Journal of Volcanology and Geothermal Research 110 (2001) 101119 www.elsevier.

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Geochemical survey of medium temperature geothermal resources xico from the Baja California Peninsula and Sonora, Me
n R. a,*, P. Birkle a, E. Portugal M. a, V.M. Arellano G. a, J. Alvarez R. b R.M. Barraga
a b

ctricas, Unidad de Geotermia, Reforma 113, Col. Palmira, 62490 Temixco, Mor., Mexico Instituto de Investigaciones Ele n Federal de Electricidad, Residencia de Estudios, Campo Geote rmico Cerro Prieto, Cerro Prieto, B.C., Mexico Comisio Received 4 April 2000; accepted 22 January 2001

Abstract to Waters from hot springs and deep wells from Cerritos in the northern Baja California Peninsula and deep wells from the Ri zone (Sonora state) were studied in order to classify medium temperature geothermal resources to be exploited in NW-Mexico. Geochemical characteristics of San Felipe and Punta Estrella coastal springs indicate the mixing of seawater and meteoric components with secondary leaching of evaporates. Reservoir temperatures for both zones were estimated up to 2258C. Mixing of high portions of seawater (.80 wt%) with local waters could be the origin for the Puertecitos coastal spring, with a reservoir temperature estimation of 1958C. The El Coloradito coastal spring is composed of meteoric water with a reservoir temperature of 1278C. The formation of thermal manifestations along the Baja California coast could be related to the heating up of convecting seawater along extensional tectonic structures, as observed for submarine hydrothermal vents at the Gulf of California and along the East Pacic Rise. Volcanic steam-heated waters with a reservoir temperature of 1358C were found at the Valle Chico inland springs from the Baja California Peninsula. to zone originated by evaporation of inltrated waters with similar characteristics to those located in Deep uids from the Ri to deep wells ER-1B (ER) and R-1, the Mexicali Valley. Reservoir temperature of 192 and 1268C are estimated for the Ri to artesian wells M-1, M-2 and M-4 indicate reservoir temperatures from 109 to 1188C. Isotopic data dene respectively. The Ri the artesian wells as typical surface water or shallow groundwater from the Mexicali Valley. The Cerritos deep uids of the Mexicali Valley show a close chemical and isotopic relationship to the adjacent Cerro Prieto reservoir uids suggesting a similar origin and a possible connection of both aquifer systems. Conductive cooling of Cerro Prieto discharge uids could originate the cooler Cerritos system (1308C). to According to the reservoir temperature estimations, electricity could be generated at San Felipe, Punta Estrella and Ri zones using conventional or binary cycle while the direct application of uids in heat pumps and industrial processes is feasible for the other sites. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Mexico; Baja California; Sonora; uid geochemistry; isotopes; medium temperature geothermal resources

1. Introduction Exploration of medium temperature geothermal

* Corresponding author. n). E-mail address: rmb@iie.org.mx (R.M. Barraga

xico considerresources has become important in Me ing the increase in energy demand, and present concerns on diversifying primary fuel sources in order to minimize environmental impact. The national n Federal de electrical utility company, the Comisio Electricidad (CFE) has identied more than 1500

0377-0273/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0377-027 3(01)00205-0

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sites with geothermal characteristics although not all of them have been explored (Arellano, 1996). At present, geothermal energy provides 3.2% of the n total electric capacity in the country (Quijano-Leo rrez-Negr n, 2000). High temperature and Gutie geothermal resources include the Cerro Prieto (620 MWe), Los Azufres, (93 MWe) and Los Humeros (42 MWe) geothermal elds (Quijano n and Gutie rrez-Negr n, 2000). The Las Tres Leo rgenes geothermal eld, located in the state of V Baja California Sur was recently developed by CFE n and generation of 10 MWe is planned (Quijano-Leo rrez-Negr n, 2000). and Gutie Besides the exploited high temperature reservoirs, medium temperature geothermal energy could satisfy local demands, especially when the resource is located near population centers. As some population centers are located far from the power distribution network, electricity needs are solved by combustion of fossil pez, 1996). fuels with high operating costs (Lo Several studies were performed to evaluate the feasibility for the direct use of geothermal energy to provide heating/cooling facilities in new developed resort sites on the Baja California peninsula. The lvarez (1995). local geology was described by A Geophysical and geochemical studies were carried n and Portugal out by Flores et al. (1999), and Barraga (1995), respectively. The elevated thermal gradient of irrigation wells at to zone, located south of the Cerro Prieto the Ri geothermal eld, as well as the high heat ux and the existence of geothermal anomalies at the Imperial and Mexicali valleys areas, have been known since 1975 (Soto, 1975). Gabbroic or basaltic intrusions are suggested to provide the heat source for the thermal manifestations of Cerro Prieto (Pelayo et al., 1985). lvarez (1995) published chemical characteristics A of coastal water samples and their geological environment. Gastil and Bertine (1982) provided chemical composition of the coastal water samples and a brief review for every site with silica and, Na/K and Ca/Na ratios to estimate reservoir temperatures, they concluded that moderately high reservoir temperatures could be found at San Felipe. Based on tritium analyses of Punta Estrella uids, the same authors concluded that the water has not been in contact with atmosphere for some decades. For Puertecitos, past reservoir temperatures of 2503008C were

estimated close to the surface, from deposition of clinozoisite. For this site, Flores et al. (1999) reported the presence of low resistivity probably caused by a saline intrusion, and they suggested the occurrence of a possible geothermal conductor north of the Puertecitos spring. For El Coloradito spring, Gastil and Bertine (1982) pointed out that compared with Punta Estrella, San Felipe and Puertecitos, the water is the hottest and least saline. This paper presents the chemical and isotopic composition of waters from four coastal hot springs (Puertecitos, El Coloradito, Punta Estrella and San Felipe), two inland springs (Valle Chico), and one deep well (Cerritos) from the NE part of the Baja California Peninsula, as well as from ve deep wells to zone in the Sonora state (Fig. 1 and from the Ri Table 1). In order to identify their possible origins, their chemical and isotopic compositions are compared with marine water from the Gulf of California, with published data from the Cerro Prieto reservoir uids, as well as with local precipitation and shallow aquifer data from the Mexicali Valley. Reservoir temperatures are estimated for every site to classify the geothermal resources in the NW-part of the country. 2. Tectonic and geological setting The tectonic history of the NE part of Baja California is associated with a NWSE-trending strikeslip boundary between North American and Pacic plates. This caused the formation of extensional rift system and pull-apart basins of the Extensional Gulf Province (Stock et al., 1991) (Fig. 1). Morphological depressions, such as Salton Sea, the Cerro Prieto basin in the Mexicali Valley and the coastal plane of San Felipe are related to the activity of lateral shear faults, such as the San AndreasImperial system, the Cerro Prieto and San Miguel Faults (Lomnitz et al., 1970; Elders et al., 1972; Halfman et al., 1984). The Extensional Gulf Province is separated from the Transpeninsular Province by NNWSSE-trending faults, such as the rtir Fault. San Pedro Ma The Valle de San FelipeValle Chico is a 100 kmlong valley along the NNWSSE-trending San Pedro rtir Fault and separates the batholithic rocks of the Ma rtir), on the Peninsular Ranges (Sierra de San Pedro Ma

 n et al. / Journal of Volcanology and Geothermal Research 110 (2001) 101119 R.M. Barraga
Sa
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117

Fig. 1. Area map with structural information from Elders et al. (1972), Halfman et al. (1984), as well as sampling sites.

west, from the lower elevation basins and ranges of the Extensional Gulf Province to the east (Sierra San Felipe) (Stock, 1989) (Fig. 1). The Valle de San FelipeValle Chico may be considered an oblique pull-apart basin formed by the right lateral motion of the strikeslip fault systems to oblique normal displacement along rtir Fault (Stock, 1989). the San Pedro Ma 3. Lithology The lithology of the Mexicali Valley, which is

IC

PUERTECITOS VOLCANO PRIETO

O
o

116

115

114

limited to the west by the Sierra Cucapah and to the east by the Colorado River, is formed by: (a) a Paleozoic basement of limestone, sandstone, conglomerate and metamorphic units, which crop out in the Sierra Cucapah; (b) an upper Cretaceous granitic intrusion, which corresponds to the Baja California batholith and forms large parts of the Sierra Cucapah; (c) a tertiary sedimentary sequence of intercalated sandstones, silstones and shales; and (d) Pleistocene to Recent, non consolidated, extensive alluvial sediments (sand, clay, lime, gravel) and rhyodacites associated with the Cerro Prieto volcano.

104 n et al. / Journal of Volcanology and Geothermal Research 110 (2001) 101119 R.M. Barraga

Table 1 Chemical composition (mg/kg) of samples

Sample Site Type Sampling T date (8C) 10/08/95 10/08/95 29/06/95 09/08/95 09/08/95 10/08/95 29/06/95 28/06/95 28/06/95 28/06/95 02/11/95 21/11/95 14/11/95 63 63 52.4 48 33 58 28 50 47.5 41.5 27 50 91 pH E. C. Na (mS/cm) 8.8 1.45 8.5 1.42 6.6 38.5 5.8 123.2 5.8 47 7.5 7.66 8.2 60.5 7.9 3.1 7.8 2.9 7.8 1.03 5 107.2 6 122.8 6 26.4 K Ca Mg Li Rb Cl SO4 HCO3 SiO2 B F d 18 O (D ()smow ()smow 29.8 29.6 22.4 21.8 25.8 28.3 20.7 210.4 29.9 29.8 26.4 26.0 210.1 278 269 224 238 263 267 25 278 282 277 258 258 298

VCA VCAZ P SF PE C SP MA-1 MA-2 MA-4 R-1 ER C-9

Valle Chico Valle Chico Puertecitos San Felipe Punta Estrella El Coloradito Puertecitos to Ri to Ri to Ri to Ri to Ri Cerritos

Spring(inland) Spring(inland) Spring(coast) Spring(coast) Spring(coast) Spring(coast) Sea water Artesian well Artesian well Artesian well Deep well Deep well Deep well

240 8.9 24 0.04 0.4 0.3 219 8.8 26 0.03 0.3 0.7 8600 534 878 456 3.9 0.3 14000 1636 2411 222 26.9 31.4 7200 916 1943 69.4 16.7 20 2000 43 264 2.5 3.9 0.7 11428 472 396 1369 0.17 0.4 700 10 36 1.3 0.2 , 0.02 480 12 46 1.6 0.4 , 0.02 500 11 60 2.4 0.2 , 0.02 16667 471 5658 1122 7.6 6 18750 1620 6842 257 16.4 26 4032 141 400 117 7.1 2.5

126 112 15086 27935 15378 2920 19539 836 619 652 35841 41335 6788

313 328 1282 529 21.6 62 2560 113 134 170 279 248 25

43.9 62.8 139 647 570 37.2 134 148 128 104 17 114 165

73 75.6 60.4 53.2 99.6 48.9 8.8 37.2 37.2 81.5 27.2 125 71.2

1.6 4.6 1.6 5.9 5.3 22.9 15 41 13.2 22.8 4.5 8.5 4.01 , 0.1 , 0.1 1.18 0.117 1.15 , 0.1 1.94 7.3 44.6 10.9 68.1 7.3 15.9

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The volcanic province of Puertecitos along the coastal border, including the San FelipeValle Chico area, is formed by three lithological units (Stock et al., 1991; Martin Barajas and Stock, 1993): (a) andesites and dacites of the volcanic arc from early to middle Miocene; (b) rhyolitic domes and the tuff formation El Canelo; and (c) pyroclastic ignimbrite ows from the Pliocene period, forming the plains of the Gulf coast. Pre-batholitic, Paleozoic metamorphic units of pelitic, quartzitic, and calcareous metasediments form the basement in the San FelipeValle Chico area (Gastil et al., 1975). In the coastal area, marine sandstone sequences interlayer and cover the volcanic units (Stock et al., 1991). About 10 km south of Puertecitos, the volcano Prieto and some andesitic ows reect the nal volcanic activity of the region, beginning in the Pleistocene period (Stock et al., 1991). 4. Location of the thermal sites Fig. 1 shows the location of the thermal spring and well sites. The sample sites can be divided in following sub-areas: 4.1. Eastern coast of the Baja California Peninsula The springs San Felipe (SF), Punta Estrella (PE), El Coloradito (C) and Puertecitos (P) are aligned close to the eastern shore line of the Baja California Peninsula. The hot springs of San Felipe boil at various places along the shoreline. According to Gastil and Bertine (1982), the springs are located on the south side of a ridge of oxide-bearing meta-carbonic rocks. Some of the springs are accessible exclusively during low tide. Gastil and Bertine (1982) describe mostly CO2 gas bubbles. In addition, shermen have reported the existence of submarine hot springs (Gastil and Bertine, 1982). The Punta Estrella spring is located at the western seashore of the Gulf of California in granitic rock lvarez, 1995) and is characterized by poor gas (A exhalations. According to Gastil and Bertine (1982), Punta Estrella waters contain dissolved H2S and have low Mg/Ca ratio due to passage through carbonate rocks. The sediments contained small amounts of barite (Gastil and Bertine, 1982), which probably precipitated as a result of mixing with local seawater.

The El Coloradito hot spring is located directly at the seashore of the Gulf of California within a conglomerate sandstone bedrock. The spring is characterized by evaporation and the lack of gas exhalations. The spring forms small pits, which are lvarez, associated with NNWSSE-trending faults (A 1995). Slight hydrothermal deposition of silica and lvarez, 1995). The spring sulfur was observed (A waters have no CO2, little HCO3, and high Ca/Mg ratios (Gastil and Bertine, 1982). NNWSSE-trending structures dene the orientation of the natural pools of the Puertecitos springs at the border of the ocean. The temperature uctuation from 55 to 668C is related to tidal effects. Reddish and brown colored, hydrothermal strongly altered ignimbrites form the bedrock of the spring area lvarez, 1995). According to Gastil and Bertine (A (1982), the Pliocene rhyodacites are partially hydrothermally altered to form silica, pyrite, barite and clinozoisite. rtir 4.2. Sierra de San Pedro Ma The Valle Chico is located within the mountain rtir in the interior range of the Sierra de San Pedro Ma part of Baja California state. Two springs, Valle Chico A (VCA) and Valle Chico AZ (VCAZ) with similar thermal characteristics were found, but only VCAZ is affected by hydrothermal surface alteration. Here, precipitated sulfate and silica are found along small lvarez, fractures of granitic and metamorphic rocks (A 1995). 4.3. Valle de Mexicali (Cerritos) Cerritos is located in the plain of the Valle de Mexicali, about 3 km northwest of the Cerro Prieto geothermal eld close to the Cerro Prieto volcano. The Cerritos name is derived from the presence of small round shaped sandstone hills, formed by former lvarez, 1995). Eight wells hydrothermal activity (A were drilled by CFE (depth: 204615 m) to verify the presence of hydrothermal activity. At a depth of 180 m, a temperature anomaly of 1528C was identied in the well C-2. This thermal anomaly decreases with depth and it was suggested to be caused by the rise of Cerro Prieto reservoir uids or by the existence of a geothermal reservoir, located north of the Morelia lvarez, pers. commun., 1996). As part of Fault (R.J. A

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this study, a water sample was taken from the well C-9 at a depth of 1074 m. to) 4.4. Colorado River plain (Ri to zone is located on the eastern side of the The Ri Colorado River in the northwest part of the Sonora state. Three water samples were taken from artesian thermal wells (MA-1, MA-2, MA-4) and two samples from deep wells (R-1, ER). Depths for artesian wells MA-1, MA-2 and MA-4 are 250, 615 and 600 m, respectively. The deep wells ER and R-1 reach depths of 3791 and 1230 m, respectively.

diagram is used to compare relationships between samples (Truesdell, 1992). 6. Results and interpretation 6.1. Ionic balance and uid classication Table 1 shows the sampling sites, sample names, measured electrical conductivity, pH, temperature, and chemical and isotopic compositions of the water samples. Table 2 shows the chemical analysis of the gas sample taken from San Felipe spring. The salinity of the samples ranged widely: from 100 of the Valle Chico springs to more than to ER well. The Ri to 40 000 mg/kg Cl of the Ri deep wells, Cerritos C-9 well, and San Felipe and Punta Estrella springs show slightly acid pH values. to Almost neutral pH values were measured for the Ri artesian wells and for the Puertecitos and El Coloradito springs, whereas seawater and the Valle Chico samples are slightly alkaline. Except the sodium-sulfate type waters from Valle Chico, all samples are classied as sodium chloride waters by the Piper method (Piper, 1944). The ClSO4 HCO3 classication diagram (from Giggenbach, 1988) is shown in Fig. 2. Most of the samples are located in the upper Cl corner (mature water). The Puertecitos sample is located close to the seawater point. The artesian well uids MA-1, MA-2 and MA-4 are located outside of the equilibrated mature water area, while Valle Chico samples are classied as volcanic sulfate waters. In general, this type of uid is formed by the absorption of magmatic gases in relatively shallow aquifers with subsequent rock dissolution (Giggenbach, 1988). The Schoeller diagram for spring waters and seawater is presented in Fig. 3, while well water samples are shown in Fig. 4. The composition of the Puertecitos, San Felipe and Punta Estrella samples is similar to seawater, but with increased K, Ca and HCO3 concentrations and some depletion in Mg and

5. Methods The following standard techniques were used for the chemical analysis of water samples at the Instituto ctricas (IIE), Cuernavaca, de Investigaciones Ele xico: Me Cations (Na, K, Ca, Mg, Si, Rb) were analysed by atomic absortion spectrometry (AAS) and the anions (F, Cl, NO3, SO4) by ion chromatography. B was determined by the Mannitol method, As by spectrophotometry, and CO3, HCO3 and pH by alkalinity titration according to the Mexican norms NOM-AA63-1981, NOM-AA-46-1980 and AA-36-1980, respectively. Non-condensable gases (CH4, H2, Ar, O2 and N2) were determined by gas chromatography (Giggenbach and Goguel, 1989). Other non-condensable gases were determined by titration (CO2), by the iodinesodium thiosulfate method (H2S) and Nessler spectrophotometry (NH3). The stable isotopes 18O and deuterium were measured by mass spectrometry. The computer program clasif.for (Mercado et al., 1981) was used to calculate the chemical ionic balance and to classify uids according to Piper (1944). The Piper method classies the samples according to their major ion composition. The logarithmic scale of ion concentrations in the Schoeller

Table 2 Gas analysis of San Felipe sample. Concentrations in mmol/mol of dry steam. XG gas/steam ratio in mg/kg Sample SF Date 8/08/95 XG 472 700 CO2 992 H2S 0.038 NH3 0.000 H2 0.000 He 0.000 Ar 0.411 N2 6.51 CH4 0.993

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Fig. 2. ClSO4 HCO3 ternary diagram for the samples (after Giggenbach, 1988).

SO4 (Fig. 3). This is especially valid for the Punta Estrella site. The Ca increase in high temperature reservoirs can be due to the conversion of anorthite to albite with a slight loss in Na, while the decrease in SO4 and Mg is related to the temperature inverse solubility of anhydrite and incorporation of Mg in secondary alteration minerals (clays) (Truesdell, 1995). The enrichment in HCO3 can be due to moderate temperature reactions between CO2 and rock minerals (Truesdell, 1995) according to: CO2 1 H2 O 1 Na-silicate Na1 1 HCO2 3 1 H-silicate This reaction is characteristic for waters in contact

with dissolved CO2 at temperatures conditions below 2008C. In high temperature reservoirs, HCO3 is highly depleted due to boiling processes and the separation of CO2 (Truesdell, 1995). The El Coloradito sample is less mineralized than the other coastal springs. The Valle Chico samples have very low Mg and Cl contents, which indicate a dilute meteoric composition. Samples from the artesian wells MA-1, MA-2 and MA-4 show a similar chemical composition which suggests a common aquifer for them (Fig. 4). The R-1 and ER deep well samples are more concentrated than the shallower artesian well uids. The relatively low bicarbonate content and acidic character of sample R-1 are typical for chloride type geothermal

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Fig. 3. Schoeller diagram for spring samples.

waters whose pH ranges from 4 to 9, according to Henley et al. (1984). Fig. 5 shows the LiClB composition of samples as proposed by Giggenbach (1992). Li, Cl and B can be used as conservative tracers due to minor modications of their composition by secondary alteration processes. Except the Valle Chico samples, all samples are located in the Cl corner. The low B/Cl ratio of the samples is typical for seawater or seawater mixing (Giggenbach, 1992). 6.2. Geothermometry Geothermometers are based on the equilibrium of temperature-dependent reactions in the reservoir. These reactions become slower as waters cool during ascent allowing the temperature at which they occur to be estimated. Geothermometers can provide erroneous temperature values if waters mix after the equilibrium was attained. The cationic composition

geothermometer (CCG) (Nieva and Nieva, 1987) has shown estimated temperatures close to measured temperatures in a number of cases, especially for deep uids, diluted during ascent with shallow cold water. The CCG is considered to be a good method of temperature estimation (OLADE, 1994). It applies four equations, depending on the proportion between Na, K, Ca and Mg. In the case of high temperature geothermal uids with low Mg-content, the expression to be used is a function of the Na/K ratio, whereas Mg based geothermometers tend to reect recent equilibrium and not the actual reservoir temperature (Truesdell, 1995). Temperatures of springs and wells from the study areas were calculated by following geothermometers: CCG (Nieva and Nieva, 1987), NaKCa (Fournier and Truesdell, 1973), silica (Fournier and Potter II, 1982), and LiMg (Kharaka and Mariner, 1989). The geothermometers TKN (based on the K/Na ratio) and TKM (based on the Mg/K ratio), proposed by Giggenbach (1988), are

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109

Fig. 4. Schoeller diagram for well samples.

presented in Fig. 6. Table 3 shows the estimated reservoir temperatures for the samples and for seawater as a reference. According to Fournier (1992), the LiMg geothermometer is useful for well samples, while for hot spring samples it provides lower than actual reservoir temperatures due to rapid re-equilibration. The NaKMg ternary diagram (Giggenbach, 1988) denes the equilibrium of waters using the relationship between Na/1000, K/100 and Mg (Fig. 6). None of the thermal springs and wells plots on the full equilibrium line, indicating: (a) partial equilibrium with the host rock and (b) possible mixing of different water types. San Felipe and Punta Estrella uids show the highest reservoir temperature (245 and 2528C, respectively), indicated by the TKN geothermometer (Fig. 6). For San Felipe, the CCG geothermometer resulted in a reservoir temperature of 2178C, which is slightly lower than TNaKCa estimation (2308C). TCCG

and TNaKCa geothermometers result in 2258C for Punta Estrella uids. Lower TSI temperatures of 1058C are possibly caused by silica precipitation during sampling or mixing with low silica content water. Gas geothermometers proposed by rsson (1992) were applied to gas samples from Arno San Felipe. The CO2 and H2S-based geothermometers resulted in 199 and 2228C, respectively. Reservoir temperatures for this site are estimated to be medium. The Puertecitos sample is located far from the full equilibrium line and relatively close to the seawater point, which suggest a close interrelationship (Fig. 6). TKN and TNaKCa temperatures between 192 and 1978C probably overestimate the reservoir temperature and may suggest the presence of seawater since TKN and TNaKCa geothermometers indicate 162 and 1738C for seawater, respectively. As other geothermometers disagree, it is suggested a short residence time for the uid in the reservoir, where

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Fig. 5. ClLiB ternary diagram for the samples (after Giggenbach, 1988).

most reactive components re-equilibrate (Fournier, 1992). At the El Coloradito site, the close agreement between cationic geothermometers indicates a reservoir temperature of about 1278C. For Valle Chico, TCCG, TNaKCa and TKM geothermometers indicate reservoir temperatures between 133 and 1398C. Lower Na-content of the VCAZ sample causes lower TNaKCa-temperature of 988C. TNaKCa and TCCG suggest reservoir temperato artesian tures in the range of 1041258C for the Ri wells. Slightly higher temperatures are obtained with TKN, while TKM, TLiMg and TSi indicate lower

values. TKN and TNaKCa indicate a reservoir temperature of 1488C for the deep well R-1. Considto samples, only well ER was classied as ering the Ri high temperature geothermal water according to the CCG (192), TKN (221), and TNaKCa (2068C) geothermometers. The CCG result for this well agrees well with temperature estimation of 1958C lez, based on hydrothermal mineralogy (Gonza 1995). Reservoir temperature estimations for the C-9 well are rather low. TNaKCa and TKN indicate 155 1608C, while TSi and TLiMg showing the last equilibrium for the uid at 1178C.

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Na/1000

TKN
220 240 260 280 300 320 340

180 200

160 140

120 100 80 60
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VCAZ VCA

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ER

Rito
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P

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C9 MA4 SW

Puertecitos

K/100
300
o

Mg
240
o

200

180

160

140

120

100 o

80 o

TKM
Fig. 6. NaKMg ternary diagram for the samples (after Giggenbach, 1988).

Table 3 Reservoir temperature estimations (8C) for the samples (see references in text) Sample VCA VCAZ P SF PE C MA-1 MA-2 MA-4 R-1 ER C-9 Seawater TCCG 133 138 154 217 225 127 104 118 112 126 192 130 128 TNKCA 136 98 192 230 224 126 109 125 118 147 206 155 172.7 Mg correction 136 98 34 160 203 126 109 125 118 70 181 56 TLiMg 153 147 81 149 153 160 80 95 73 87 130 116 25.7 TSI 121 122 111 105 137 89 89 89 126 73 140 117 TKN 164 169 197 245 252 134 114 142 135 148 221 160 162 TKM 139 144 121 172 172 123 91 93 86 104 168 102 96

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6.3. Isotopic uid composition Fig. 7 shows the isotopic composition of the water samples in a dD vs. d 18O graph. Also shown for comparison are the global meteoric line (GMWL), as well as the isotopic composition of surface and irrigation water from the MexicaliImperial Valley a, 1977). The central (Crosby et al., 1972; Garc Mexicali Valley ground waters in this gure origi-

nated as Colorado River water was progressively altered by evaporation processes to heavier isotopic compositions (Truesdell et al., 1979). Isotopic data for total discharge samples from Cerro Prieto a (Truesdell et al., 1979) and b reservoirs (Verma et al., 1996) as well as data for Salton Sea brines (Lippmann et al., 1999) are also illustrated. The Cerro Prieto reservoir uids were interpreted to originate from a mixture of evaporated hypersaline marine

Fig. 7. d D vs. d 18O of studied samples in comparison with the global meteoric water line, precipitation, groundwater of the Mexicali Valley, Colorado River water, Cerro Prieto and Salton Sea reservoir uids and seawater.

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Fig. 8. dD vs. Cl of the samples, shallow groundwater of Mexicali Valley, precipitation, Cerro Prieto uids and seawater.

brine with Colorado River water (Truesdell et al., 1981). A seawater evaporation curve is shown in Fig. 9. Seawater concentrated by evaporation to about six times its normal salinity would have the required Cl concentration for the hypersaline brine component of the Cerro Prieto uids (Truesdell et al., 1981). The Salton Sea uids are interpreted as inltrated hypersaline brines of previously evaporated Colorado River water (Lippmann et al., 1999). Very negative deuterium values are caused by secondary thermal metamorphism of evaporites (McKibben et

al., 1988). Figs. 8 and 9 show the chloride vs. dD and chloride vs. d 18O composition for the same samples. 6.3.1. Eastern coast of the Baja California Peninsula In general, the location of springs in the coastal zone suggests the mixture of altered seawater with local continental waters. In Fig. 7, the El Coloradito (C) spring water composition is similar to local precipitation and irrigation water affected by evaporation, whereas that of Puertecitos (P) spring is similar to

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Fig. 9. d 18O vs. Cl of the samples, shallow ground waters of Mexicali Valley, precipitation, Cerro Prieto uids and seawater.

seawater. According to the coastal mixing line in Fig. 7, the proportion of seawater for Puertecitos seems to be more than 80%, whereas El Coloradito water is of meteoric origin. The Punta Estrella (PE) and San Felipe (SF) uids with slightly elevated d 18O-values are located to the right hand side of the coastal spring mixing line (Fig. 7). The offset of the PE and SF points from the coastal trend (Fig. 8), was used to estimate an amount of excess chloride (or chloride gain) of 11 400 and

16 700 mg/kg, respectively, contributed by interaction with evaporate minerals. Besides, the slightly positive oxygen shift indicates waterrock interaction at moderate temperatures. From Fig. 7, the oxygen shift for the samples is 1.9 and 2.73 for PE and SF waters, respectively. Because of the small amounts of hydrogen present in rocks, it is likely that no change in d 2H has occurred as a result of water/rock interaction. The original d 18O and chloride compositions of PE water are estimated to be

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27.7 and 4000 mg/kg, and those for SF water are 24.5 and 11 300 mg/kg (Fig. 9). rtir 6.3.2. Sierra de San Pedro Ma The Valle Chico springs VCA and VCAZ are located close to the GMWL and do not show the oxygen isotopic shift characteristic of high-temperature geothermal waters (Fig. 7). These samples are low in solutes, especially in Cl, and are isotopically intermediate between evaporated shallow groundwater and rainwater (Figs. 8 and 9). This shows the meteoric character of the spring waters. In addition, the elevated sulfate content indicates heating of shallow ground water by ascending steam with H2S and its subsequent oxidation to SO4. to) 6.3.3. Colorado River plain (Ri The d 18O and dD values of the deep wells R-1 and ER are much higher than those of local groundwater from the Mexicali Valley and of waters from the adjacent artesian wells M-1, M-2 and M-4 (Fig. 7). The to shallow artesian isotopic composition of the Ri wells (M1-, M2-, M-4) is close to the GMWL and to evaporated surface water from the Mexicali Valley (Fig. 7). The small oxygen isotope shift is due to low to moderate temperature conditions. The relationship between waters from artesian wells and deep wells suggests that deep waters were possibly originated by the inuence of little meteoric water, which can to Mixing Line (Figs. 8 and 9). be described as the Ri 6.3.4. Valle de Mexicali (Cerritos) The deep well C-9 shows an isotopic composition close to the Cerro Prieto reservoir uid in Fig. 7, which indicates a similar origin for both uids. According to Truesdell et al. (1981), the Cerro Prieto uids originated from partially evaporated Colorado River water mixed with strongly evaporated fossil seawater. In contrast, Giggenbach (1992) explains the isotopic composition of the Cerro Prieto aquifer uids by a 20 times dilution of Salton Sea uids, with further oxygen-18 exchange at 3508C. However, Cl/ Br ratios of Salton Sea uids are different from those of Cerro Prieto uids while ratios are similar for both seawater and Cerro Prieto water (Truesdell et al, 1981), which supports the occurrence of seawater in Cerro Prieto uids. The Cerritos sample is aligned along the Cerro Prieto mixing line, proposed by

Truesdell et al. (1981) (Fig. 7). In Fig. 9, the oxygen shift of the C-9 well indicate similar waterrock interaction processes as shown for the Cerro Prieto reservoir uids. As conductive cooling of uids does not affect signicantly their chemistry and isotope composition (Truesdell, 1992), the similar composition of the Cerro Prieto a reservoir uids and Cerritos waters could be explained by conductive cooling of Cerro Prieto discharging uids. As uid cools down, Mg concentration increases and silica concentration decreases, as observed for the Cerritos sample. 6.4. Geothermal potential Based on their isotopic and chemical characteristics, the geothermal potential of the individual hot springs and wells is evaluated as follows (Table 4; Lindal, 1973): 6.4.1. Eastern coast of the Baja California Peninsula The chemical and isotopic composition of the Puertecitos waters, as well as geothermometer temperatures indicate a primary marine origin with an estimated contribution of 8090%. The seawater is subsequently heated by a thermal source. The direct use of hot uids in absorption heat pumps is feasible. The San Felipe and Punta Estrella uids consist of a mixture of seawater and meteoric surface water with further positive oxygen shift due to waterrock interaction processes at moderate to high temperatures. Reservoir temperature estimations for both liquid and gas samples from the San Felipe site indicate a values between 217 and 2228C, which denes the reservoir as a medium to high temperature type. With this energetic resource, electricity could be generated by conventional or non-conventional technology for both sites. Most portions of the El Coloradito uids are composed of meteoric water. The relatively low reservoir temperature (,1008C) is not sufcient for electricity generation by conventional technology, however binary cycle plants can operate above 858C (Dickson and Fanelli, 1995). Direct use of the resource is possible. The origin of thermal springs along the coast of the Baja California Peninsula could be explained by processes similar to the formation of hydrothermal vents in the shallow zone of the Gulf of California

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Table 4 The Lindal diagram (Lindal, 1973) Source temperature (8C) 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 Potential uses

Evaporation of highly concentrated solutions Refrigeration by ammonia absorption Digestion paper pulp, kraft Heavy water via hydrogen sulde process Drying of diatomaceous earth Drying of sh meal Drying of timber Alumina via Bayer's process Drying farm products at high rates Canning of food Evaporation in sugar rening Extraction of salts by evaporation and crystallization Fresh water by distillation Most multiple effect evaporations, concentration of saline solutions Drying and curing of light aggregate cement slabs Drying of organic materials, seaweeds, grass, vegetables, etc. Washing and drying of wool Drying of stock sh Intense de-icing operations Space heating Greenhouses by space heating Refrigeration (lower temperature limit) Animal husbandry Greenhouses by combined space and hotbed heating Mushroom growing Balneological baths Soil warming Swimming pools, biodegradation, and fermentations Warm water for year-round mining in cold climates De-icing Hatching of sh, sh farming

and along the East Pacic Rise about 200 km south of ndez, 1988). In Cabo San Lucas (Mercado and Ferna the latter case, extensional tectonic structures facilitate the heating of inltrating seawater by a shallow magma chamber, forming mineral depositions by black smokers and maximum water temperatures of ndez, 1988). 3308C (Mercado and Ferna It is recommended to continue exploration at the sites described. Shallow wells should be drilled in the San Felipe and Punta Estrella zones in order to obtain more representative samples, which allow the quantitative evaluation of the resource potential. rtir 6.4.2. Sierra de San Pedro Ma The relatively low reservoir temperature of 1358C,

the moderate isotopic shift in dD and d 18O, as well as the low mineralized sodium-sulfate type of the Valle Chico springs indicates the heating up of shallow groundwater and recent meteoric water by ascending steam with H2S. Due to the low temperature estimated electricity could be generated only by binary cycle and direct use of the hot uids is possible. 6.4.3. Valle de Mexicali (Cerritos) Relatively low reservoir temperatures (1308C) were found for this sample (C-9), which could originate from conductive cooling of the adjacent Cerro Prieto uids. Structural features indicate communication between the a and b zones: the ascent and circulation of the hot Cerro Prieto uids with surface discharge

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west of the eld is facilitated by a vertical NS fault (Stallard et al., 1987; Goldstein et al., 1989). A lateral ow migration from east to west was described by Lippmann et al. (1991). Thus, the similar chemical and isotopic composition of Cerro Prieto and Cerritos uids, as well as the existence of vertical and lateral pathways may allow connection between the Cerro Prieto reservoir at a depth between 3000 and 1000 m and the deep well C-9 (depth: 1074 m) of the Cerritos zone. However, it is recommended that additional samples from the Cerritos site be obtained to conrm the discharge of Cerro Prieto geothermal uids. The direct use of the resource in industrial processes is suggested for this zone. to) 6.4.4. Colorado River plain (Ri The deep well waters ER and R-1 have less inuence of meteoric water than the artesian wells M-1, M-2 and M-4, and are probably affected by highly saline sedimentary waters such as those of Cerro Prieto. Medium to high temperature reservoir conditions (1958C) allow the application of conventional technologies for electricity generation. The slight heating process is reected by low reservoir temperatures from 110 to 1158C, thus the resource can be classied as medium temperature type. Electricity can be generated by using non-conventional technology such as the binary cycle. 7. Conclusions A geochemical study of uids from springs and wells was carried out in order to investigate the possibility of exploiting low to medium temperature geothermal resources in NW-Mexico. A wide range of uid salinity was found: low salinity uids (,1000 mg/kg Cl), such as the Valle Chico springs to zone, moderate and artesian wells from the Ri salinity (29006800 mg/kg Cl) waters in Cerritos and El Coloradito, and hypersaline (15 000 to .40 000 mg/kg Cl) springs in the coastal zone of Baja California (Puertecitos, San Felipe, Punta to zone. Except Estrella) and deep wells in the Ri the sodium-sulfate composition of the Valle Chico hot springs in the central part of the northern Baja California, all uids are of sodium chloride composition. All thermal sites are related to adjacent fault

systems, such as the Cerritos zone to the Imperial to zone to the Cerro Prieto Fault, and Fault, the Ri the coastal springs of San Felipe and Punta Estrella to the San Miguel Fault. The extensional character of these lateral fault systems facilitates the rise of deep heat sources, as observed for the submarine hydrothermal vents in the Gulf of California and along the East Pacic Rise. The Valle Chico springs are related to the NNWSSE trending shear fault of San Pedro rtir. The origin of the Cerritos water can be Ma described as a mixing process of Colorado River water with fossil seawater, as proposed for the Cerro Prieto geothermal uids. The coastal springs of the Baja California originated by seawater mixing with local meteoric water. The high salinity of the San Felipe and Punta Estrella springs is explained by leaching of evaporate sediments. to deep uids represented high saline The Ri sedimentary waters, which are little affected by meteoric water and with similar characteristics to those of the Mexicali Valley. The Valle Chico springs show characteristics of recent meteoric water, heated by ascending H2Svapor. Acknowledgements This study was part of the project `Geochemical study to zones of hydrothermal uids from the Puertecitos-Ri in Baja California', supported by CFE, Gerencia de ctricos, Residencia de Estudios Proyectos Geotermoele rmico Cerro Prieto. Authors acknowldel Campo Geote edge the CFE for providing information and allowing to be published. Special thanks are given to Eng. H. rrez Puente and Dr D. Nieva G. for valuable Gutie support. Thanks are also given to Dr A.H. Truesdell and an anonymous reviewer for useful comments, which improved this work. References
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