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Authors requiring further information regarding Elsevier’s archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright Author's personal copy Lithos 115 (2010) 153–162 Contents lists available at ScienceDirect Lithos j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / l i t h o s Hydrothermal alteration of deep fractured granite: Effects of dissolution and precipitation Shoji Nishimoto a,⁎, Hidekazu Yoshida b a b Nagoya City Science Museum, 2-17-1 Sakae, Naka, Nagoya, 460-0008 Japan Nagoya University Museum, Furocho, Chikusa, Nagoya, 464-8601 Japan a r t i c l e i n f o Article history: Received 21 April 2009 Accepted 27 November 2009 Available online 6 December 2009 Keywords: Hydrothermal alteration Granite Water–rock interaction Fracture Orogenic belt a b s t r a c t This paper investigates the mineralogical effects of hydrothermal alteration at depth in fractures in granite. A fracture accompanied by an alteration halo and filled with clay was found at a depth of 200 m in a drill core through Toki granite, Gifu, central Japan. Microscopic observation, XRD, XRF, EPMA and SXAM investigations revealed that the microcrystalline clays consist of illite, quartz and pyrite and that the halo round the fracture can be subdivided into a phyllic zone adjacent to the fracture, surrounded by a propylitic zone in which Fephyllosilicates are present, and a distinctive outer alteration front characterized by plagioclase breakdown. The processes that result in these changes took place in three successive stages: 1) partial dissolution of plagioclase with partial chloritization of biotite; 2) biotite dissolution and precipitation of Fe-phyllosilicate in the dissolution pores; 3) dissolution of K-feldspar and Fe-phyllosilicate, and illite precipitation associated with development of microcracks. These hydrothermal alterations of the granite proceed mainly by a dissolution–precipitation process resulting from the infiltration of hydrothermal fluid along microcracks. Such infiltration causes locally high mobility of Al and increases the ratio of fluid to rock in the alteration halo. These results contribute to an understanding of how granitic rock becomes altered in orogenic fields such as the Japanese island arc. © 2009 Elsevier B.V. All rights reserved. 1. Introduction Hydrothermal alteration affects the geochemical properties of granitic rocks (Ferry, 1979; Boyce et al., 2003). Granitic rocks in the Japanese orogenic field are altered more than continental granite because they are part of an active geothermal system with a higher density of fractures (Yoshida et al., 2005). However, granitic rock underlying a geothermal field obtained from a depth of 3000 m below the surface was found to be remarkably fresh and not permeable enough to allow hydrothermal circulation (Fujimoto et al., 2000). This suggests that fracture development is an important factor in the establishment of hydrothermal circulation and the facilitation of hydrothermal alteration by the interaction between fluid and rock within the granitic body. Although numerous studies related to hydrothermal alteration have been carried out, most are concerned with porphyry copper deposits, epithermal gold deposits or geothermal fields lying outside the body of the granite (e.g. Adams and Moore, 1987; Hedenquist et al., 1996; Doi et al., 1998). Within the body of granitic rocks, the interaction between the rock and external fluids has, however, been studied in the context of hot dry rock (HDR) power generation (Savage et al., 1987; Bando et al., ⁎ Corresponding author. Tel.: +81 52 201 4486. E-mail address: [email protected] (S. Nishimoto). 0024-4937/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.lithos.2009.11.015 2003), the underground storage of carbon dioxide (Ueda et al., 2005; Suto et al., 2007) and radioactive waste disposal (Yoshida et al., 2005; Sandström et al., 2008; Yoshida et al., 2009). In the case of HDR reservoirs used for electricity generation, flow-path stability controlled by fluid–rock interaction is important for the performance of reservoirs through their lifetime (Savage et al., 1987; Richards et al., 1992). The interaction of rock and fluid containing CO2 at elevated temperatures has been studied in order to better understand a possible underground storage of CO2 (Suto et al., 2007). Fractures in granitic rocks and the minerals that fill them are also critical in their effect on the isolation of radioactive waste in sites of deep geological disposal. The frequency, geometry and filling of fractures are significant factors that control solute migration in geological environment (Steefel and Lichtner, 1994; Mazurek, 1994; Yoshida et al., 2000). The long-term stability of structural features and the interaction between fluid and rock should therefore be taken into account in modeling the processes of element mobility in deep granitic bodies. In order to develop such a model, the way fractures are generated and subsequently stabilized needs to be better understood. So also does the way in which each mineral in granite is altered by hydrothermal fluid along fractures, a change made more complex to understand because of the actions of multiple alteration processes. This study has, therefore, focused on the mineralogical changes to granite caused by the penetration of hydrothermal fluid along fractures in the deep underground environment. We have investigated a Author's personal copy 154 S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 simple alteration halo in granite along a fracture filled with compacted clay from a drill hole excavated at the Mizunami Underground Research Laboratory (MIU) in central Japan. The presence of a clayfilled fracture without subsequent deformation implies that it has been stable since its formation. This makes it an ideal site for investigating how hydrothermal fluid affects the rock as it infiltrates fractures, and therefore the long-term stability of sealed fractures in the deep underground environment. In this paper we show the chemical and mineralogical changes across the alteration halo and discuss the process of hydrothermal alteration that results from fracturing and microcracks in granite. In broader terms, this study is a contribution to the understanding of the long-term stability of fractures in granitic rocks. such granitic rock in which a considerable part of the granite body is concealed beneath the Late Cretaceous ash-flow deposits of the Nohi Rhyolite (Kawada et al., 1961; Yamada et al., 1971), forming several cauldrons (Koido, 1991). The similarity of the petrology between the Nohi Rhyolite and the surrounding Naegi–Agematsu granite indicates that they were formed as a series of large magmatic events on the eastern margin of the Eurasian continent (Sonohara and Harayama, 2. Geological setting Late Cretaceous–Paleogene granitoids are widely distributed in central Japan (Fig. 1). In Nakajima's (1994) interpretation, based on studies of the isotopic ages of granitic and metamorphic rocks, these granitoids were formed during the subduction of the Kula–Pacific ridge beneath the Eurasian continent. Naegi–Agematsu granite is one Fig. 1. Geological map showing location of the Toki granite body part of the Naegi– Agematsu granite intruding into Nohi rhyolite. MIU: Mizunami Underground Laboratory. Simplified from Geological Survey of Japan (2007) and Ishihara and Wu (2001). Fig. 2. Illustration of the alteration halo and chemical compositions of mineral assemblage. a) Paragenetic sequence of secondary minerals. b) sample photo; c) SXAM compositional maps of Ca, Fe and K; d) bulk compositional of Fe2O, CaO, Na2O, K2O and LOI within the alteration halo. *ff: fracture filling. Author's personal copy S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 155 Table 1 Bulk composition of individual zones within the hydrothermal alteration halo. Sample number 1 2 3 4 5 6 7 8 Unaltered SiO2 TiO2 Al2O3 Fe2O3* MnO MgO CaO Na2O K2O P2O5 LOI Total 78.1 0.16 12.63 1.52 0.01 0.11 0.16 3.86 3.82 0.05 0.57 100.97 77.02 0.17 12.3 1.69 0.02 0.12 0.16 3.42 4.23 0.05 1.2 100.38 76.98 0.19 12.76 1.86 0.02 0.16 0.2 3.11 4.45 0.05 1.52 101.3 75.84 0.17 13.16 2.17 0.02 0.17 0.23 3.12 4.57 0.05 1.64 101.15 74.55 0.21 13.46 2.69 0.03 0.22 0.33 2.83 4.73 0.05 1.61 100.71 74.96 0.21 13.33 2.93 0.05 0.28 0.61 3.11 4.43 0.05 1.22 101.15 74.4 0.2 13.21 2.5 0.07 0.29 0.82 3.31 4.87 0.05 0.6 100.31 73.01 0.19 13.37 2.15 0.07 0.27 1.06 3.43 4.92 0.05 0.75 99.26 73.7 0.17 13.28 2.06 0.07 0.26 1.02 3.16 4.86 0.04 0.77 99.38 73.15 0.18 13.39 2.01 0.07 0.28 0.97 3.17 5.06 0.04 0.83 99.15 Sample numbers are shown in Fig. 2c. LOI: loss on ignition. Fe2O3*: total Fe as Fe2O3. 2007). They are interpreted as a volcano-plutonic complex formed in a shallow crust at the active continental margin. The Toki granite body is one component of the Naegi–Agematsu granite. It has a circular exposure of about 140 km2 and intruded discordantly into the Jurassic accretionary complex of the Mino Terrain (Wakita, 2000). The granite body mostly consists of medium to coarse-grained biotite granite. It contains a small amount of pegmatite but lacks economic-grade ore deposits (Ishihara and Wu, 2001). Magnetite is not observed, indicating that it belongs to the ilmenite-series (Ishihara, 1977). The peraluminous chemical composition (A/CNK = 1.09–1.16: Ishihara and Wu, 2001) is consistent with S-type granite (Chappell and White, 1974). The Rb–Sr whole rock age is 72.3 Ma (Shibata and Ishihara, 1979) while the K–Ar age of the biotite is 60–63 Ma (JNC, 2002) and the fission track age of the zircon is 59–61 Ma (Sasao et al., 2006). The high initial 87Sr/86Sr ratio (0.7106) compared with other granites in southwest Japan (0.706– 0.709) implies the existence of an old basement at depth in this region (Ishihara and Matsuhisa, 2002). Toki granite is unconformably covered with Miocene of the Mizunami Group (20–15 Ma) and Pliocene of the Seto Group (0.7–5 Ma). There is a highly weathered zone less than 10 m thick in the upper part of the Toki granite beneath the unconformity. The Tsukiyoshi Fault, an E–W striking reverse fault dipping 70° to the south, cuts the Toki granite and the Mizunami Group (Onishi and Shimizu, 2005). The granite in the vicinity of major faults is fractured and altered (Nakamata et al., 2007) suggesting association of alteration with faults. Within the granitic body, Iwatsuki and Yoshida (1999) recognized two fracture systems, an intact, moderately fractured part and an intensely fractured part, based on both the degree and frequency of fracturing. Mineralogical study showed that the moderately fractured and intensely fractured parts are associated with chlorite/montmorillonite and kaolinite respectively as fracture fillings. Even in the intact part of the granite, however, weak illitization of some plagioclase and chloritization of biotite grains are observed under the microscope (Nishimoto et al., 2008). Based on the O and C-isotopic composition of fracture-filling calcites, it appears that the Toki Granite has been altered by three types of fluid: hydrothermal fluids, seawater, and groundwater (Iwatsuki et al., 2002). The present underground water in the granite is of Na–(Ca)–Cl type and the temperatures at depths of 500 to 1000 m are about 30 °C (Iwatsuki et al., 2002). geological disposal of high level radioactive waste. The granite is mainly composed of brownish gray quartz, with pale pink K-feldspar, white plagioclase, and biotite. The open fracture that we studied is filled with unsolidified, compacted pale green clay without pores. No slip trace was observed on the fracture surface between the infilling clay and the wall rock. An alteration halo is symmetrically developed on both sides of the clay-filled fracture (Fig. 2). Visually, the halo is divided into a 3 cm wide whitened internal part and a 2 cm wide greenish external zone. The drill core sample was divided into two halves. One half was sliced and polished for chemical analysis. Bulk chemical composition was measured on eight cut pieces of the core sample near the fracture and two cut pieces of unaltered granite for comparison by XRF (Shimadzu SXF-1200) equipped with an Rh X-ray tube. The instruments were calibrated against rock reference samples issued by the Geological Survey of Japan. Compositional maps of Ca, K and Fe of the whole sliced sample surface were obtained using a scanning X-ray analytical microscope (SXAM, Horiba XGT-2000), an X-ray fluorescence analyzer that shows the distribution of elements across the surface of a sample (Hosokawa et al., 1997). A high- 3. Sample description and analytical methods The sample was collected from a borehole /v192-(6)/ drilled horizontally at a depth of 200 m in a shaft of the MIU which is being constructed by the Japan Atomic Energy Agency (JAEA) in order to establish techniques for investigation, analysis and assessment of Fig. 3. Isocon diagram for the each zone of the alteration halo along the fracture in the Toki granite. Cunaltered granite is an average of two analysis of unaltered granite. Caltered granite is the average analysis of each zone. Each analysis is multiplied by an appropriate factor: 0.3 for SiO2, 1.5 for Al2O3, 5 for Fe2O3, 18 for CaO, 3 for K2O, 4 for Na2O, 40 for TiO2, 20 for MgO, 50 for MnO and P2O5. Author's personal copy 156 S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 intensity continuous X-ray beam (Rh anode 50 kV, 1 mA), 100 μm in diameter, is focused with a guide tube and directed onto the surface of the sample on a PC-controllable X–Y stage. The second half of the drill core sample was used for mineralogical investigation. Thin sections were cut to observe mineral texture by polarizing microscope. Some sections were polished to analyze chemical composition and element distribution in plagioclase and biotite grains by electron microprobe (EPMA, JEOL JXA-8800). Mineral compositions were acquired using a focused electron beam of 1 µm diameter with an accelerating voltage of 15 kV and a beam current of 12 nA. Some mineral grains were drilled with a mini-drill to identify clay minerals. The powder X-ray diffraction pattern was measured by diffractometer (XRD, Multiflex, Rigaku) set at a CuKα radiation of 40 kV and 20 mA in the range of 2– 50° 2θ. 4. Results 4.1. Overall sequence of mineralogical and chemical changes The development of mineral and chemical features within the hydrothermal alteration halo is summarized in Fig. 2. Based on paragenesis (Fig. 2a) and occurrence (Fig. 2b), the alteration halo can be subdivided into three zones: an outer zone, a propylitic zone and a phyllic zone, although the mineralogical sequence of the alteration halo is less sharp. The outer zone is distinguished by plagioclase breakdown. The propylitic zone is greenish and characterized by secondary Fe-phyllosilicates such as chlorite, corrensite and smectite that are typical of propylitic alteration. The phyllic zone is distinguished by whitened K-feldspar that results from the breakdown and illitization of plagioclase. Compositional mapping by SXAM (Fig. 2c) revealed an abrupt decrease of Ca in the outer zone, and also a depletion of Ca in propylitic and phyllic zones. K is detected in alteration products of plagioclase within the phyllic zone while Fe is distributed in alteration products of plagioclase throughout the propylitic zone. The bulk composition of the eight cut pieces examined by XRF is shown in Table 1. The ratios of CaO, Fe2O3(total), K2O and Na2O in the eight portions to those in “unaltered” host granite are shown in Fig. 2d. As shown in SXAM maps, CaO-depletion is significant in the alteration halo. Fe2O3 is enriched in the propylitic zone and depleted in the phyllic zone. Na2O is enriched along the fracture and K2O progressively depleted from the outer zone to the fracture surface. LOI increases between the phyllic and propylitic zones. Since calcite has not been identified, LOI represents crystallochemical OH or water. The isocon plots (Grant, 1986) of each zone, based on Table 1, are shown in Fig. 3. The points of Ti and P which are generally considered immobile, show indeed the least scatter of all elements. Overall, the element distribution suggests a weak volume loss. The concentration for Al, which is also commonly considered immobile, differs somewhat from the isocon, suggesting that Al is mobile especially in the phyllic zone. The loss of Si is the most in the outer zone. Ca depletion implies a substantial dissolution of plagioclase and its removal. The loss of Mn and Mg in the propylitic and phyllic zones indicate that biotite dissolved during the alteration process. The chemical composition of illite is phengitic (2–3 wt.% as FeO) and shows no significant changes within the alteration halo (Table 2, Fig. 4a). However, the molar Fe/(Fe + Mg) ratio of corrensite and chlorite in the alteration halo is higher than that in “unaltered” wall rock (Fig. 4b). The compacted clay that fills the fracture is pale green in color and is a mixture of illite, quartz and pyrite along with fragments of plagioclase and quartz grains. Although it is hard to separate fragments from secondary minerals, albite can also be identified. Calcite, smectite and kaolinite are absent in the clay fillings. 4.2. “Unaltered” wall–rock granite The bulk composition of unaltered granite outside the alteration halo is similar to that given in previous reports (Ishihara and Wu, 2001; Nishimoto et al., 2008), although it is slightly poorer in Si and Na, and richer in Al. The molar Fe/(Fe + Mg) ratio of the biotite varies between Table 2 Representative chemical composition of the secondary minerals. Mineral zone Illite Smectite Mixed-layer (corrensite) Chlorite Fracture Phyllica Phyllicb Propylitica Propylitica Propylitica Propyliticb outer Analysis no. 95 78 77 47 22 45 56 18 SiO2 TiO2 Al2O3 FeOc MnO MgO CaO Na2O K2O total 49.48 0.03 32.01 2.92 0.00 1.06 0.20 0.10 6.23 92.03 50.63 0.03 33.50 2.60 0.07 0.67 0.06 0.08 7.79 95.42 49.44 0.00 34.78 1.78 0.02 0.50 0.04 0.08 7.74 94.38 48.77 0.16 29.67 3.44 0.00 1.30 0.10 0.11 6.86 90.41 31.24 0.00 21.32 28.79 0.22 2.15 0.52 0.09 1.45 85.78 26.12 0.09 17.78 33.39 1.11 1.72 0.25 0.10 0.04 80.60 27.09 0.00 17.71 33.64 0.49 1.38 0.21 0.91 0.03 81.46 25.56 0.14 16.48 34.18 1.10 6.24 0.03 0.03 0.09 83.85 3.32 0.68 1.85 0.00 0.16 0.00 0.11 0.01 0.01 0.53 0.61 3.30 0.70 1.87 0.00 0.14 0.00 0.07 0.00 0.01 0.65 0.69 3.24 0.76 1.93 0.00 0.10 0.00 0.05 0.00 0.01 0.65 0.67 3.36 0.64 1.77 0.01 0.20 0.00 0.13 0.01 0.01 0.60 0.60 2.66 1.34 0.80 0.00 2.05 0.02 0.27 0.05 0.02 0.16 0.88 2.82 1.18 1.09 0.01 3.02 0.10 0.28 0.03 0.02 0.01 0.92 2.89 1.11 1.12 0.00 3.00 0.04 0.22 0.02 0.19 0.00 0.93 3.00 1.00 1.35 0.01 3.35 0.11 1.09 0.00 0.01 0.01 0.75 Atoms per formula unitd Si Al(IV) Al(VI) Ti Fec Mn Mg Ca Na K Fe/(Fe + Mg) a b c d Present in altered plagioclase. Present in altered biotite. All Fe as Fe2+. Calculated based on O10(OH)2 for illite and smectite, O10(OH)5 for corrensite, O10(OH)8 for chlorite. Author's personal copy S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 157 occurs throughout the granite body and is not related to the alteration along clay-filled fractures. 4.3. Outer zone In the outer zone of the alteration by infiltration of hydrothermal fluid from the fracture, breakdown is readily observed in the inner part of plagioclase grains, even by naked eye (arrow in Fig. 2b). Ca decreases (Figs. 2d and 3) suggesting that the dissolution of plagioclase occurred already at this stage of the alteration. Because of the higher solubility of Ca-rich plagioclase in water (Blum and Stillings, 1995), the prediction is that plagioclase would be dissolved from the Ca-rich core progressively towards the rim by the infiltrating fluid, and would form pores in the inner part of the grains. Indeed, selective dissolution, where there is a Ca-rich core of plagioclase grains, has been reported in granite (Nishimoto et al., 2008). Some biotite is partly replaced by chlorite and corrensite along the cleavage (Fig. 5f). Such alteration of the biotite may well be developed in the outer zone. 4.4. Propylitic zone Fig. 4. Plots of Fe/(Fe + Mg) ratio to Si for illite and tetrahedral Al in Fe-phyllosilicates. 0.7 and 0.8. The composition of the plagioclase is Ab80–91An7–20Or1–3 with a zonal structure. K-feldspar, showing a pale pinkish color, is fresh; its composition is Or90–92. Calcite is absent. The granite appears unaltered by naked eye but under the microscope both plagioclase and biotite are partly altered. Plagioclase is often altered to illite in the central part of the grains. Epidote is also observed in the plagioclase. Biotite is partly altered to chlorite, epidote and titanite. The presence of epidote and chlorite implies that the formation temperature is more than 220 °C, based on comparison with geothermal fields (Henley and Ellis, 1983; Goko, 2000; Mas et al., 2006). The Fe/(Fe+ Mg) ratio of chlorite is similar to that of parental biotite. This suggests that the chloritization took place as a solid-state transformation (Altaner and Ylagan, 1997) preserving the Fe/(Fe+ Mg) ratio and crystallographical orientation of the parental biotite. Chloritization is ubiquitous in the Toki granite (Nishimoto et al., 2008), implying that incipient alteration The propylitic zone is characterized by the formation of Fephyllosilicates such as chlorite, corrensite and smectite. The assemblage of these Fe-phyllosilicates corresponds to a propylitic alteration widely reported from hydrothermal fronts in geothermal fields or ore deposits (e.g. Inoue, 1995). The XRD pattern of powder extracted from replaced biotite and plagioclase grains shows an expansion from 2.9 nm to 3.1 nm upon ethylene-glycol saturation, indicating corrensite (Fig. 7). Corrensite is a trioctahedral phyllosilicate of regular, 1:1 mixed-layer chlorite–smectite. The number of octahedral cations ranges from 4.4 to 4.7, corresponding to 44–55% smectite (assuming that there are 3 octahedral cations per O5(OH)2 for smectite and 6 per O5(OH)8 for chlorite). This is consistent with the designation as corrensite. The corrensite is rich in Fe and its Fe/(Fe + Mg) ratio reaches 0.9 (Table 2). The ubiquity of fine, Fe-rich corrensite and chlorite in the zone suggests that the greenish color is caused by these minerals. Corrensite is often observed as amygdaloidal or colloform aggregates of very fine (b 100 μm) green crystals under the optical microscope (Fig. 5e, f). The form resembles that reported in other granitic rocks (Meunier et al., 1988; Lindqvist and Harle, 1991; Sugimori et al., 2008; Sandström et al., 2008). It occurs not only in plagioclase and biotite but also in the pores in K-feldspar (Fig. 6d). Its presence, without association with a particular mineral, implies direct precipitation from fluid rather than replacement through an in situ fluid–mineral reaction. Its additional occurrence in fracture filling and dissolution pores as an amygdaloidal aggregate supports the idea that it is directly precipitated from the hydrothermal fluid in dissolution pores. Biotite is almost completely replaced by corrensite, chlorite, illite, and rutile. Small (b100 μm) amygdaloidal aggregates of corrensite and chlorite occur between the cleavage surfaces, while biotite that has been replaced by illite preserves the parental crystal orientation (Fig. 5f), probably due to the similarity of structure between these two minerals. Plagioclase has a unique zoning (Fig. 5b,c) which probably formed during the progress of the alteration. XRD analysis revealed the presence of corrensite and an illite/smectite interstratified mineral (Fig. 7). The alteration zoning indicates replacement of plagioclase by illite in the central part of the grain, surrounded by corrensite and smectite (Fig. 6b), although some grains lack the illite core. This can also be identified by naked eye in some plagioclase grains as an ivory core with a grayish green mantle. Illite is seen to form lines that cut through the corrensite within the plagioclase (Fig. 5b). Thus, the alteration zoning in the plagioclase grains suggests that precipitation follows a sequence from corrensite through smectite to illite in the Author's personal copy 158 S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 Fig. 5. Photomicrographs showing hydrothermal alteration progress in plagioclase (a–c) and biotite (d–f) within the alteration halo. a) illitized plagioclase in the phyllic zone; b) linear arrangement of illite suggesting illitization along a microcrack in altered plagioclase in the propylitic zone; c) plagioclase showing alteration zoning with corrensite, smectite and illite in the propylitic zone; d) dissolved chlorite and illite altered from a biotite pseudomorph with a pore filled with quartz in the phyllic zone; e) illitized and partly dissolved corrensite and chlorite aggregates altered from biotite in the propylitic zone (without analyzer); f) biotite with chlorite and corrensite in the outer zone (without analyzer). dissolution pores. This is consistent with the bulk composition, assuming that the LOI and Fe-rich components (Fig. 2) correspond to the abundance of smectite and corrensite/chlorite, respectively. Thus the alteration zoning indicates that illitization progresses as microfractures develop, even within plagioclase grains. 4.5. Phyllic zone Significant dissolution of K-feldspar and precipitation of illite and quartz are striking features of the phyllic zone. Microcracks are common in this zone and are infilled by Fe-bearing illite and quartz (Fig. 6c) indicating that the hydrothermal fluid infiltrated along this pathway. K-feldspar shows a whitish color and ragged breakdown, suggesting dissolution with the loss of K, Al and Si. Biotite is absent and even the replacing chlorite and corrensite are dissolved, while the dissolution pores are filled with quartz (Fig. 5d). Plagioclase is strongly illitized (Fig. 5a; Fig. 6) and surrounded by a Na-rich (Ab95) marginal zone (Fig. 6) probably due to residual Na. The illite composition is similar to that in the fractures, and the grains are generally larger than those of corrensite. Na and Ca zoning of plagioclase grains is not seen. Dissolution pores like etch pits are commonly observed in plagioclase near the fracture. Corrensite and smectite have not been detected in the plagioclase. Chlorite and corrensite replacing biotite are broken down and replaced by quartz, consistent with a gradual decrease of Fe and LOI and an increase of SiO2 in the phyllic zone (Fig. 2d). These facts indicate that dissolution and outflow are significant near the fracture. K is transported to form illite, Si is added to form quartz, and then Fe is released and dissolution of previously formed hydrous silicates occurs. The illitization front revealed by the distribution of K in the plagioclase (Fig. 2c) is not sharp, indicating that it progresses gradually to reach the propylitic zone. 5. Discussion 5.1. Composition and temperature of the hydrothermal fluid The clay minerals that fill a fracture, and the minerals that are secondarily formed in the vicinity of the fracture, allow us to infer the temperature and composition of the hydrothermal fluid. Many studies have shown that illite is stable at temperatures between about 200 and 350 °C (Velde, 1985; Izawa et al., 1990; Hedenquist et al., 1996). Applying a chlorite geothermometer (Cathelineau, 1988), the temperature is estimated approximately 260 °C. Sass et al. (1987) showed experimentally that illite and smectite can coexist stably with microcline at more than 200 °C. The formation temperatures of corrensite and smectite are estimated lower than 250 °C in the fossil geothermal field (Inoue et al., 1991; Robinson and Santana, 1999) and in active geothermal fields (Lindqvist and Harle, 1991; Goko, 2000; Mas et al., 2006). It is reasonable to conclude that the hydrothermal fluid injected into the fracture we have studied was at approximately 200–300 °C. Kaolinite, which would indicate acidic conditions, is not observed. Whereas, absence of calcite indicates that the fluid was not alkaline. Therefore, it is reasonable to infer that the infiltrating hydrothermal fluid was neutral or slightly acidic. Harder (1976) showed that the formation of Fe-containing phyllosilicates is only possible under reducing conditions by the synthesis of clay minerals. The presence of pyrite in the propylitic zone also indicates that local conditions were reducing during precipitation. Preserved Na-rich marginal zone of the plagioclase suggests that Na was not released to the hydrothermal fluid. The fluid inclusion in quartz from the Toki granite is reported to be at a NaCl equivalent of 0.2–10.5% (Takagi et al., 2008). Fluid containing NaCl is common in geothermal fields at deep sites (Hedenquist and Lowenstern, 1994; Fujimoto et al., 2000). Savage et al. (1993) demonstrated that the Author's personal copy S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 159 Fig. 6. Representative EPMA compositional maps of Fe, Na and K showing the phyllic zone (a: Fe, b: Na, c: K) and the propylitic zone (d: Fe, e: Na, f: K). Symbols: ill = illite; cor = corrensite; pl = plagioclase; Kf = K-feldspar; bi = biotite; chl = chlorite; ab = albite (plagioclase). reaction of granite with diluted NaCl solution (0.008–0.028 M) at 200 °C produces sparsely developed illitic clay (as a secondary solid product) and K-feldspar is much more easily attacked than plagioclase. These results are consistent with the conclusion that the fluid in our site was diluted saline. The probable origin of the hydrothermal fluid is circulating meteoric water, as reported in geothermal thermal studies (e.g. Hedenquist and Lowenstern, 1994). 5.2. Progress of the hydrothermal alteration Based on the paragenesis of each zone within the alteration halo, a schematic model of alteration by the infiltration of hydrothermal fluid into granite is proposed in Fig. 8. At the onset of the alteration, plagioclase starts to dissolve, leaving pores and biotite undergoes chloritization (outer zone). This has probably occurred under nearly isochemical conditions at relatively low fluid/rock ratios. In the next stage, biotite is dissolved and Fe phyllosilicates (chlorite, corrensite and smectite) precipitated in the pores (propylitic zone). Since, smectite is observed only within plagioclase in the propylitic zone, the inference is that the precipitation of smectite is driven by the local mineralogical environment. In the last stage, K-feldspar is dissolved and illite and quartz precipitate as the Fe-phyllosilicates break down. The result is that illite and quartz fill the microcracks. Since K-feldspar and plagioclase break down to provide a local source of Al, and the mobility of Al is high, it is reasonable to conclude that Al is efficiently transported through the fluid in the microcracks and pores. The conclusion is therefore that the dissolution–precipitation process controls the hydrothermal alteration of granite. The development of the microcrack network from the fracture allows the hydrothermal fluid to infiltrate the wall rock, and the consequent formation of pores by dissolution results in a higher fluid/rock ratio. Previous work has shown that propylitic alteration is common at the margins of alteration zones produced at low fluid/ rock ratios, and that the fluid/rock ratio of rocks in phyllic alteration is higher than that in propylitic alteration (Lowell and Guilbert, 1970; Berger and Velde, 1992; John et al., 2008). Hence the increasing fluid/rock ratio resulting from the development of microcracks promotes the alteration. Most studies report that corrensite is a stable mineral under hydrothermal conditions (e.g. Kimbara, 1975; Inoue et al., 1991; Beaufort et al., 1997) and that it is the product of a dissolution–recrystallization reaction (Meunier et al., 1991). Schiffman and Staudigel (1995) considered that corrensite occurs under high flux (fluid/rock) conditions. These studies also support the hypothesis that the alteration sequence is associated with an increase of the fluid/rock ratio. Because it is hard Author's personal copy 160 S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 by the precipitation of Fe-pyllosilicates through the limited mobility of elements in the stagnant fluid of dissolution pores at relatively low fluid/rock ratios because of poor connectivity between the microcracks. Subsequent development of microcracks would result in the precipitation of illite and quartz to form the phyllic zone. 5.3. Implications for hydrothermal alteration in orogenic belts Our results have important implications for understanding the hydrothermal alteration of granite and the stability of fractures in orogenic belts. The presence of self-sealed fractures with unsolidified, compacted clay formed by hydrothermal alteration indicates that fractures can remain stable without deformation during cooling and uplift of the granitic body. Studies on the subsurface underlying stock of Quaternary granite (ca. 5 × 8 km) in the Kakkonda geothermal area in northeast Japan provide evidence for the state of the granitic body soon after its emplacement. Drilled samples from the hot zone (N320 °C) at ca. 3000 m depth are fresh (Kanisawa et al., 1994; Sasaki et al., 2003) and there is a brittle–ductile transition zone that corresponds to this temperature (Matsushima and Okubo, 2003). Thus, hydrothermal alteration related to fractures within granitic bodies is likely to occur after cooling below 320–350 °C at depths shallower than ca. 3000 m (Doi et al., 1998). It is also the case that hydrothermal alteration accompanied by illite and quartz occurs at around this temperature. Because the fission track age of the zircon (ca.60 Ma; Sasao et al., 2006) indicates an age when the temperature of the granite had dropped to ca. 200 °C, the fracture we studied has stayed in a relatively stable condition for about 60 million years after hydrothermal alteration at a relatively deep level and high temperature. Although fractures are implicated in the alteration of granite by affecting its permeability, once a fracture is sealed with clay, the process of alteration may be inhibited. Similar hydrothermal alteration haloes along fractures filled with clay (illite) have previously been reported in both Japan and Korea (Kitagawa et al., 2001) but less often in continental settings. Usually, quartz, calcite, laumontite, chlorite, epidote and prehnite are common as fracture-filling minerals (Yoshida et al., 2000, 2008; Sandström et al., 2008). Yoshida et al. (2005) pointed out that the density of fractures of granitic rock in an environment of orogenic stress is higher by almost one order of magnitude than that in the granitic rock of stable continental regions. Although further studies are required to confirm the origin of clay-filled fractures in granite, we believe that hydrothermal alteration through clay-filled fractures in granitic rock is associated with this specific tectonic setting. 6. Conclusion Fig. 7. XRD patterns of replacement products of plagioclase (a) and biotite (b) from the phyllic zone, propylitic zone and outer zone within the hydrothermal alteration halo along fracture from the Toki granite, Japan. EG: after ethylene-glycol treatment; Symbols: ill = illite; chl = chlorite; sme = smectite; cor = corrensite; bi = biotite. to conceive of a thermal gradient within such a limited space, the various zones of the alteration halo probably simply reflect different fluid/rock ratios. The unique alteration zoning of plagioclase observed in the propylitic zone is evidence of the progress of the alteration process. Murakami et al. (2004) showed in a dissolution experiment under reducing conditions that Fe-rich smectite or vermiculite is precipitated at the edge of biotite. They also demonstrated that, after biotite dissolution, the concentration of Fe in the fluid increases by more than one order of magnitude and that the Fe/Mg ratio is higher under reducing conditions. So it is possible that the propylitic zone is formed An alteration halo along a fracture filled with compacted clay at depth in Toki granite has been investigated. Petrographic and geochemical evidence suggests that the halo was formed by a hydrothermal, reducing, neutral to slightly acidic fluid. Within the alteration halo, reaction progress formed three zones: the outer, propylitic and phyllic zones. Once the hydrothermal fluid is injected into a fracture, it infiltrates the host granite through developing microcracks. At the onset of the alteration plagioclase is dissolved, thus forming pores inside the grains and facilitating the chloritization of biotite. In the next stage, biotite is dissolved and Fe-phyllosilicates (chlorite, corrensite and smectite) are precipitated and fill the pores. In the last stage, K-feldspar and the Fe-phyllosilicates dissolve and illite precipitates, causing the development of microcracks. Hydrothermal alteration is controlled by an increasing fluid/rock ratio which is due to an increasing connectivity between microcracks and a process of dissolution–precipitation which causes locally high mobility of Al during uplift of the host rock. There is, however, evidence that fractures self-sealed by the clay remain stable in the granitic body for long periods of time. These results contribute to an Author's personal copy S. Nishimoto, H. Yoshida / Lithos 115 (2010) 153–162 161 Fig. 8. Schematic diagram illustrating the hydrothermal alteration process of granite along a fracture. understanding of how fractured granitic rock can be altered and the way it behaves in the long term in orogenic fields such as the Japanese island arc. Acknowledgements We gratefully acknowledge Drs. K. Amano and T. Tsuruta of the Japan Atomic Energy Agency for their assistance and for discussion during this study. We would like to thank Dr. N. Katsuta of Gifu University and Mr. S. Yogo of Nagoya University for technical assistance. Professors M. Adachi, M. Takeuchi, K. Yamamoto and K. Tsukada of Nagoya University for valuable discussion. Dr. G. Clarke of The Natural History Museum, London is also acknowledged for his assistance during the preparation of this paper. In addition, I wish to thank to two anonymous reviewers for valuable comments to improve the manuscript. References Adams, M.C., Moore, J.N., 1987. 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