solute geothermometers from (out of total 28), respectively, non-equilibrated and partially
these spring waters have presented comparatively better per- equilibrated geothermal well waters of LHGF have predicted
formance in predicting the reservoir temperatures (Table 2). In reliable reservoir temperatures (Table 2). This is in contrary to
the case of geothermal well waters of CPGF, 11 and 8 solute the generally expected better performance by more equilibrat-
geothermometers (out of total 28), respectively, from partially ed waters. However, similar contrary behavior is also
517 Page 10 of 11 Arab J Geosci (2016) 9: 517

observed in spring waters of LAGF and Cerritos Colorados the result of existing water mixing process at shallower
(La Primavera) geothermal fields (CCGF), Mexico. In depths. These processes have to be considered in the studies
LAGF, non-equilibrated spring waters have indicated the relating to the evaluation on the performance of solute
reservoir temperatures closer to average BHT (Pandarinath geothermometers in predicting reservoir temperatures from
2014) whereas, non-equilibrated and partially equilibrated springs and well waters of different chemical composition
spring waters of CCGF (Pandarinath and Domnguez- and equilibrium conditions.
Domnguez 2015) have indicated more reliable reservoir
temperatures than those of partially and fully equilibrated
waters, respectively. This type of performance of the sol- Conclusions
ute geothermometers by spring waters, in relation to the
existing equilibrium conditions, may be due to the prevail- Springs and well waters of CPGF are chemically different to
ing mixing process at the shallower depths. Mixing of those of LHGF. Irrespective of the chemical types of these
ascending thermal fluids with colder groundwater in waters, Na/K geothermometers have predicted more reliable
shallower aquifers is reported in Cerro Prieto geothermal reservoir temperatures than other solute geothermometers in
field (Lippmann et al. 1991). The spring waters from both fields. More number of solute geothermometers from
CPGF and LHGF appear to be mixed with shallow mete- non-equilibrium spring waters and partially equilibrated well
oric water which resulted in to inconsistent reservoir tem- waters have presented reliable reservoir temperatures than,
peratures obtained by all the solute geothermometers, ex- respectively, partially equilibrated spring waters and fully
cept Na/K geothermometers. When the spring water rises equilibrated well waters of CPGF. Similarly, in the case of
to the surface, probably is being diluted by mixing of LHGF, more numbers of solute geothermometers from non-
shallower meteoric water (Burgos 1999). Spring water dur- equilibrated well waters have predicted reliable reservoir tem-
ing rise to the surface may cool by conduction, boiling, peratures than from partially equilibrated well waters. The
mixing with colder water, or a combination of these pro- obtained solute geothermometry from springs and well waters
cesses. Fournier (1979) has reported that the temperature of different chemical composition and equilibrium conditions
of the resulting mixed spring water may be above or suggests that the thermal water composition reflect the lithol-
below the boiling temperature (at atmospheric pressure), ogy of the reservoirs and dilution of deep thermal waters, as
and after mixing, chemical re-equilibrium (fully or partial) they ascend to the surface, by shallow meteoritic waters.
may or may not occur. Attaining of chemical re-equilibrium
by the mixed spring water may be possible if the temperature Acknowledgment America Yosiris Garca-Soto and Jos Enrique
after mixing is greater than 100 C. Thermal waters of Marrero would like to thank Mirna Guevara Garca of IER-UNAM for
chloride type from high-temperature reservoirs (>180 C) 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.
are generally considered suitable for Na/K geothermometers Armstrong-Altrin for reviewing and providing their valuable comments
(for example, Karingithi 2009). The better performance of on the earlier version of the manuscript.
Na/K geothermometry and very poor performance by
quartz geothermometry in predicting the reservoir temper-
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