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Home , Mena (Mercurian crater), Nevado de Toluca, Oriental Basin, Popocatepetl, Volcanic crater lake

Journal of Volcanology and Geothermal Research 97 (2000) 105–125 www.elsevier.nl/locate/volgeores

Chemical characteristics of the crater of Popocatetetl, El Chichon, and Nevado de volcanoes,

M.A. Armienta*, S. De la Cruz-Reyna, J.L. Macı´as

Instituto de Geofı`sica, Cuidad Universitaria CA, Delegacion de Coyoacan, UNAM, C.U., Mexico DF 04510 Codigo, Mexico

Abstract Three crater lakes from Mexican volcanoes were sampled and analyzed at various dates to determine their chemical characteristics. Strong differences were observed in the chemistry among the three lakes: , considered as dormant, El Chicho´n at a post-eruptive stage, and Popocate´petl at a pre-eruptive stage. Not surprisingly, no influence of volcanic activity was found at the Nevado de Toluca , while the other volcanoes showed a correlation between the changing level of activity and the evolution of chemical trends. Low pHs (Ͻ3.0) were measured in the water from the active volcanoes, while a pH of 5.6 was measured at the Nevado de Toluca Sun . Changes with time were observed at Popocate´petl Ϫ 2Ϫ Ϫ and El Chicho´n. Concentrations of volcanic-gas derived species like Cl ,SO4 and F decreased irregularly at El Chicho´n 2Ϫ from 1983 until 1997. Major cations concentrations also diminished at El Chicho´n. A 100% increase in the SO4 content was measured at Popocate´petl between 1985 and 1994. An increase in the Mg/Cl ratio between 1992 Mg=Cl ˆ 0:085† and 1994 Mg=Cl ˆ 0:177† was observed at Popocate´petl, before the disappearance of the in 1994. It is concluded that chemical analysis of crater lakes may provide a useful additional tool for active-volcano monitoring. ᭧ 2000 Elsevier Science B.V. All rights reserved.

Keywords: Mexican volcanoes; crater lakes; Popocate´petl; El Chicho´n; Nevado de Toluca; volcano monitoring

1. Introduction believed to result from the varying-angle subduction of the and Cocos plates under the North Holocene volcanism in Mexico is varied and wide- American plate. Volcanism, in the southeast of Me´xico spread. In the northwest of the country, recent vol- is parallel to the trench marking the subduction of the canoes are associated with the spreading process Cocos plate under the Caribbean plate (Fig. 1). that is currently opening the Gulf of Corte´s, or due Thousands of volcanic structures have been formed to remnants of the subduction of the Farallon plate. by these processes. Of those, only a few have crater The show some acid volcanism lakes. Three main types of crater lake may be recog- whose origin is difficult to explain. Most of the recent nized: those associated with Xalapasco or , inac- volcanism occurs along the Trans-Mexican Volcanic tive or long-time dormant volcanoes, and currently Belt (TMVB), which has an oblique position with active . In this paper, chemical analyses of respect to the trench in the Pacific coast that is one lake of a dormant volcano and two of active volcanoes are discussed to relate the measured chem- ical features with their state of activity. The dormant * Corresponding author. Tel.: 525-622-4114; fax: 525-550-2486. E-mail address: @tonatiuh.igeofcu.unam.mx lake is located at the summit of (M.A. Armienta). Nevado de Toluca volcano. The other lakes discussed

0377-0273/00/$ - see front matter ᭧ 2000 Elsevier Science B.V. All rights reserved. PII: S0377-0273(99)00157-2 106 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 are at Popocate´petl and El Chicho´n, which were vol- built upon the remains of older, destroyed craters, due canoes in a pre-eruptive and a post-eruptive stage, to repetitive sector collapse of the edifice. At least respectively, at the time of this study. three sector collapses of the volcanic edifice have been reported of which the most recent one occurred between 24,000 and 22,000 years ago (Siebe et al., 2. Geological setting and volcanic history 1995). Several geological studies of the volcano have dealt mainly with the geological record of the present 2.1. Popocate´petl Volcano (19ЊN; 99ЊW; cone ( and Heide-Weise 1973; Lambert and 5426 m.a.s.l.) Valastro, 1976; Boudal, 1984; Miehlich, 1984; Robin, 1984; Boudal and Robin, 1989; Siebe et al., Popocate´petl Volcano is located 60 km southeast of 1995; Siebe et al., 1996). and 40 km west of the City of . According to Siebe et al. (1997), Popocate´petl The construction of the andesitic–dacitic stratovol- Volcano has had intense volcanic activity during the cano started around 1 Myr ago (Demant, 1981; last 23,000 years, with at least eight cataclysmic erup- Robin and Boudal, 1987). The volcano is sitting tions dated at ca. 14,000, 10,700, 9100, 7100, 5000, upon a Mesozoic basement of limestone, evaporites, 2150, 1700, and 1200 yr. BP. The last four eruptions and sandstones of Cretaceous age. have largely influenced the development of prehispa- Popocate´petl Volcano has a central elongated crater nic cultures in this part of central Mexico. In addition, with an approximated dimension of 820 × 650 m and important historic activity has been observed at the 100–300 m deep walls. Prior to its eruption on volcano since prehispanic times (De la Cruz-Reyna December 21, 1994, it contained an internal crater et al., 1995). on its crater floor formed after its last historic activity In the 20th century, Popocate´petl has had two that occurred between 1919 and 1927. The northern similar episodes of activity. The first one from 1919 flank of the volcano is covered by a of about to 1927 and the current one, which began with an 0.05 km3. increase in the fumarolic emissions in 1993, and The present cone of Popocate´petl volcano has been was followed by ash emissions in 1995 and dome

Fig. 1. Map of Me´xico showing the Trans-Mexican (TMVB), the Volcanic Arc (CVA) and the Central-America Volcanic Arc (CAVA). Open triangles indicate Holocene volcanoes. (1) Ceboruco, (2) Colima, (3)Paricutı´n, (4) Jocotitla´n, (5) , (6) San Martı´n and (7),Tacana´.MCˆ Me´xico City. M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 107 growth that continues up to date. Currently, over one El Chicho´n as potentially active. After the 1982 erup- hundred thousand people live in an area that could be tion, Duffield et al. (1984) analyzed drilled logs directly affected in the event of a major eruption, and obtained from nearby exploration boreholes by nearly 20 million live within a radius of 80 km, where PEMEX (the national oil company) and established they may be affected by significant ash fall (De la the geological setting of El Chicho´n. Regarding its Cruz-Reyna and Siebe, 1997). volcanic history, Rose et al. (1984) and Tilling et al. Between the 1919–1927 and the 1993 episodes, a (1984) found at least three periods of volcanic activity seasonal crater lake formed at the floor of Popocate´- during the last 2000 years. Recent stratigraphic petl’s crater. The presence of that lake was reported in studies suggest that El Chicho´n volcano has had at 1986 (SEAN Bulletin, 1986). This report describes a least 10 episodes of explosive volcanic activity small, clear, greenish, roughly circular lake, about which occurred at ca. 550, 850, 1250, 1400, 1700, 40 m in diameter and 10 m deep, with a temperature 1800, 2000, 2400, 3100 and 3700 yr. BP (Macı´as et of 29ЊC. Increased fumarolic activity caused the total al., 1997a). evaporation of the crater lake in 1994. The most recent eruption of El Chicho´n developed as an episode having six pulses during the week 28 0 0 2.2. El Chicho´n Volcano (17 Њ21 N; 93Њ41 W; –4 April, 1982. This episode had a relatively ϳ 3 1100 m.a.s.l.) low magnitude (juvenile mass ejected 0.3 km DRE) and a high intensity (maximum mass ejection El Chicho´n is an isolated volcano located in the rate ϳ105 ton/s,Yokoyama et al., 1982). The effects of northwestern edge of the state of Chiapas, in the these eruptions were disastrous, causing an almost middle of sedimentary province. It is the youngest total devastation in a radius 10 km around the active volcano SE–NW of Chiapas Volcanic Arc volcano. About 2000 people were killed by pyroclas- (Damon and Montesinos, 1978). El Chicho´n is located tic flows and tephra falls, and about 20,000 lost their in the Chiapas anticlinorium, which dips towards the homes. Ashfalls extended over several hundred kilo- Gulf of Mexico with direction NW–SE and is buried meters and rain-triggered produced additional by Post-Miocene sediments in the coastal plains damage weeks after the end of the eruption. (Macı´as et al., 1997a). The basement rocks of the On April 25, 1982, the first views of the crater floor volcano are early Cretaceous evaporites and lime- after the 1982 eruption showed three small lakes. By stones, dolomitic limestones of Middle to Late- November 1982, the level of the water rose forming Cretaceous age, with interbedding of epiclastic one bigger lake with a surface area of 1:4 × 105 m2 sandstones and limestones of Tertiary age. General (Casadevall et al., 1984). In January 1997, the area geological features of the volcano can be found else- had decreased to approximately 0:5 × 105 m2: where (Canul and Rocha, 1981; Duffield et al., 1984). Variations in the level and shape of the lake have El Chicho´n volcano has an older somma rim with been observed since its appearance, as shown in dimensions of 1:5 × 2 km that before the eruption was Figs. 2 and 3. closed by a forest-covered dome. The crater produced 0 0 by the 1982 eruptions lies within the . 2.3. Nevado de Toluca Volcano (19Њ09 N; 99Њ45 W; This crater is 1 km wide and about 200 m deep. The 4565 m.a.s.l.) highest elevation of the crater is at 1100 m.a.s.l. with its floor placed at 860 m.a.s.l. Nevado de Toluca volcano is located at 23 km SW Before the 1982 eruption, little was known about of the City of Toluca, it is an andesitic–dacitic the volcano and its eruptive history. Mu¨lleried (1932) of Late Pleistocene age (Bloomfield studied the region after some seismic unrest was and Valastro, 1974; Cantagrel et al., 1981). Nevado reported, and concluded that El Chicho´n was an active de Toluca is built upon a volcanosedimentary basement volcano. Damon and Montesinos (1978), dated the of Jurassic–Tertiary age, which has been affected by a somma crater at 0:209 ^ 0:019 Ma Canul and Rocha complex set of three fault systems (Garcı´a et al., (1981) while doing fieldwork for Comisio´n Federal de 1996). Electricidad (The National Power Bureau) identified The crater has an E–W-elongated form (1–1.5 km 108 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Fig. 2. Views of El Chicho´n crater lake from the southeastern rim. (A) August, 1985 (photo – S. De la Cruz-Reyna). Notice the intense fumarolic activity and sulfur sublimates. (B) January 1997 (photo – J.L. Macı´as). Arrows point to the sampling site. in diameter) with a horseshoe-shaped opening during the Holocene also affected the volcano’s towards the east. The oval central crater is emplaced morphology (Heine, 1988). on top of two older amphitheater-shaped craters The first studies of Nevado de Toluca described whose remains are still visible on the SE and NE general geological features of the volcano (Ordon˜ez, flanks of the volcano. Glacial advances occurring 1902; Otis, 1902; , 1906; Waitz, 1909). M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 109

Fig. 3. Aerial views towards the northeast of El Chicho´n crater. (A) November, 1982. The lake area is about 1:4 × 105 m2: The thick arrow shows the 1982 crater, and the thin arrow points to the somma crater. (B) September, 1986 (approximate lake area ˆ 0:5 × 105 m2†:

Bloomfield and Valastro (1974,1977) and Bloomfield BP, and for this reason Nevado de Toluca had been et al. (1977) attempted for the first time to define the considered an extinct volcano. Recent studies, indicate volcanic events that occurred at Nevado de Toluca, as that Nevado de Toluca has had at least two episodes of well as its eruptive history. These authors concluded cone destruction by major sector collapse older than that the last cycle of activity occurred about 11,500 yr. 40,000 yr. BP; several explosive episodes including 110 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Fig. 4. Aerial photograph of Nevado de Toluca crater (INEGI, 1989). Simbols are: SL ˆ Lago del Sol, ML ˆ Lago de la Luna, and DD ˆ Dacitic Dome “El Ombligo”. The black line represents the present crater rim. dome-destruction events at ca. 37,000 and 28,000 yr. Two lakes lie inside the crater “Lago de la BP; and two plinian eruptions recorded at 24,000 and Luna” and “Lago del Sol” which are separ- 11,600 yr. BP. These eruptions occurred during the ated by two dacitic dome intrusions (Fig. 4). Pleistocene but a young eruption characterized by Although their morphology changes with time, surge and ash flows occurred ca. 3300 yr. BP, and there- their areas are approximately 0.025 km2 and fore Nevado de Toluca should be considered as dormant about 0.175 km2, respectively (Caballero-Miranda, (Macı´as et al., 1997b). 1996). M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 111 3. Methodology 4. Results

Water samples were taken from the crater lakes at Large differences were observed in the chemical different dates, depending upon accessibility to the composition of the three crater lakes. In order to areas. At El Chicho´n, water sampling began in 1985 emphasize the relevant differences and their time and continued with an irregular periodicity until 1997. evolution, the results are presented comparatively. Two samples from Popocate´petl Lake were taken in 1985 and in April, 1992. Finally, a sample from 4.1. Nevado de Toluca Nevado de Toluca was obtained in August, 1997. The Nevado de Toluca crater lake showed stability Temperature and pH were measured in the field. pH when compared with a previous sample obtained by was determined potentiometrically, the pH-meter Caballero-Miranda (1996) in 1991. It presented a very calibration was made with buffer solutions submerged low conductivity (18 mS/cm), and pH ˆ 5:6 (Fig. 5). in the lake to allow equilibrium with the water In August, 1997 the temperature in the crater lake temperature. Water was directly poured in poly- water of Nevado de Toluca was 11.7ЊC. Nevado de ethylene bottles. One liter was used for the determin- Ϫ Ϫ Toluca water type was mixed in anions and calcium– ation of alkalinity, conductivity, Cl ,F , SiO2, B and 2Ϫ: magnesium in cations. Lithium, boron and fluoride SO4 Another 500-ml aliquot of water was added to Ϫ 2Ϫ were below the detection limits. Cl and SO4 1 ml of concentrated HNO and used for the analyses Ϫ 3 concentrations were also very low (Cl ˆ 1:5mg=l; of metals. Finally, a 125-ml aliquot with Na CO and Ϫ 2 3 SO2 ˆ 3:3mg=l†: zinc acetate added, was also taken for sulfide deter- 4 Њ minations. All the bottles were refrigerated at 4 C 4.2. El Chicho´n and Popocate´petl after sampling. Chemical analyses were performed by wet Regarding acidity, conductivity and temperature, methods, basically following the procedures El Chicho´n crater lake water showed an increasing described in APHA (1989). Bicarbonates were pH from 1983 to 1986. Conductivity varied in the measured by acid titration to pH 4.6, using a mixed opposite direction. Dark and light triangles in Fig. 5 indicator of methyl red and bromcresol green. Iron show those trends. Water temperatures varied from concentration was measured by colorimetry using 56ЊC in 1983 to 35.4ЊC in 1997. the phenantroline method until 1990. After that year, Popocate´petl crater lake water did not change its Fe was determined by atomic absorption spectro- acidity much in the pre-eruptive phase, and the pH scopy. Sulfates were determined by turbidimetry. measured values were never as low as the immediate Magnesium and calcium concentrations were post-eruptive phase of El Chicho´n, but the conductiv- obtained by complexometric titration with EDTA. ity of Popocate´petl water was 123,700 mS/cm in April Boron was colorimetrically measured through its 1992, higher than any measured value at El Chicho´n. reaction with carminic acid. Chloride was potentio- Water temperature at Popocatepetl lake increased metrically determined with an ion-selective elec- from 29ЊC in January 1986 (SEAN, 1986) to 65ЊC trode, adding a 5 M solution of NaNO3 as ionic in 1994 (Smithsonian Institution, 1994). strength adjuster. Fluoride concentrations were Water-type evolved differently in both crater lakes: determined also with an ion selective electrode, from analyses of Casadevall et al. (1984) the El adding a TISAB solution for decomplexing and Chicho´n water can be classified as acid, calcium- adjusting the ionic strength. Sodium, potassium chloride in 1983, and in 1997, it was acid, sodium- and lithium were measured by atomic emission chloride type. spectroscopy. Silica and sulfide were colorimetri- Popocate´petl water was magnesium-sodium- cally determined; using the molibdosilicate chloride-sulfate in 1985, and acid, magnesium- method for the former, and the methyl blue reac- chloride-sulfate in 1994 as may be inferred from the tion for the latter. Detection limits were as analyses of Werner et al. (1997). Fig. 6 shows these ˆ : = ; ˆ : = Ϫ ˆ follows: B 0 5mgl SiO2 2 5mgl, F types along with water types of other crater lakes Ϫ 0:05 mg=l; S2 ˆ 0:5mg=l, Li ˆ 0:05 mg=l: around the world. 112 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Fig. 5. Conductivity (light symbols) and pH (dark symbols) values of El Chicho´n, Popocate´petl, and Nevado de Toluca crater lakes at different dates. The 1983 conductivity was calculated from TDS vs. conductivity trends.

2Ϫ Ϫ The major anions SO4 and Cl varied over time at 23,660 mg/l in 1994). The magnesium content at El Chicho´n and at Popocate´petl (Table 1). Popocate´petl diminished slightly between 1985 and A decreasing trend with time was observed for 1992, but increased above 100% between 1992 and sulfate and chloride concentrations at El Chicho´n 1994 (1239 mg/l in 1992, and 2520 mg/l in 1994) (Fig. 7). The chloride concentration decreased from (Fig. 8). Iron also increased from 2550 mg/l in 1992 24,030 mg/l in 1983 to 3740 mg/l in 1997. The sulfate to 3770 mg/l in 1994 (Table 1). content diminished from 3550 mg/l in 1983 to At El Chicho´n, boron diminished irregularly from 469 mg/l in 1997. Rock derived elements like Ca, 433 mg/l in 1983 to 37 mg/l in 1997. Lithium showed Mg and Fe also showed a decreasing trend at El a decreasing trend until 1992 (0.76 mg/l in 1983 to Chicho´n. 0.28 mg/l in August 1992), but increased in May 1995 At Popocate´petl an increase in chloride was to 1.64 mg/l, and has been keeping high values since. observed between 1985 and 1994 (from 12,400 mg/l Fluoride increased between 1983 and 1985 (0.16 mg/l to 14,200 mg/l), and a greater increase was detected in in 1983 to 4.5 mg/l in 1985), decreasing afterwards up the sulfate content (from 11,100 mg/l in 1985 to to less than 0.05 mg/l in January, 1997 (Table 1).

Fig. 6. Triangular diagrams of (A) cations and (B) anions. The numbers correspond to: (1) Sirung Lake, 1984 (Poorter et al., 1989); (2) Anak Krakatau, 1933 (Poorter et al., 1989); (3) Soufrie`re, 1971 (Sigurdsson, 1977); (4) Albano (Martini et al., 1994); (5) (Martini et al., 1994); (6) Poa´s, 1987 (Rowe et al., 1992); (7) Ruapehu, 1988 (Christenson and Wood, 1993); (8) Kawah 1964 (Delmelle and Bernard, 1994); (9) Yugama, 1992 (Ohba et al., 1994); and (10) Kusatsu-Shirane, 1976 (Ossaka et al., 1980). (Pa) Chicho´n, January, 1983. (Casadevall et al., 1984). (Pb) Chicho´n, January, 1993. (Pc) Chicho´n, January, 1997. (Bd) Popocate´petl, November, 1985. (Be) Popocate´petl, April, 1992. (Bf) Popocate´petl February, 1994 (Werner et al., 1997). (V) Nevado de Toluca, August, 1997. M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 113 114 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 Al 2 2.52.5 – – Ͻ Ͻ 0.5 – – Ͻ 0.050.05 50 37 5.50 3.5 22 12 251 212 – 4.40 0.05 – – – Ͻ Ͻ Ͻ 0.5 – Ͻ 1.0 Ͻ 0.8 3.9 Ͻ 1.0 Ͻ Cl Ca Mg Na K F B Li Fe SiO 4 SO 3 CO n and Nevado de Toluca Crater Lakes (concentrations in mg/l) ´ 3 petl, El Chicho S/cm) HCO ´ m (

L C) Њ ( T Ͼ 1.5 650.56 56 – 83,800 0 0 0 0 23,660 3550 14,200 24,030 781 21105.90 2520 7 424 1835 607 329 24.6 232 11.5 12.2 0 0.16 54 433 3.31 0.76 3770 – 914 295 257 2210 745 n a petl b c ´ ´ Werner et al., 1997. Casadevall et al., 1984. Caballero-Miranda, 1996. a c b Nov 1985Apr 1992 –Feb 1994 1.37 – – 12,3700 – 0 0 0 17,000 0 14,500 11,100 997 12,400 1239 1020 3438 1347 2280 575 141 0.48 73 2.12 – 38 – 2550 – – – – – Popocate Jan 1983 Date pH El Chicho May 1985Aug 1985 1.74Nov 1985 1.48 –Sep 1986 1.24 –Nov 1991 29.5 2.33May 23,560 1992 2.46 –Aug 16,500 1992 2.15 – 5650Jan 1993 32.1 2.20 0May 1995 0 – 2.29 3358Mar 41,100 0 1996 2.15 0 30.7 3320Jan 1997 33 2.87 0 26,650 0 0 28.3 0 46,400Nevado 2.10 de Toluca 0 345Jan 35.4 1991 25,850 6640 0 0 0 554 0 170 0 10,450 4338 0 0 0 0 1577 818 1368 6092 420 0 484 0 0 1368 12,250 243 9200 684 390 293 0 2517 2019 320 637 110 13,200 529 671 6900 – 317 775 200 469 2660 92 1590 – 4220 3400 986 – 363 3740 217 – – 22 691 670 228 – 1325 3000 502 2.00 100 114 – 4.50 210 0.52 38 410 2.93 – 106 176 1839 23 165 – 1189 460 0.16 0.18 – 0.68 262 0.36 0.46 190 188 210 0.37 115 184 108 0.17 146 – – 330 248 248 0.28 5 – – 273 450 17.7 0.14 15.2 – – 146 550 10 13.3 250 – – –- 1.64 71 – 1.02 23 – – 111 13.11 Table 1 Chemical composition of Popocate Aug 1997 5.59 11.7 18.0 2.3 0 3.3 1.5 1.6 0.7 0.6 0.5 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 115

Ϫ 2Ϫ Fig. 7. Cl (light symbols) and SO4 (dark symbols) concentrations (mg/l) at El Chicho´n, Popocate´petl and Nevado de Toluca crater lakes against time.

Fig. 8. Ca (dark symbols) and Mg (light symbols) concentrations (mg/l) at El Chicho´n, Popocate´petl and Nevado de Toluca crater lakes on various dates. 116 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Fig. 9. Logarithm of Saturation Indexes (LSI) of quartz, gypsum, anhydrite, goethite, halite and thenardite at El Chicho´n (dark symbols) and Popocate´petl (light symbols) crater lakes against time.

At Popocate´petl, the boron concentration varied Ϫ3:69† and in 1994 LSI ˆ Ϫ4:44†: Gypsum precipi- from 38 mg/l in 1985 to 73 mg/l in 1992, and to tation at Popocate´petl was evidenced by its presence 54 mg/l in 1994. Fluoride increased almost 30 fold in the non-juvenile ashes erupted in 1994 and early between 1992 and 1994 (0.48 mg/l in 1992 to 1995 (Martin-del Pozzo et al., 1995). The precipi- 11.5 mg/l in 1994) (Table 1). tation of anhydrite, gypsum and goethite at El The geochemical modeling programs Wateq4f Chicho´n was predicted by Casadevall et al. (1984). (Ball and Nordstrom, 1991) and Minteqa2 (1991) Nevertheless, no studies have been made on the sedi- were used for calculating saturation indices and ment of the crater lake that may reveal the actual predominance of species. The results obtained at El formation of those minerals at El Chicho´n. Chicho´n since 1983 and at Popocate´petl in 1992 and Differences in the predominance of species were 1994 are shown in Fig. 9. observed between 1983 and 1997 at El Chicho´n Oversaturation of quartz was determined for all the (Table 2). The most important change occurred in 2Ϫ samples at El Chicho´n and Popocate´petl. A logarithm the sulfate distribution. In 1983 SO4 was present Ϫ; of saturation index (LSI) of goethite greater than 0.9 mainly as HSO4 while in 1997 the higher percen- 2Ϫ Ϫ: was calculated for all the El Chicho´n samples except tage was SO4 followed by HSO4 for the first one in 1983. El Chicho´n lake was satu- At Popocate´petl the geochemical modeling, made rated with anhydrite in 1983, and undersaturated, without the input of the Al concentration, showed an Ϫ though near saturation with anydrite and gypsum increase on the percentage of HSO4 and a decrease of 2Ϫ since 1986. Anhydrite and gypsum were around the SO4 in 1994 with respect to 1992 (Table 3). On the saturation values for the 1992 and 1994 Popocate´petl other hand, if the Al concentration (2210 mg/l) samples. At El Chicho´n, thenardite had a lower LSI in reported by Werner et al. (1997) is introduced in the 1983 (Ϫ6.71) than in 1997 (Ϫ5.69). Popocate´petl lake input file, stronger differences in the species distri- ˆ 2Ϫ showed undersaturation of thenardite in 1992 LSI bution of SO4 are obtained between 1992 and M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 117

2Ϫ Table 2 1994. The complexing of Al with SO4 reduces even Percentage distribution of components among species at El Chicho´n 2Ϫ: 2ϩ more the percentage of sulfate as SO4 Finally, Ca crater lake and Mg2ϩ distributions increased their percentages as Component Species Percentage (1983) Percentage (1997) free ions in 1994 with respect to 1992. The chemical geothermometers developed by Four- 2Ϫ 2Ϫ SO4 SO4 4.0 52.0 nier and Truesdell (1973), Fouillac and Michard CaSO aq 2.7 14.5 4 (1981) and Fournier and Potter (1982), were applied MgSO4 aq 4.4 NaSO4 4.7 for the El Chicho´n and Popocate´petl lakes. The results Ϫ HSO4 91.3 23.4 are shown in Table 4. The Na/Li vs T equation for Ϫ H4SiO4 H4SiO4 100 100 Cl Ͻ 0:2 M was used for the 1997 El Chicho´n H3BO3 H3BO3 100 100 Ϫ ϩ ϩ sample, the equation for Cl Ͼ 0:3M was applied Fe2 Fe2 97.8 94.5 for the rest of the samples. FeSO4 aq 2.2 5.5 HF HF 99.6 98.6 ClϪ ClϪ 100 100 ϩ ϩ Ca2 Ca2 98.1 94.3 5. Discussion CaSO4 aq 1.9 5.7 Mg2ϩ Mg2ϩ 98.3 95.0 Chemical changes in crater lake related to MgSO4 aq 1.7 5.0 Naϩ Naϩ 99.8 99.6 volcanic activity have been observed at several vol- Kϩ Kϩ 99.6 99.3 canoes of the world. Changes in inputs of magmatic heat and volatiles are generally reflected in the

Table 3 Distribution of components among species at Popocate´petl crater lake

Component Species Percentage (1992) Percentagea (1994) Percentageb (1994)

Fe2ϩ Fe2ϩ 65.9 60.3 66.6

FeSO4 aq 34.1 39.7 33.4 2Ϫ 2Ϫ SO4 SO4 28.3 16.3 11.2 MgSO4 aq 9.8 13.2 10.9 CaSO4 aq 5.2 2.7 2.3 Ϫ NaSO4 5.3 1.9 1.4 FeSO4 aq 8.8 10.9 9.2 Ϫ HSO4 41.9 54.6 39.5 ϩ AlSO4 10.9 †Ϫ Al SO4 2 14.4 ClϪ ClϪ 100 100 100 Ca2ϩ Ca2ϩ 62.8 65.4 71.2

CaSO4 aq 37.2 34.6 28.8 Mg2ϩ Mg2ϩ 65.9 68.7 74.2

MgSO4 aq 34.1 31.3 25.8 Naϩ Naϩ 93.8 94.2 95.7 Ϫ NaSO4 6.2 5.8 4.3 Kϩ Kϩ 91.5 88.7 91.4 Ϫ KSO4 8.5 11.3 8.6 FϪ FϪ 2.5 1.7 MgFϩ 1.5 4.9 HF 95.9 93.1 AlF2ϩ 85.8 ϩ AlF2 14.1 H3BO3 H3BO3 100 100 100

a Werner et al., 1997. Calculations without Al concentration input. b Werner et al., 1997. Calculations including Al concentration. 118 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Table 4 Chemical geothermometers at El Chicho´n and Popocate´petl

Geothermometer Chicho´n Chicho´n Chicho´n Popocate´petl Popocate´petl Popocate´petl 1983 T(ЊC) 1993 T(ЊC) 1997 T(ЊC) 1985 T (ЊC) 1992 T (ЊC) 1994 T(ЊC)

T measured 56 31 35.4 – – 65 Quartza 179 177 181 – – 189 Na/Lib 257 – 133 – – 298 Na–K–Cac 242 180 219 166 233 226

a Fournier and Truesdell (1973). b Fouillac and Michard (1981). c Fournier and Potter (1982). temperature and chemistry of the lakes (Rowe et al., from redox-reactions of sulfur or from dissolution– 1992). At Yugama crater lake, Takano and Watanuki precipitation reactions, since gypsum and anhydrite (1990) found a decrease in the polythionate and an were close to saturation over the sampled period. increase in the sulfate concentrations of the lake Precipitation of sulfate could take place through: water before its 1982 eruption. During the 1971– ϩ Ϫ Ca2 ϩ SO2 $ CaSO anhydrite† 1972 eruption of Soufrie`re volcano the concentration 4 4 Ϫ 2Ϫ of Cl and SO4 increased (Sigurdsson, 1977). and Increases in the Mg/Cl ratio during and after eruptive 2ϩ ϩ 2Ϫ ϩ $ † periods have been observed at Ruapehu volcano Ca SO4 2H2O CaSO4·2H2O gypsum (Giggenbach, 1983). Chemical changes in the lake The presence of sulfur sublimates on the crater floor water from Kusatsu-Shirane volcano were detected (Fig. 2) suggests that oxidation–reduction processes one year before its 1976 eruption (Ossaka et al., 1980). of sulfur occur within the lake. The crater lakes act as condensers that trap the more Except for the large initial drop in concentrations, soluble or reactive magmatic volatiles (mainly SO2,H2S, no correlation was found between sulfate and chloride Ϫ HCl, HF and HBO2) (Delmelle and Bernard, 1994). Char- at El Chicho´n since 1985. The predominance of Cl 2Ϫ acteristics of crater lakes situated over actively degassing over SO4 in the water samples is unexpected from volcanoes are extreme acidity, a sulfur-rich chemistry the huge emission of SO2 during the 1982 eruptions of and elevated concentrations of dissolved rock-forming El Chicho´n. Ash leachates from samples collected in elements (Rowe et al., 1992; Ohba et al., 1994). April 1982 had a S/Cl weight ratio of 2.6 (Varekamp The decreasing volcanic influence on the El et al., 1984). Although the S/Cl ratio in the lake water Chicho´n crater lake water is mostly reflected in the varied with time, it has always been much lower than increasing pH, and decreasing temperature. The over- in the leachates. In January, 1983 the measured ratio all concentration decrease from 1983 to 1997 of in the water was S=Cl ˆ 0:049 and in 1997, S=Cl ˆ Ϫ 2Ϫ Ϫ -related ions such as Cl ,SO4 and F also 0:042: The highest ratio was obtained in the Novem- indicates that the dissolution of volcanic gases has ber, 1991 sample S=Cl ˆ 0:504† which had the lowest diminished on average. Furthermore, fumarolic and conductivity of all the sampling period. bubbling gas isotopic and chemical measurements The lower, varying S/Cl ratios observed at El made by Taran et al. (1998) from May 1995, to Chicho´n crater lake may result from different effects. January, 1997, suggested a transition from magmatic The ash leachates reveal the conditions during the to hydrothermal conditions. eruption. The water samples reveal a post-eruptive The similar trends observed for calcium and condition. The co-eruptive condition implies cata- magnesium (Fig. 8) indicate the same source for strophic degassing of large volumes of sulfur-rich both ions, probably related with trachyandesite disso- magma. The post-eruptive condition implies a much lution in the lake water, as proposed by Casadevall et lower, remanent degassing of a volatile-depleted al. (1984). Sulfate variations with time could result magma through a system containing liquid water. M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 119

Fig. 10. Conductivity (mS/cm) and rainfall (mm/month) from 1983 to 1997 at El Chicho´n. Rainfall data corresponds to the Pichucalco metereological station (CNA, 1998) located about 20 km from El Chicho´n volcano.

Even gases having a relatively high S/Cl ratio may hand, from 1991 higher conductivities were obtained reduce their SO2 concentration, when bubbling in times of lower rainfall rates, indicating more influ- through a thick body of water. SO2 may react in the ence of seasonal effects. Boron concentration behaved deeper parts of the water body forming other sulfur similarly to conductivity with a clear decreasing trend compounds and the surface water may yield lower S/ until 1985 (Fig. 11), and a minimum value in Novem- Cl ratios. ber 1991, after a heavy rain period. Additional effects producing variations in the S/Cl Iron concentration at El Chichon (Fig. 11) is ratio may be the precipitation of gypsum, anhydrite controlled by dissolution–precipitation reactions. and sulfur. As an example, the increase in that ratio in This may be inferred from the oversaturation of November 1991 may have been a result of a higher goethite that was obtained for all the samples after dilution of the lake water at the end of the rainy 1983. The precipitation of goethite is pH-dependent season, decreasing the formation of sulfate minerals, through: and allowing more sulfate with respect to chloride to 3ϩ ϩ $ ϩ ϩ be in solution. Fe 2H2O FeOOH 3H The irregular behavior of the conductivity of El 2ϩ Chicho´n water could result from both changes in the besides, the Eh of the water influences the ratio Fe / magmatic influence on the lake, and variations in the Fe3ϩ, and hence the extent of the goethite formation. amount of water in the crater as a result of seasonal The changes observed at Popocate´petl crater lake and variable rainfall effects (Fig. 3). The decreasing of might be related with the restart of its activity since the conductivity from 1983 to 1985, despite the 1993. A sulfate increase in spring water was observed diminishing of the rainfall (Fig. 10) suggests a prior to eruptive events at Tacana´,Me´xico (De la decrease of the magmatic influence. On the other Cruz-Reyna et al., 1989), Poa´s crater lake, Costa 120 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

Fig. 11. B (dark symbols) and Fe (light symbols) in mg/l at El Chicho´n, Popocate´petl and Nevado de Toluca lakes against time.

Rica (Rowe et al., 1995), and Yugama crater lake, December. The magnesium input was also reflected (Takano and Watanuki, 1990). During the in the water type change from sodium-chloride- 1971–1972 eruption of Soufrie`re volcano on St. sulphate in 1992 to magnesium-chloride-sulphate in 2Ϫ Vincent Island, the SO4 concentration in the crater 1994. 2Ϫ lake water also increased (Sigurdsson, 1977). At The variations in the predominance of SO4 Popocate´petl, the sulfate was more than 100% higher species at El Chicho´n between 1983 and 1997 are in 1994 than in 1986. This increase preceded the due mainly to the increase of the pH that allowed 2Ϫ December 21, 1994 ash eruption, which initiated the more SO4 to form aqueous species with cations ϩ current activity. Besides, at Poa´s the SO4/Cl ratio other than H . The same effect, but in the opposite presented a peak prior to the disappearance of the sense, was observed at Popocate´petl, since the percen- 2Ϫ; Ϫ; crater lake (Rowe et al., 1995). An increment in this tage of SO4 bound as HSO4 shifted from 41.9 in ratio was also observed at Popocate´petl, since the SO4/ 1992 to 54.6 in 1994 (without the Al concentration Cl ratio was 1.17 in 1992 and 1.66 in 1994. input). By including the data of Al concentration Variations in the Mg/Cl quotient in crater lake (probably resulting from Al-silicate dissolution due water have been correlated with the activity of to the low pH) in the geochemical model, the form- Ruapehu volcano (Giggenbach, 1983). An increase ation of aluminium complexes with sulfate is evident; in this ratio was detected just prior to ash eruptions. these complexes might also had been present in 1992, The magnesium content was related with the degree of but could not be modelled for the lack of Al data. interaction of lake waters with high-temperature Application of chemical geothermometers to the andesitic material (Giggenbach, 1983). lake waters may give results far from the real tempera- In the crater lake water of Popocate´petl, the Mg/Cl ture at depth. Both El Chicho´n and Popocate´petl were also increased, varying from 0.085 in 1992 to 0.177 in oversaturated in quartz, resulting in fairly constant 1994, before the ash emission which occurred in calculated temperatures through time. Following the M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 121 criteria given by Giggenbach (1988) on the degree of lakes, reflect the stage of their volcanic activity. thermodynamic fluid–rock equilibrium of thermal Magmatic influence in active volcanoes such as Popo- waters, these lakes were placed in the field of cate´petl and El Chicho´n is reflected in the very low pH immature waters (Fig. 12A). Fig. 12B shows that El and high conductivity values of their crater lakes. Chicho´n in 1983 was close to the line of rock disso- Reduced magmatic influence in a post-eruptive stage lution, but farther from that line ten years later. Popo- allows fluctuations of the conductivity derived from cate´petl in 1992 and 1994 was placed next to the external factors, such as rainfall. Higher measured Ruapehu water produced during an eruptive period temperatures corresponded to lake water more influ- (Giggenbach, 1988). The sample from Nevado de enced by magmatic gases. The dormant stage of Toluca was below the full equilibrium line and very Nevado de Toluca was revealed by the chemical far from the volcanic waters depicted by Giggenbach features of its crater lake water, with low conductiv- (1988) in this diagram. Nevertheless, by applying the ities and low concentrations of magma-related ions, as Na–K–Ca geothermometer, a decreasing trend in the well as a water temperature close to the environment. temperature between 1983 and 1997 could be inferred The decrease in the volcanic-related species like at El Chicho´n. This trend agrees with the tendency of sulfate, chloride, boron and fluoride since 1983 at El the measured temperatures and also with the results Chicho´n indicates a lowering of the magmatic con- from the empirical Na/Li geothermometer (Foullac an tribution in the crater lake, though its current general Michard, 1981). At Popocate´petl, a temperature chemistry reflects that such contribution is still increase was obtained with the Na–K–Ca geotherm- present. ometer between 1985 and 1994. The readings made in At Popocate´petl, its reawakening was evident from January 1986 (SEAN Bulletin, 1986), and in 1994 by the chemical changes observed in the crater lake that Werner et al. (1997), showed also the same trend. The preceded the ash eruption occurred in December, application of the three geothermometers to the 1994 1994. Sulfate was the anion showing more correlation Popocate´petl sample gave different temperatures. with volcanic activity at Popocate´petl. The ratio S/Cl Probably the best temperature estimate is obtained rised mainly as an effect of sulfate increase, since Cl- from the Na/Li geothermometer (Foullac and concentrations varied erratically and in a lower Michard, 1981). Although it was developed including proportion. The evolution of major cations rep- only data from springs and wells in geothermal areas, resented in Giggenbach diagrams also reflected the some of them were acid sulfate waters, like Popo- changes of the magmatic influence at El Chicho´n cate´petl lake water in 1994. and Popocate´petl. In contrast with Popocate´petl and El Chicho´n, The Mg/Cl quotient revealed to be an important minor changes were observed at Nevado de Toluca ratio in the assessment of the level of volcanic activ- with time. The pH and conductivity measured in 1997 ity. At El Chicho´n, this value decreased persistently pH ˆ 5:59; L ˆ 18 mS=cm† were slightly lower than between 1985 and 1991 from 0.157 to 0.068, and then the values measured by Caballero-Miranda (1996) in kept a low value. Magnesium content has been related January, 1991 pH ˆ 5:90; L ˆ 24:6 mS=cm†: This with interactions of lake-water with high-temperature difference might be due to seasonal effects, as the andesitic material (Giggenbach, 1983). However, at 1997 sample was obtained in the rainy season. The Popocate´petl, the crater lake evaporated months concentrations of boron and FϪ below detection levels before solid andesitic ash was emitted. The higher as well as the low concentrations of dissolved ions contribution of magnesium was probably derived indicate no influence of volcanic products at Nevado from heating of the andesitic lake basin at the crater de Toluca lake. bottom by hot fumarolic gases. Two other factors frequently used to measure the level of magmatic influence in crater lake waters, S/Cl 6. Conclusions ratio and water type, poorly reflected the decrease in the magmatic influence at El Chicho´n, while they The chemical characteristics determined at El showed a better correlation with the increasing activ- Chicho´n, Popocate´petl and Nevado de Toluca crater ity of Popocate´petl. Water type change at El Chicho´n 122 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125 123 crater lake water has been controlled by a relative Boudal, C., Robin, C., 1989. Volcan Popocate´petl: Recent eruptive increase of Na with respect to other cations. Since history, and potential hazards and risks in future eruptions. In: this increase occurs along with a clear decrease of Latter, J.H. (Ed.), Volcanic Hazards. IAVCEI, Proceedings in Volcanology 1, Springer, Berlin, pp. 110–128. the magmatic influence, this effect ought to be Caballero-Miranda, M., 1996. The diatom flora of two acid lakes in increasingly hydrothermal. In contrast, water type at central Me´xico. Diatom Res. 11, 227–240. Popocate´petl has been controlled by higher dissolu- Cantagrel, J.M., Robin, C., Vincent, P., 1981. Les grandes etapes tion of magmatic sulfur gases and increased tempera- dı´evolution dı´un volcan andesitique composite: Exemple du tures enhancing the dissolution of magnesium. Nevado de Toluca. Bull. Volcanol. 44, 177–188. Canul, R., Rocha, V.S., 1981. Informe Geologico de la Zona Even though Popocate´petl and El Chicho´n lakes Geotermica de “El Chichonal”, Chiapas, Mexico. Comisio´n can be classified as immature waters, the Na–K–Ca Federal de Electricidad. Rep. 32–81 (unpublished). geothermal thermometer reflected the same trends of Casadevall, T.J., De la Cruz-Reyna, S., Rose Jr., W.I., Bagley, S., the surface measured temperatures, suggesting that it Finnegan, D.L., Zoller, W.H., 1984. Crater Lake and post-erup- can render useful results in active volcanoes. tion hydrothermal activity, El Chicho´n Volcano, Me´xico. J. Volcanol. Geotherm. Res. 23, 169–191. Christenson, B.W., Wood, C.P., 1993. Evolution of a vent-hosted Acknowledgements hydrothermal system beneath Ruapehu Crater Lake. N.Z. Bull. Volcanol. 55, 547–565. CNA, Comisio´n Nacional del Agua, 1998. Precipitacio´n, Estacio´n The authors are grateful to A. Aguayo, N. Ceniceros Pichucalco, Gerencia Regional Golfo Sur, Subgerencia Regio- and O. Cruz for their skillful chemical analyses of the nal Te´cnica de Tuxtla Gutierrez, Tuxtla Gutierrez, Me´xico. water samples, to A. Doger for the difficult task of Damon, P., Montesinos, E., 1978. Late Cenozoic volcanism and sampling the Popocate´petl crater lake, to S. Ramos metallogenesis over an active Benioff Zone in Chiapas, Mexico. Ariz. Geol. Soc. Dig. 11, 155–168. for obtaining the rainfall data, and to S. Hughes for De la Cruz-Reyna, S., Siebe, C., 1997. The giant Popocate´petl Stirs. the revision of English and valuable suggestions. Nature 388, 227. De la Cruz-Reyna, S., Armienta, M.A., Zamora, V., Jua´rez, F., 1989. Chemical changes in spring waters at Tacana´ Volcano, References Chiapas, Mexico: a possible precursor of the may seismic crisis and phreatic explosion. J. Volcanol. Geotherm. Res. 38, 345– APHA, AWWA, WPCF, 1989. Standard Methods for the Examin- 353. ation of Water and Wastewater, Prepared and Published jointly De la Cruz-Reyna, S., Quezada, J.L., Pen˜a, C., Zepeda, O., by the American Public Health Association, the American Sa´nchez, T., 1995. Historia de la actividad del Popocate´petl Water Works Association and the Water Pollution Control (1354–1995). In: Comite´ Cientı´fico Asesor (Ed.), Volca´n Popo- Federation, , DC. cate´petl: Estudios Realizados Durante la Crisis de 1994–1995. Ball, J.W., Norstrom D.K., 1991. Wateq4f—User’s manual with Sistema Nacional de Proteccio´n Civil, Centro Nacional de revised thermodynamic data base and test cases for calculating Prevencio´n de Desastres, UNAM Me´xico, pp. 3–22. speciation of major, trace and redox elements in natural waters. 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Fig. 12. (A) Giggenbach (1988) diagram for the evaluation of Na–K and K–Mg equilibration temperatures. Symbols are the same as those of = ϩ † = ϩ † V Fig. 6. (B) Plot of 10CMg 10CMg CCa vs. 10CK 10CK CNa of Popocate´petl, El Chicho´n and Nevado de Toluca Volcanoes. ( ) Nevado de Toluca. El Chicho´n and Popocate´petl symbols are the same as those of Fig. 6 (after Giggenbach, 1988). 124 M.A. Armienta, S. De la Cruz-Reyna / Journal of Volcanology and Geothermal Research 97 (2000) 105–125

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