versión On-line ISSN 2007-2902
versión impresa ISSN 1026-8774
Rev. mex. cienc. geol vol.24 no.1 México abr. 2007
Revista Mexicana de Ciencias Geológicas
Mineralogical and geochemical effects due to hydrothermal alteration in the Los Azufres geothermal field, Mexico
Efectos mineralógicos y geoquímicos impuestos por alteración hidrotermal en el campo geotérmico de los Azufres, México
Ignacio S. TorresAlvarado1, Kailasa Pandarinath2, Surendra P. Verma2, and Peter Dulski3
1 Departamento de Sistemas Energéticos, Centro de Investigación en Energía, Universidad Nacional Autónoma de México, Priv. Xochicalco s/no., Col. Centro, Apartado Postal 34, 62580 Temixco, Morelos, Mexico. email@example.com
2 Departamento de Sistemas Energéticos, Centro de Investigación en Energía, Universidad Nacional Autónoma de México, Priv. Xochicalco s/no., Col. Centro, Apartado Postal 34, 62580 Temixco, Morelos, Mexico.
3 GeoForschungsZentrum Postdam, Telegrafenberg, 14473 Potsdam, Germany.
Manuscript received: March 14, 2006
Corrected manuscript received: August 30, 2006
Manuscript accepted: August 31, 2006
To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, we analyzed the whole rock chemical composition (major and trace elements, including rareearth elements REE) of two distinct portions of a drill well core sample from the Los Azufres geothermal field, Mexico. This highly hydrothermallyaltered sample allowed us to study, for the first time, the mineralogical and chemical effects imposed by hydrothermal alteration on the mm scale in this important geothermal system. Mineralogically, hydrothermal alteration in the sample is mainly represented by chloritization of primary olivine and pyroxene, argillitization of primary plagioclase, as well as banded chlorite and quartz, with significant amounts ofepidote and hematite. The "altered" part of the sample contains intensely altered remnants of the fresh rock, which show intense silicification, hematization, and dissolution boundaries. Most major and trace elements were mobilized from the original rock. Major element composition reflects the silicification, chloritization, and epidotization processes taking place in the geothermal system. The rareearth elements La and Ce, as well as Yb and Lu were probably partially redeposited during alteration. The positive anomaly of Eu may suggest that Eu is being concentrated in hydrothermal epidote after its release from plagioclase to the geothermal fluid. The highfield strength elements such as Zr, Ti, and P, show as well significant hydrothermal alterationrelated decrease in the highlyaltered rock. The geothermal fluid responsible for this hydrothermal alteration was probably oxidizing, of high temperature (>250° C), and enriched in REE and other trace elements.
Key words: geothermal systems, element mobility, waterrock interaction, HFSE, REE, Los Azufres, Mexican Volcanic Belt, Mexico.
Los efectos de los procesos de alteración hidrotermal en la composición química de rocas volcánicas fueron investigados por medio del análisis químico de roca total (elementos mayores y traza, incluyendo los elementos de las tierras raras) de dos partes diferentes de un mismo fragmento de núcleo de pozo proveniente del campo geotérmico de Los Azufres, México. Esta muestra, con intesa alteración hidrotermal, nos permitió estudiar por primera vez los efectos mineralógicos y químicos impuestos por la alteración en una escala de milímetros para este importante sistema hidrotermal. Desde el punto de vista mineralógico, la alteración hidrotermal de la muestra está evidenciada por la cloritización de olivino y piroxeno primarios, la alteración de plagioclasa primaria a minerales arcillosos, la presencia de clorita y cuarzo en bandas, así como la presencia de abundante epidota y hematita. La porción alterada de la muestra contiene un remanente intensamente alterado de la roca fresca, el cual presenta silicificación intensa, hematización y bordes de disolución. La mayoría de los elementos mayores y traza fueron movilizados de la roca original. La concentración de los elementos mayores es un reflejo de los procesos de silicificación, cloritización y epidotización que afectaron a la roca. Los elementos de las tierras raras La y Ce, así como Yb y Lu, fueron parcialmente redepositados durante la alteración. La anomalía positiva de Eu sugiere que este elemento fue concentrado en la epidota después de haber sido extraído por el fluido geotérmico desde la plagioclasa. Los HFSE como Zr, Ti y P muestran, de la misma manera, importantes reducciones en su concentración relacionadas con la alteración. El fluido geotérmico responsable de esta alteración hidrotermal fue probablemente oxidante, de alta temperatura (>250° C) y enriquecido en tierras raras y otros elementos traza.
Palabras clave: sistemas geotérmicos, movilidad de elementos, interacción aguaroca, HFSE, REE, Los Azufres, Cinturón Volcánico Mexicano, México.
The Los Azufres geothermal field (LAGF) is located in the central part of the Mexican Volcanic Belt (MVB; Figure 1), approximately 200 km northwest of Mexico City. The LAGF has been extensively explored and developed since 1975. Nowadays, it represents the second most important geothermal field in Mexico, with a total installed capacity for electricity production of about 100 MW (GutiérrezNegrín and QuijanoLeón, 2005).
Even though the Los Azufres area has been the focus of numerous geological, hydrogeological, and geophysical studies (see Verma et al., 2005 and references therein), the geochemical composition of rocks has received relatively less attention. Hydrothermal alteration at the LAGF has been described, among others, by Cathelineau et al. (1985) and TorresAlvarado (2000, 2002). A purely mineralogical study of samples from wells Az5, Az28, and Az31, based on Xray diffraction analysis, was recently carried out by Pandarinath et al. (2006), which, however, presented no chemical data to characterize the related chemical effects of hydrothermal alteration. Geochemical studies from the LAGF have reported major and a few trace elements (DobsonandMahood, 1985; Cathelineau et al., 1987, 1991; Pradal and Robin, 1994; TorresAlvarado and Satir, 1998), whereas only Cathelineau et al. (1987) and TorresAlvarado and Satir (1998) discussed hydrothermal alteration effects in the chemical composition of rocks.
Recently, Verma et al. (2005) reported a systematic study of the hydrothermal alteration effects for major and trace elements as well as Sr, Nd, and Pb isotopic compositions in rocks from the LAGF, comparing the chemical composition of outcropping (i.e., fresh) rocks to that of relatively morealtered (i.e., shallow <1000 m depth) ones. This comparison was based on the assumption that the shallow, hydrothermallyaltered rocks had a "beforealteration" chemistry very similar to the chemical composition of the surface rocks from the LAGF. Using a strict statistical methodology, these authors showed that significant element mobility has taken place in rhyolitic rocks at the LAGF, especially for the alkalis Na and K, the highfield strength elements Zr, Ti, and P, as well as for Pb and Nd isotopic ratios. Thus, Verma et al. (2005) necessarily based their conclusions on the statistical comparison of the chemical composition of fresh rocks (from the surface) to that of the altered ones (from the shallower part of the geothermal field) due to the unavailability (at that time) of a single volcanic rock which could show both fresh and altered portions, and consequently, could allow us to quantify the chemical changes imposed by hydrothermal alteration processes at a much shorter scale. In other words, the existence of such a single volcanic rock would eliminate the necessity of the assumption (implicit in Verma et al., 2005) that prior to the alteration process, the shallow drill well rocks, on the average, had the same major and trace element composition as the same type of surface rocks from the LAGF area.
We report here, for the first time for the LAGF and probably for any geothermal system in the world, a comparative geochemical study between a nearly fresh (or lessaltered) rock and its "highly" altered equivalent, both coming from a single core sample of well Az48 at 2,678 m alongthewell depth. Although the study of a single rock sample can not be considered as representative for all rock units present at the LAGF, it is pertinent to note that such a methodology (study of a single rock sample having both "fresh" and "altered" parts) has been highly successful to study the chemical and isotopic effects of lowtemperature seawater alteration in oceanic basalts (Verma, 1981, 1992; Jochum and Verma, 1996). These results on alteration effects have been widely used by other researchers, who have cited these references in their studies of oceanfloor rocks (see e.g., Borisova et al., 2001), oceanisland and islandarc volcanism (e.g., Kersting and Arculus, 1995; Nikolaeva, 1997), ophiolites (e.g., Hatzipanagiotou and Tsikouras, 2001; Srivastava et al., 2004; Tsikouras et al. 2006), hydrothermal alteration (e.g., Kikawada et al., 2001), older Precambrian rocks (e.g., Srivastava and Singh, 2004; Kamber et al., 2003), subduction and recycling processes (e.g., Kamber and Collerson, 2000), and Earth's mantle evolution (e.g., Hofmann and White, 1983; Geist et al. 1986; Ren et al., 2006).
The special rock sample from the LAGF reported in this work, allowed us to observe at mm scale the mineralogical changes caused by hydrothermal alteration and to quantify the chemical changes imposed to this single volcanic rock after alteration. Petrographic studies and geochemical analyses of major, several trace elements including the rareearth elements (REE) and highfield strength elements (HFSE) presented in this study helped us: (1) to describe mineralogical changes that the fresh rock has undergone due to hydrothermal alteration; (2) to study compositional variations of the rock; and (3) to obtain a better understanding of the water/rock interaction processes occurring in this active hydrothermal system.
Los Azufres is one of the several Pleistocene silicic volcanic centers with active geothermal systems in the Mexican Volcanic Belt (MVB; Dobson and Mahood, 1985; Verma, 1985; Anguita et al., 2001). The volcanic rocks at the Los Azufres have been studied by different workers (Cathelineau et al., 1987; Dobson and Mahood, 1985;López Hernández, 1991). Geologically, two principal units can be distinguished (Figure 1): (1) a 2,700 m thick interstratification of lava flows and pyroclastic rocks, of andesitic to basaltic composition with ages between 18 and 1 Ma (Dobson and Mahood, 1985), forming the local basement; and (2) a silicic sequence which partially overlies the mafic unit, characterized by rhyodacites, rhyolites and dacites with ages between 1.0 and 0.15 Ma and a thickness up to 1,000 m. The mafic unit provides the main aquifer with fluid flow through fractures and faults, sometimes reaching the surface in the form of hydrothermal manifestations, accompanied by strong kaolinitization and silicification.
Three different fault systems, which confer secondary permeability to the geological units, can be distinguished (Figure 1; Ferrari et al., 1991): NESW, EW, and NS. The EW system is the most important one for geothermal fluid circulation. Geothermal manifestations (fumaroles, solfataras, and mudpits), geophysical anomalies, as well as important geothermal production zones (the intersection between faults and geothermal wells) are related to this fault system.
The geothermal fluids at the LAGF are sodiumchloride rich waters with high CO2 and H2S contents, and a pH around 7.5 (Birkle et al., 2001). Average Cl contents are 3,100 mg/kg and CO2 can attain as much as 90% of the total gas phase. Fluid temperatures can reach values as high as 320°C; however, 240 to 280°C are normally observed temperatures in the field.
Hydrothermal alteration has affected most rocks in the geothermal field to varying extent. Studies of hydrothermal alteration at the LAGF carried out, among others, by Cathelineau et al. (1985), and TorresAlvarado (2002) have shown that partial to complete hydrothermal metamorphism has occurred. Most important alteration assemblages with increasing depth are: argillitization/silicification, zeolite/calcite formation, sericitization/chloritization, and chloritization/epidotization.
SAMPLING AND ANALYTICAL DETAILS
Sampling and sample preparation
The studied sample was taken from a drill core from well Az48 (coordinates: 100°39'48" W, 19°49'27" N) at 2,678 m depth along drilling direction (Figure 1). It was carefully divided into two pieces avoiding contamination between the highlyaltered portion of the core and the lessaltered rock (Figure 2a). All handpicked pieces were cleaned with distilled water to remove any adhering dust particles, oven dried at about 60°C, and pulverized for geochemical analyses. For petrographic purposes, a standard thin section was carefully prepared to include the contact area between the highlyaltered and the lessaltered portions of the sample, together with the remnant of the original rock enclosed by the altered section (see central bottom part of sample in Figure 2a).
Minerals present in both altered and fresh portions of the rock sample were identified by Xray diffraction. The powdered samples were scanned from 2 to 60° 2θ in a Bruker Xray diffractometer (ModelD8 ADVANCE) with Nifiltered Cu Kα radiation at the Ocean Science and Technology Cell (Marine Geology and Geophysics), Mangalore University, India.
Major elements were analyzed by Xray fluorescence spectrometry (XRF) on duplicate lithium metaborate fused discs, using a Philips MAGIX PRO spectrometer at the Centro de Investigación en Energía, Universidad Nacional Autónoma de México (procedure similar to the one reported by Verma et al., 1992, except that here we explicitly took into account the loss on ignition (LOI) values for the preparation of fused disks so that the final XRF results are obtained on an anhydrous basis). The REE and other trace elements were measured by inductivelycoupled plasma mass spectrometry (ICPMS) at GeoForschungsZentrum Potsdam, Germany (for details about the analytical procedure see Dulski, 2001). For analytical accuracy estimates, the chemical analyses of International Reference Material JR1 (Imai et al., 1995) and the internal standard TUX07 (Verma, 2006) are reported in Table 1. Precisions were better than these accuracy estimates.
RESULTS AND DISCUSSION
The relatively fresh rock sample in hand specimen is an aphanitic volcanic rock, dark gray in color (Fig. 2a). Under the microscope it shows a pilotaxitic to porphyritic texture. Phenocrysts of olivine and pyroxene (probably augite, as reported by TorresAlvarado, 2000, for similar basaltic rocks from the LAGF) are embedded in a matrix of microlitic plagioclase, zircon, apatite, and magnetite, which is mostly altered to hematite. Olivine and pyroxene phenocrysts are totally altered to chlorite and hematite, frequently as pseudomorphs after the primary minerals. Microlitic plagioclase is only partially altered to clay minerals allowing us to estimate, for this sample, a degree of alteration of about 30% (using charts for estimating area % of minerals in thin section; Shelley, 1992). Several chlorite and quartz veins cut the sample, showing thickness between ˜1.0 and ˜0.1 mm. A chlorite vein was observed to be additionally cut by a vein of cryptocrystalline quartz (Figure 2b), providing evidence for the existence of at least two fluid flow events during hydrothermal alteration precipitation.
The highlyaltered section of the sample (altered to nearly 100%) is aphanitic as well, showing a light greenishgray color. Under the microscope, this rock section is built up by banded chlorite, clay minerals, and cryptocrystalline to microcrystalline anhedral quartz. They all may contain anhedral to subhedral epidote crystals and rarely some small amphibole crystals of acicular texture. Opaque minerals (mainly hematite) are also present in the altered sample, although in lesser amounts than in the original one (Figure 2c). Within this highlyaltered sample section, a remnant of the lessaltered rock is present, showing original plagioclase crystals to be totally altered to cryptocrystalline quartz or clay minerals, as well as more abundant hematite in the matrix (comparing its abundance in the lessaltered rock; Figure 2d). Close to the quartz or chlorite veins, the rock shows intense silicification along with dissolution, showing that chlorite and clay minerals contribute to the complete replacement of the original volcanic rock (Figure 2d).
The Xray diffraction analysis supports the petrographic observations. The lessaltered rock sample shows a dominant proportion of plagioclase, followed by quartz and chlorite. Plagioclase is probably of labradoritic composition, as suggested by the predominant peak at 3.18 Å, and supported by plagioclase microprobe analyses (An5278) reported by TorresAlvarado (2000) for similar basaltic rocks from other wells of the LAGF. Epidote, hematite, and amphibole are present in minor quantities. Tremolite is probably the amphibole phase present in the sample, as indicated by its main peak at 8.3 Å, and by the chemical composition reported by TorresAlvarado (2000) for amphibole crystals observed in other wells at the LAGF. On the other hand, the Xray diffraction analysis of the highlyaltered part of the rock sample shows a predominant presence of quartz and, in lower proportions, of Kfeldspars, plagioclase, and amphibole. The hydrothermal plagioclase may have an albitic composition, as suggested by the main peak at 3.14 Å, and microprobe chemical analyses reported for hydrothermal plagioclase (Ab8798) from other areas of the LAGF (TorresAlvarado, 2000). Though the hydrothermal amphibole is present inboth the lessaltered and the highlyaltered portions of the sample, its content is more elevated in the highlyaltered portion.
The actually measured major and trace element abundances for the relatively fresh (482678F) and the highlyaltered (482678A) samples are given in Table 1. According to the TAS classification (Le Bas et al., 1986; Le Bas, 2000), the lessaltered rock shows a basaltic composition.
Major elements show a general decrease in the altered sample compared to the lessaltered rock. Exceptions to this are SiO2, MgO, and MnO, which are important elements incorporated into the highlyaltered rock due to silicification, chloritization, and epidotization, respectively (TorresAlvarado, 2000), in agreement with the importance of these alteration processes in the LAGF (TorresAlvarado, 2002). Loss of alkalis seems to be an important alteration effect for the LAGF as well, as already pointed out by Verma et al. (2005).
Figure 3 shows the differences in the REE chemical compositions between both samples, normalized to the chondritic composition (values from McDonough and Sun, 1995). All REE are present at lower concentrations in the highlyaltered rock compared to the lessaltered one (Table 1, Figure 3). Whereas the original rock shows a smooth, light REEenriched pattern with no Eu anomaly (typical of surface basaltic rocks from the LAGF; Verma et al., 2005), the highlyaltered rock shows lower rock/chondrite concentration ratios for all elements, with a remarkable positive Eu anomaly. For the highlyaltered rock, light REE (LREE), particularly La and Ce, show higher concentration compared to other LREE (Table 1), indicated by a negative slope for the REE pattern in the leftmost section (LREE) of the diagram (Figure 3). Yb and Lu present the opposite behavior, as their normalized concentration ratios are relatively higher than the rest of HREE (Table 1), represented by a positive trend at the rightmost section of the diagram (Fig. 3).
For quantitatively evaluating waterrock interaction processes occurring in the field, it would be interesting in future to measure the actual concentration of these elements in the Los Azufres geothermal fluids and hydrothermal minerals. However, based on the available information for the LAGF, REE were possibly partially leached from the original rock and precipitated again with the hydrothermal alteration in lower concentrations, explaining in this way the generally lower concentrations for all REE, along with the relatively higher concentrations of La and Ce compared to other LREE in the highlyaltered sample. A similar process seems to have occurred for heavy REE (HREE), where Yb and Lu show relatively higher concentrations in the highlyaltered sample. This observation stresses the caution that has to be taken when assuming REE as relatively immobile under hydrothermal conditions and emphasizes the necessity of determining REE concentrations of the geothermal fluids at the LAGF for a better understanding of the alteration processes.
Eu in the highlyaltered sample reaches almost the same concentration as in the fresh rock. This positive Eu anomaly has been also observed in some hydrothermal ore deposits (e.g., Palacios et al., 1986) and in hydrothermal fluids from midocean ridges (e.g., Klinkhammer et al., 1994). Klinkhammer et al. (1994) opined that the partition of REE3+ and Eu2+ is dominated by the chemical substitution for Ca2+ and Sr2+ in plagioclase, respectively, during the transition from Anrich plagioclase to Abrich hydrothermal plagioclase. Furthermore, Palacios et al. (1986) considered epidote as the principal hydrothermal mineral containing REE, and pointed out that its REE concentration is controlled by the REE content in the hydrothermal fluid with probably oxidizing characteristics. Both the previous statements agree with our results, suggesting a predominant role for epidote at the LAGF, allocating REE which have been perhaps mobilized from plagioclase by hydrothermal alteration processes. According to Palacios et al. (1986) this could suggest an oxidizing, REEenriched geothermal fluid, which could be the source for the precipitation of hydrothermal assemblages at the LAGF. Abundant hydrothermal hematite supports this hypothesis. The fact that Eu is not considerably depleted in the highlyaltered rock may indicate that Eu was retained in hydrothermal epidote and albite. However, some other studies have shown that REE mobilization may also take place under reducing conditions (e.g., Parr, 1992; Jiang et al., 2003). The presence of hydrothermal pyrite in other regions of the LAGF reservoir indicates the existence of fluids with relatively low fO2 (TorresAlvarado, 2002). Considering this uncertainty, REE chemical analyses of geothermal fluids and hydrothermal minerals in the LAGF are needed to accept or refuse these hypotheses.
Quantitative estimates of the chemical changes between the lessaltered and the highlyaltered rock samples are presented in Figure 4 (see also Table 1) for all elements analyzed for this work. Only Mg, Ca, Si, Mn, and Pb increased in their concentration in the highlyaltered portion of the rock as a result of hydrothermal effects. Si enrichment of about 50% observed in the highlyaltered rock (as compared to the lessaltered one) reflects the main silicification process that occurred in this sample (see also Figure 2d). Higher Mn concentration in the altered portion of the sample seems to reflect Mn enrichment related to the presence of Mnrich epidotes in the LAGF, as analyzed by TorresAlvarado (2000). Chlorite was observed as the most widespread mineral in the highlyaltered zone of the sample. Its presence in the LAGF agrees with the higher contents of Mg in the highlyaltered sample, because chlorites from the LAGF show variable Mg concentration ranging between Feclinochlore and Mgchamosite (TorresAlvarado, 2000).
Significant losses were observed for most of the analyzed elements (Figure 4). About 75% of the alkalis were removed from the fresh rock by means of hydrothermal alteration. Na loss might be even more significant, considering that it was not possible to chemically quantify this element in the highlyaltered rock because it was found to be under the detection limit of our XRF analytical procedure (˜0.01%; Table 1). Sr and Ba behaved differently than the other alkalineearth elements (Mg and Ca, which are enriched in the highlyaltered rock), and showed decrements of about 30 and 75%, respectively. In the same way, Al and Fe presented a decrease of about 34 and 79%, respectively. As mentioned above, all REE behaved as a relatively consistent group presenting a decrease (from 50 to 83%) in their concentrations, with the exception of Eu whose decrement reached only about 14%. HREE presented the lowest concentration changes within the REE group.
The highest concentration changes were interestingly observed for the highfield strength elements (HFSE), considered to be immobile during hydrothermal alteration process (e.g., Rollinson, 1993). Ti, Nb, Zr, Hf, P, and Th concentrations decreased to about 100%. In fact, Ta concentration in the highlyaltered sample was found to be below the detection limit (~0.04 ppm) of our ICPMS procedure, whereas U decreased to about 80%.
Considering that this volcanic rock was altered in different events, as shown by crossed veins of hydrothermal minerals (Figure 2b), it is likely that the rock reacted with hydrothermal fluids at several occasions and, therefore, the alteration processes, which form this alteration mineral assemblages, may have occurred under rather large water/rock ratios ( > 1). More precise estimates of waterrock ratios will strongly depend on the chemistry of the geothermal fluids. Strong silicification and almost complete replacement of the observed rock remnant (Figure 2d) indicate that fluids had sufficient time to react with this rock. Moreover, the rates of waterrock reactions might have been increased by high temperatures (perhaps higher than 250 °C, as indicated by the presence of hydrothermal epidote and amphibole).
We should emphasize that the hydrothermal alteration conditions observed in this probably unique highly hydrothermallyaltered sample cannot be extrapolated to the rest of the field. The geothermal fluid responsible for the hydrothermal alteration in the LAGF may widely vary in trace element composition, both on spatial and temporal basis (Birkle et al., 2001). However, our study indicates that the geothermal fluid could have, besides the expected high concentrations of the alkalis, significantly high concentrations of all REE and HFSE. Again, specific chemical analyses of geothermal fluids and minerals will help to accept or refuse these hypotheses.
Important chemical losses were observed for P, Ti, and Zr, which have been typically considered as immobile elements. Significant decrease is also observed in the concentrations of Hf andNb. Similar conclusions were recently reached by Verma et al. (2005) by statistically comparing the fresh (outcropping) to the hydrothermallyaltered rhyolitic rocks from the LAGF. Mobilization of HFSE due to hydrothermal alteration has been reported by several authors (e.g. Salvi y WilliamsJones, 1996; Jiang, 2000; Salvi et al., 2000; Jiang et al., 2003). This observation is noteworthy because these elements, especially the HFSE, are widely used for petrogenetic studies; therefore, caution must be exercised for samples which are hydrothermallyaltered, such as in older metamorphic terranes.
A core sample from well As48 at 2,678 m alongdrill well depth allowed us to study, for the first time for the Los Azufres geothermal field, the mineralogical and chemical variations imposed by hydrothermal alteration processes to a basaltic rock sample.
Mineralogically, banded chlorite and quartz built up the highlyaltered part of the rock sample, having significant amounts of epidote, hematite, and calcic amphibole (probably tremolite). The lessaltered rock sample has been partially altered as well (˜30%), mainly by chloritization and hematization of olivine and pyroxene phenocrysts, and partial argillization of plagioclase.
Most major and trace elements were mobilized from the original rock. Silicification, chloritization, and epidotization processes account for the majorelement composition of highlyaltered rock. Most REE, if not all, were probably mobilized by hydrothermal processes. Additionally, La and Ce, as well as Yb und Lu, probably mobilized from the original volcanic rock, were partially redeposited from geothermal fluids during deposition of hydrothermal minerals, as well as during the alteration of the sample. A remarkable positive anomaly of Eu suggests that this element is being concentrated in hydrothermal epidote after being released from plagioclase to the geothermal fluid. Highfield strength elements were mobilized as well during hydrothermal alteration, stressing the necessity of caution using these trace elements for petrogenetic studies of igneous and metamorphic rocks.
The geothermal fluids responsible for this alteration may have been characterized by a high temperature (> 250°C, as evidenced by the presence of hydrothermal epidote and amphibole), oxidizing conditions (as suggested by significant amounts of hematite), and enrichment of both REE and HFSE.
K. Pandarinath and I. S. TorresAlvarado are grateful to DGAPAUNAM forpartial support (projects IN104703 and IN1055023). Thanks are also extended to Mirna Guevera for her help performing the major element analyses. We wish to thank C. Krishnaiah and K.S. Jayappa, of the Ocean Science and Technology Cell (Marine Geology and Geophysics), Mangalore University, India, for XRDlaboratory facility. Constructive reviews by Carles Canet and an anonymous reviewer greatly improved the final version of this manuscript.
Anguita, F., Verma, S.P., Márquez, A., VasconcelosF., M., López, I., Laurrieta, A., 2001, Circular features in the TransMexican Volcanic Belt: Journal of Volcanology and Geothermal Research, 107, 265274. [ Links ]
Birkle, P., Merkel, B., Portugal, E.,TorresAlvarado, I.S., 2001, The origin of reservoir fluids in the geothermal field of Los Azufres, Mexico isotopical and hydrological indications: Applied Geochemistry, 16, 15951610. [ Links ]
Borisova, A.Y., Belyatsky, B.V., Portnyagin, M.V., Sushchevskaya, N.M., 2001, Petrogenesis of olivinephyric basalts from the Aphanasey Nikitin Rise: Evidence for contamination by cratonic lower continental crust: Journal of Petrology, 42, 277319. [ Links ]
Cathelineau, M., Oliver, R., Nieva, D., Garfias, A., 1985, Mineralogy and distribution of hydrothermal mineral zones in Los Azufres (Mexico) geothermal field: Geothermics, 14, 4957. [ Links ]
Cathelineau, M., Oliver, R., Nieva, D., 1987, Geochemistry of volcanic series of the Los Azufres geothermal field (Mexico): Geofísica Internacional, 26, 273290. [ Links ]
Cathelineau, M., Izquierdo, G., Vázquez, G.R., Guevara, M., 1991, Deep geothermal wells in the Los Azufes (Mexico) caldera; volcanic basement stratigraphy based on majorelement analysis: Journal of Volcanology and Geothermal Research, 47, 149159. [ Links ]
Dobson, P.F., Mahood, G. A., 1985, Volcanic stratigraphy of the Los Azufres geothermal area, Mexico: Journal of Volcanology and Geothermal Research, 25, 273287. [ Links ]
Dulski, P., 2001, Reference materials for geochemical studies; New analytical data by ICPMS and critical discussion of reference values: Geostandards Newsletter, The Journal of Geostandards and Geoanalysis, 25, 87125. [ Links ]
Ferrari, L., Garduño, V.H., Pasquarè, G., Tibaldi, A., 1991, Geology of Los Azufres caldera, Mexico, and its relationships with regional tectonics: Journal of Volcanology and Geothermal Research, 47, 129148. [ Links ]
Geist, D.J., White W.M., McBirney, A.R., 1986, Plumeasthenosphere mixing beneath the Galapagos Archipelago: Nature, 333, 657660. [ Links ]
GutiérrezNegrín, L.C. A., QuijanoLeón, J.L., 2005, Update of Geothermics in Mexico, in World Geothermal Congress, Antalya, Turkey: International Geothermal Association, 10 pp. [ Links ]
Hatzipanagiotou, K., Tsikouras, B., 2001, Rodingite formation from diorite in the Samothraki ophiolite, NE Aegean, Greece: Geological Journal, 36, 93109. [ Links ]
Hofmann, A. W., White, W.M., 1983, Ba, Rb and Cs in the Earth's mantle: Zeitschrift für Naturforschung, 38A, 256166. [ Links ]
Imai, N., Terashima, S., Itoh, S., Ando, A., 1995, 1994 Compilation of analytical data for minor and trace elements in seventeen GS J geochemical reference samples, "igneous rock series": Geostandards Newsletter, 19, 135213. [ Links ]
Jiang, S.Y., 2000, Controls on the mobility of high field strength elements (HFSE), U, and Th in an ancient submarine hydrothermal system of the Proterozoic Sullivan PbZnAg deposit, British Columbia, Canada: Geochemical Journal, 34, 341348. [ Links ]
Jiang, N., Sun, S., Chu, X., Mizuta, T., Ishiyama, D., 2003, Mobilization and enrichment of highfield strength elements during late and postmagmatic processes in the Shuiquangou syenitic complex, Northern China: Chemical Geology, 200, 117128. [ Links ]
Jochum, K.P., Verma, S. P., 1996, Extremely high enrichment of Sb, Tl and other trace elements in altered MORB: Chemical Geology, 130, 289299. [ Links ]
Kamber, B.S., Collerson, K.D., 2000, Role of 'hidden' deeply subducted slabs in mantle depletion: Chemical Geology, 166, 241254. [ Links ]
Kamber, B.S., Collerson, K.D., Moorbath, S., Whitehouse, M.J., 2003, Inheritance of early Archaean Pbisotope variability from longlived Hadean protocrust: Contributions to Mineralogy and Petrology, 145, 2546. [ Links ]
Kersting, A.B., Arculus, R. J., 1995, Pb isotope composition of Klyuchevskoy volcano, Kamchatka and North Pacific sediments; Implications for magma genesis and crustal recycling in the Kamchatka arc: Earth and Planetary Science Letters, 136, 133148. [ Links ]
Kikawada, Y., Ossaka, T., Oi, T., Honda, T., 2001, Experimental studies on the mobility of lanthanides accompanying alteration of andesite by acidic hot spring water: Chemical Geology, 176, 137149. [ Links ]
Klinkhammer, G.P., Elderfield, H., Edmond, J.M., Mitra, A., 1994, Geochemical implications of rare earth element patterns in hydrothermal fluids from midocean ridges: Geochemica et Cosmochemica Acta, 58, 51055113. [ Links ]
Le Bas, M. J., 2000, IUGS reclassification of the highMg and picritic volcanic rocks: Journal of Petrology, 41, 14671470. [ Links ]
Le Bas, M. J., Le Maitre, R. W., Streckeisen, A., Zanettin, B., 1986, A chemical classification of volcanic rocks based on the total alkalisilica diagram: Journal of Petrology, 27, 745750. [ Links ]
López Hernández A., 1991, Geología de Los Azufres: Geotermia, Revista Mexicana de Geoenergía, 7, 265275. [ Links ]
McDonough, W.F., Sun, S.s., 1995, The composition of the Earth: Chemical Geology, 120, 223253. [ Links ]
Middlemost, E.A.K., 1989, Iron oxidation ratios, norms and the classification of volcanic rocks: Chemical Geology 77, 1926. [ Links ]
Nikolaeva, O.V., 1997, KUTh systematics of igneous rocks for planetological comparisons; Oceanic islandarc volcanics on Earth versus rocks on the surface of Venus: Geokhimiya, 5, 488512. [ Links ]
Palacios, C.M., Hein, U.F., Dulski, P., 1986, Behavior of rare earth elements during hydrothermal alteration at the Buena Esperanza coppersilver deposit, northern Chile: Earth and Planetary Science Letters, 80, 208216. [ Links ]
Pandarinath, K., TorresAlvarado, I.S., Pushparani, D.E., Verma, S.P., 2006, XRay diffraction analysis of hydrothermal minerals from the Los Azufres geothermal system, Mexico: International Geology Review, 48, 174190. [ Links ]
Parr, J.M., 1992, Rareearth element distribution in exhalites associated with Broken Hillstype mineralization at the Pinnacles deposit, New South Wales, Australia: Chemical Geology, 100, 7391. [ Links ]
Pradal, E., Robin, C., 1994, Longlived magmatic phases at Los Azufres volcanic center, Mexico: Journal of Volcanology and Geothermal Research, 63, 201215. [ Links ]
Ren, Z.Y., Shibata, T., Yoshikawa, M., Johnson, K.T.M., Takahashi, E., 2006, Isotope compositions of submarine Hana Ridge lavas, Haleakala volcano, Hawaii; Implications for source compositions, melting process and the structure of the Hawaiian plume: Journal of Petrology, 47, 255275. [ Links ]
Rollinson, H., 1993, Using geochemical data; Evaluation, presentation, interpretation: Harlow, England, Longman Scientific & Technical, 352 pp. [ Links ]
Salvi, S., WilliamsJones, A.E., 1996, The role of hydrothermal processes in concentrating highfield strength elements in the Strange Lake peralkaline complex, northeastern Canada: Geochimica et Cosmochimica Acta, 60, 19171932. [ Links ]
Salvi, S., Fontan, F., Monchoux, P., WilliamsJones, A.E., Moine, B., 2000, Hydrothermal mobilization of high field strength elements in alkaline igneous systems: Evidence from the Tamazeght Complex (Morocco): Economic Geology, 95, 559576. [ Links ]
Shelley, D., 1992, Igneous and metamorphic rocks under the microscope. Chapman and Hall, 445 pp. [ Links ]
Srivastava, R.K., Singh, R.K., 2004, Trace element geochemistry and genesis of Precambrian subalkaline mafic dykes from central India craton: evidence for mantle metasomatism: Journal of Asian Earth Sciences, 23, 373389. [ Links ]
Srivastava, R.K., Chandra, R., Shastry, A., 2004, HighTi type NMORB parentage of basalts from the south Andaman ophiolite suite, India: Proceedings of Indian Academy of Sciences (Earth and Planetray Sciences), 113, 605618. [ Links ]
TorresAlvarado, I.S., 2000, Mineral chemistry of hydrothermal silicates in Los Azufres geothermal field, Mexico, in World Geothermal Congress, KyushuTohoku, Japan, Proceedings: International Geothermal Association, 18611866. [ Links ]
TorresAlvarado, I.S., 2002, Chemical equilibrium in hydrothermal systems; the case of Los Azufres geothermal field, Mexico: International Geology Review, 44, 639652. [ Links ]
TorresAlvarado, I. S., Satir, M., 1998, Geochemistry of hydrothermally altered rocks from Los Azufres geothermal field, Mexico: Geofísica Internacional, 37, 201213. [ Links ]
Tsikouras, B., Karipi, S., Grammatikopoulos, T.A., Hatzipanagiotou, K., 2006, Listwaenite evolution in the ophiolite melange of Iti Mountain (continental Central Greece): European Journal of Mineralogy, 18, 243255. [ Links ]
Verma, S.P., 1981, Sea water alteration effects on 87Sr/86Sr, K, Rb, Cs, Ba, and Sr in oceanic igneous rocks: Chemical Geology, 34, 8189. [ Links ]
Verma, S.P., 1985, On the magma chamber characteristics as inferred from surface geology and geochemistry; examples from Mexican geothermal areas: Physics of the Earth and Planetary Interiors, 41, 207214. [ Links ]
Verma, S.P., 1992, Seawater alteration effects on REE, K, Rb, Cs, Sr, U, Th, Pb and SrNdPb isotope systematics in MidOcean Ridge Basalt: Geochemical Journal, 26, 159177. [ Links ]
Verma, S.P., 2006, Extensionrelated origin of magmas from a garnetbearing source in the Los Tuxtlas volcanic field, Mexico: International Journal of Earth Sciences (Geologische Rundschau),95,5, 971901. [ Links ]
Verma, S.P., Besch, T., Guevara, M., SchulzDobrich, B., 1992, Determination of twelve trace elements in twentyseven and ten major elements in twentythree geochemical reference samples by XRay fluorescence spectrometry: Geostandards Newsletter, The Journal of Geostandards and Geoanalysis, 16, 301309. [ Links ]
Verma, S.P., TorresAlvarado, I.S., SoteloRodríguez, Z.T., 2002, SINCLAS: standard igneous norm and volcanic rock classification system: Computer and Geosciences, 28, 711715. [ Links ]
Verma, S.P., TorresAlvarado, I.S., Satir, M., Dobson, P., 2005, Hydrothermal alteration effects in geochemistry and Sr, Nd, Pb, and O isotopes of magmas from Los Azufres geothermal field, Mexico: A statistical approach: Geochemical Journal, 39, 141163. [ Links ]