WESTERN PACIFIC EARTH SCIENCES Vol.2, No.3, P.319-330, 2 Figs., 4 Pls.

, August, 2002

PROCESSES OF HYDROTHERMAL ALTERATION OF ANDESITE

LI-JUN LI1, JIANN-NENG FANG1,2, HUANN-JIH LO1, SHENG-RONG SONG1, CHI-YU LEE1, YAW-LIN CHEN1, I-CHIEH LIN1, HUEI-FEN CHEN1 AND YA-JIUN LIU1
1. Department of Geosciences, National Taiwan University 2. Department of Earth Sciences, National Taiwan Museum

ABSTRACT Hydrothermal experiments on andesite alteration have been attempted under the condition of 110 oC. to 190 oC., autogeneous pressures, 0.05 M to 2 M H2SO4 solution, keeping renewal of acid solution every six hours. Experimental results show that chemical reaction begins from the surface, and then diffuses inward in every rock chip. The rock chips become finer and finer as loose fine-grained materials appear in association with them. These materials are constituted of cristobalite, pyroxenes and groundmass in the early stage, and essentially of -cristobalite in longer runs. The weight of residual chips decreases with increasing duration of experiments, while the amounts of SiO2 and K2O increase, but those of the other oxides decrease with increasing cumulative time. In the meantime, remains of strongly reacted plagioclase become silica-rich materials. It is considered that dissolution, disintegration and rapid transformation of silica-rich residues to -cristobalite are the three essential processes of the hydrothermal alteration of the andesitic rocks. Key words: hydrothermal alteration, andesite, -cristobalite, dissolution, disintegration INTRODUCTION In fumarolic and hydrothermal areas, volcanic rocks generally react with acid solutions and suffer from different extents of alteration. Such altered volcanic rocks may gradually be enriched in SiO2 and eventually change to -cristobalite and other forms of SiO2 (Minato et al., 1959; Ossaka, 1968). Simulation of such natural processes has been attempted by many workers (Muir and Nesbitt, 1992; Walther and Woodland, 1993; Nogami and Yoshida, 1995).

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It is noted that these workers lay their main stress on the study of the migration of elements of the altered rocks. Unfortunately, investigation on the processes of hydrothermal alteration has scarcely been undertaken so far. So, this study is an attempt to study this problem by virtue of experimental examination on an andesite. In our experiments, rock chips instead of conventional uses of powdered samples were taken as the starting material for the sake of petrographic observations and weight measurements of residual rock chips. Furthermore, a revised batch system as described in the next section was designed for preventing precipitated materials from sticking on the reacting rock chips so as to facilitate studies on the processes of hydrothermal alteration. It is hoped that the results of the present study may throw some light on the essential processes of hydrothermal alteration of volcanic rocks. EXPERIMENTIAL METHODS Starting materials used in the experiments include two fractions: one is a solid and the other is a liquid. Two-pyroxene andesite from the Tatunshan volcanic area in northern Taiwan has been collected for the solid starting material in this study. Phenocrysts of the andesite include plagioclase (30.3 %), augite (6.4 %), hypersthene (6.3 %), and opaques (3.0 %) of magnetite and ilmenite, while groundmass (54.0 %) contains glass and microcrystic sanidine, plagioclase, pyroxenes and apatite. The rock samples were crushed and screened to obtain rock chips with diameters ranging from 3.4 mm to 4.0 mm. The chips were cleaned in deionized water with the aid of ultrasonic vibrator for 15 minutes. After cleaning and then drying at o 110 C. for 24 hours, they were stocked for experiments. H2SO4 solutions with concentrations from 0.05 M to 2 M were used as liquid media. Experiments were carried out in teflon-lined autoclaves, with an internal volume of about o o 300 ml. for each, under the autogenous pressures and temperatures from 110 C. to 190 C. for duration up to 372 hours. Each experiment was started with an amount of about 7.5g rock chips and 150 ml. H2SO4 solution. Sample-charged autoclaves were taken out of the oven every 6 hours to renew the acid solution for avoiding precipitated compounds or minerals to stick on the surface of the rock chips. It should be noted that precipitation can generally be observed after two hours as the experiments are proceeded, and 6 hours are found to be the longest reaction time to avoid sticking of precipitates on the rock chips so as to make the separation of precipitates from residual rock chips without any difficulty. The solid samples were collected in each scheduled reaction time for analyses. The residual rock chips in each experiment were separated from the fine-grained materials produced by reaction through a 100-mesh sieve. The weight of the residual rock chips was measured for each experiment. Chemical analyses were achieved by using an X-ray fluorescence (XRF) and an electron dispersive spectrometer (EDS). Minerals were identified by using an X-ray powder diffractometer (XRD). Mineral constituents and alteration of the rock samples were examined through petrographic observations. RESULTS Petrographic observation indicates that chemical reaction essentially begins from the

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Plate I. Micrographs showing the reaction rims of the rock chips (hyp: hypersthene, aug: augite, plag: plagioclase). o A. Thickness of the reaction rim about 0.07 mm (0.05 M, 110 C., 72 hours). o B. Thickness of the reaction rim about 0.30 mm (0.05 M, 110 C., 372 hours).

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Plate II. Micrographs showing sizes of the rock chips. o A. The mean radius about 3.6 mm (0.5 M, 190 C., 96 hours). o B. The mean radius about 2.8 mm (0.5 M, 190 C., 198 hours).

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surface of rock chips, forming wider rims as the experiments stand longer (Pl. I A, B). It is also shown that, in the course of time, the rock chips become finer and finer (Pl. II A, B) as loose fine-grained materials appear in association with them. These materials can be separated from the rock chips by passing through a 100-mesh sieve. They are constituted of pyroxenes, cristobalite and groundmass in the experiments of short cumulative time [12 hours in 0.5 M H2SO4 solution at 190oC. for instance (Pl. III A)], and become essentially of -cristobalite in the experiments of long cumulative time [84 hours in 0.5 M H2SO4 solution at 190oC., for example (Pl. III B)] as revealed through XRD and petrographic identifications. Consequently, the weights of the rock chips usually decrease with increasing duration of the experiments as shown in Figure 1. Figure 2 illustrates the wt.% of oxides versus cumulative time plots of the hydrothermally treated samples. Obviously, the amounts of SiO2 and K2O increase with increasing cumulative time, though the amount of K2O only increases up to about 60 hours, and then decreases gradually towards the end of the experiments. On the contrary, the amounts of other oxides decrease evidently as the experiments are proceeded. It is also worthy of note that the residues of the strongly reacted plagioclase become silica-rich materials as detected by EDS determination.

Figure 1. The change of wt.% of rock chips with the cumulative time of the experiments. Symbols: : 2 M, 190oC.; : 2 M, 150oC.; : 0.5 M, 190oC. and : 0.5 M, 150oC.. DISCUSSION AND CONCLUSIONS As shown in Figure 2, the amounts of oxides except SiO2 and K2O decrease obviously as the experiments are proceeded. In the meantime, a strongly reacted plagioclase only remains as

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Plate III. Micrographs illustrating the disintegrated fine-grained materials. A. The fine-grained materials being constituted of pyroxenes (py), -cristobalite (crist) o and groundmass (gm) (12 hours in 0.5 M H2SO4 solution at 190 C.). B. The fine-grained materials being constituted essentially of -cristobalite (crist) (84 hours o in 0.5 M H2SO4 solution at 190 C.).

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Figure 2. Wt.% of oxides versus cumulative time plots of the hydrothermally treated samples o (2 M H2SO4 solution at 190 C.).

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silica-rich materials. These facts imply that the rock samples have been dissolved in the acid solution during the experiments. It has long been considered that the reaction between an aluminosilicate mineral and an acid solution is a simple substitution of cations by hydrogen ions (Schott and Berner, 1983; White, 1983; Carroll-Webb and Walther, 1988; Oelkers and schott, 1995; Chen and Brantley, 1997). The easiness of substitution generally decreases in the order of P, Ca, Al, Na, Si, K, Mg, Fe, Mn and Ti in andesite (Fang et al., 2002, in press), though this order may be modified by the experimental conditions such as concentration of acid solution and temperature (Chiba, 1962; Nogami and Yoshida, 1995). Anyhow, it is due to decreasing order of susceptibility of plagioclase, augite and hypersthene to the acid solution as suggested by petrographic observations. As stated previously, the strongly reacted plagioclase remains silica-rich materials as residues which have been identified to be -cristobalite. Presumably, as a result of dissolution, the aluminosilicate minerals of the andesite may ultimately be altered amorphous silica-rich materials which tend to transform into more stable -cristobalite in the experimental conditions. This argument is supported by the experimental results which indicate that -cristobalite becomes predominant in longer runs. As mentioned above, the rock chips become finer and finer, and, as a consequence, their weight decreases with increasing duration of the experiments. Presumably, the materials lost may be separated into two parts. One is dissolved in the solution, and the other appears as loose fine-grained particles which are the altered remains (Pl. III A, B). Thus, disintegration of the rock chips during the experiments is indicated. Petrographic observations show that susceptibility of andesite minerals to the acid solution decreases in the order of plagioclase, augite, hypersthene and opaques. Phenocrysts are naturally more resistant to alteration than groundmass for the same mineral (Fang et al., 2002, in press). In the meantime, chemical attack usually starts from the surface of a rock chip on account of direct contact with the acid solutions. So, reaction occurs gradually from the rim inward. Thus, alteration is stronger in the outer part than in the inner portion, and yet the degree of alteration in both of them increases with increasing duration of the experiments (Pl. I A, B). Conceivably, the highly reacted plagioclase which is severely dissolved may cause isolation of the partly reacted pyroxenes and accessory minerals. These partly reacted minerals as well as the altered residues of the plagioclase become unsupported on account of isolation so as to fall into the reacting acid solution for the short-term experiments. So, it is easy to see that the materials less than 100-mesh are essentially constituted of -cristobalite, pyroxenes and accessory minerals in decreasing order in the early stage of reaction as previously mentioned (Pl. III A). The amount of -cristobalite increases gradually, whereas that of pyroxenes and accessory minerals decreases as the experiments are proceeded. In longer runs (84 hours, in o 0.5 M H2SO4 solution at 190 C. for instance), -cristobalite eventually becomes predominant (Pl. IIIB). Presumably, plagioclase, pyroxenes and accessory minerals are strongly reacted in the outer part of the rock chips; and the altered residues are tended to disintegrate, and consist essentially of -cristobalite. Plate IV A manifests fragments of -cristobalite of different sizes. The fine-grained fragments may possibly be derived from groundmass, while the coarse-grained ones may be inherited from phenocrysts. A closer view illustrated in Plate IV B indicates that few spherical -cristobalite (< 0.2 m) may probably form through precipitation from the solution (L. J. Li, unpublished data). On the other hand, the irregular -cristobalite of different sizes (Pl. IV A) is considered to be transformed from the silica-rich residues of the strongly altered minerals. It is evident that the altered disintegrated materials become predominant in silica in the long-term experiments. This seems not quite agreeable with the experimental results which

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Plate IV. o A. Micrograph showing irregular -cristobalite (crist) of different sizes (0.5 M, 190 C., 60 hours). o B. Micrograph showing few spherical -cristobalite (s. crist) (0.5 M, 190 C., 90 hours).

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indicate that Si is not the least mobile element (Fang et al., 2002, in press). In the studied andesite, the amount of SiO2 (55%) is far greater than that of CaO (+) Al2O3 (+) Na2O (31%) and of FeO (+) MgO (+) TiO2 (12%). It is also noted that Ca, Al and Na are more mobile, and Fe, Mg and Ti are less mobile than Si during the experiments (Fang et al., 2002, in press). It is therefore reasonable that the strongly altered residues are silica-rich. Moreover, the silica-rich residues are prevented from further dissolution in the acid solution through rapid transformation to more stable -cristobalite, as revealed by the presence of -cristobalite in the disintegrated materials of 6 hours' experiments. From the foregoing statement, it is considered that dissolution, disintegration and rapid transformation of silica-rich residues to -cristobalite are the three essential processes of the hydrothermal alteration of the andesite. The experimental results suggest that dissolution may carry away about 50 wt.% of materials from the andesite if it is completely altered. So, it is highly likely that collapse due to decrease of volume should be very common in hydrothermally active volcanic areas. As stated previously, disintegration may occur in altered andesite when dissolution arrives at a certain extent, making the altered andesite loosened. In the meantime, rapid transformation of altered residues to -cristobalite preserves silica from further dissolution, and so -cristobalite stays as the final essential residues during alteration. These are consistent with the field observation that the loose residues of hydrothermally altered andesites consist chiefly of -cristobalite though some minor constituents such as tridymite and opal etc. have also been reported (Chen, 1961; Huang, 1968; Chen and Wu, 1971) in the Tatunshan volcanics. ACKNOWLEDGMENTS The authors are deeply indebted to the National Science Council, R.O.C. for partly financial support (NSC90-2116-M-002-016). REFERENCES Carroll-Webb, S.A. and Walther, J.V. (1988) A surface complex reaction model for the pHdependence of corundum and kaolinite dissolution rates: Geoc. Cosm. Acta, 52, 26092623. Chen, C.H. and Wu, Y.J. (1971) Volcanic geology of the Tatun geothermal area, northers Taiwan: Proceedings of the Geological Society of China, 14, 5-20. Chen, P.Y. (1961) Post-volcanic alteration of andesite lavas and pyroclasts in Tatun volcanic group, Taipei-Hsien, Taiwan: Acta Geological Taiwanica Science Reports of the National Taiwan University, 9, 19-38. Chen, Y. and Brantley, S.L. (1997) Temperature- and pH-dependence of albite dissolution rate at acid pH: Chemical Geology, 135, 275-290. Chiba, S. (1962) Leaching of the components of andesite in diluted sulfuric acid: Sci. Rep., Fac. Educ., Fukushima Univ., 19-29 (in Japanese with English abstact). Fang, J.N., Lo, H.J., Song, S.R., Chung, S.H., Chen, Y.L., Lin, I.C., Yu, B.S., Chen, H.F., Lee, L.J. and Liu, C.M. (2002) Hydrothermal alteration of andesite in acid solutions: experimental study in 0.05 M H2SO4 solution at 110oC.: Journal of the Chinese Chemical Society, in press.

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Huang, W.Y. (1968) Studies of clay minerals in hydrothermal alteration zones of Chinkuashih, Chiufen and Yangmingshan: MS Thesis, Dept. Geology, National Taiwan Univ., 35p. Minato, H., Nagashima, K and Minami, E. (1959) Chemical and mineralogical change of rocks soaked in Yukawa at Tamagawa hot spring area. Gen. Stud: Tamagawa Hot Spring, 6, 37 (in Japanese). Muir, I.J. and Nesbitt, H.W. (1992) Controls on differential leaching of calcium and aluminum from labradorite in dilute electrolyte solutions: Geoc. Cosm. Acta, 56, 3979-3985. Nogami, K. and Yoshida, M. (1995) Leaching rates of rock-forming components through acidic alteration: J. Volcanol. Geotherm. Res., 65(1-2), 41-49. Oelkers, E.H. and Schott, J. (1995) Experimental study of anorthite dissolution and relative mechanism of feldspar hydrolysis: Geoc. Cosm. Acta, 59, 5039-5053. Ossaka, J. (1968) Alteration of rocks in volcanoes and hot springs area: Chinetsu, 17, 65-79 (in Japanese with English abstract). Schott, J. and Berner, R.A. (1983) X-ray photoelectron studies of the mechanism of iron silicates dissolution during weathering: Geoc. Cosm. Acta, 47, 2233-2240. Walther, J.V. and Woodland, B. (1993) Experimental determination and interpretation of the solubility of the assemblage microcline, muscovite, and quartz in superitical H2O: Geoc. Cosm. Acta, 57, 2431-2437. White, A.F. (1983) Surface chemmistry and dissolution kinetics of glassy rocks at watersheds: Geoc. Cosm. Acta, 47, 805-816.

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