Hydrothermal solutions

The flow of hydrothermal solutions iato the oceans from hydrothermal vents, ie, springs coming from the sea floor ia areas of active volcanism, and the chemical reactions occurring there by high temperature alteration of basalts ate of significance ia the mass balance of and. Eurthermore,... 

Bertrandite, 4BeO 2Si02 H20, became of importance ia 1969 when the deposits of Spor Mountain ia the Topa2 district of Utah were commercially Opened. These deposits are befieved to have been derived from fluorine-rich hydrothermal solutions at shaUow depths (2). Whereas economical beneficiation of these ores averagiag < 1% BeO has not been achieved, these deposits are commercially viable because of the large reserves present. 

Hydrothermal vents have been sampled at 21 along the East Pacific Rise. The pure end member hydrothermal solutions have a temperature of 350°C and the following major ion composition (von Damm et al. (1985). Geochim. Cosmochim. Acta 49, 2197-2220). All concentrations are in mM and the pH is 3.4. Discuss the... 

In recent years, many hydrothermal solution venting and sulfide-sulfate precipitations have been discovered on the seafloor of back-arc basins and island arcs (e.g., Ishibashi and Urabe, 1995) (section 2.3). Therefore, it is widely accepted that the most Kuroko deposits have formed at back-arc basin, related to the rapid opening of the Japan Sea (Horikoshi, 1990). 

Magnesite, dolomite and calcite occur in hydrothermally altered rocks near Kuroko orebody. The following equations are used to constrain /coa values of hydrothermal solutions (Shikazono et al., 1998) (Fig. 1.39). 

Several workers have intended to estimate the chemical compositions of Kuroko ore fluids based on the chemical equilibrium model (Sato, 1973 Kajiwara, 1973 Ichikuni, 1975 Shikazono, 1976 Ohmoto et al., 1983) and computer simulation of the changes in mineralogy and chemical composition of hydrothermal solution during seawater-rock interaction. Although the calculated results (Tables 1.5 and 1.6) are different, they all show that the Kuroko ore fluids have the chemical features (1 )-(4) mentioned above. 

Heavy Rare Earth Element). Therefore, it is considered that negative Ce and positive Eu anomalies in hydrothermally altered volcanic rocks, Kuroko ores, and ferruginous chert and LREE enrichment in the Kuroko ores have been caused by hydrothermal alteration and precipitations of minerals from hydrothermal solution responsible for sulfides-sulfate (barite) mineralization. 

The REE pattern for anhydrite is different from that of seawater, indicating that anhydrite did not precipitate due to the simple heating of seawater that was suggested by Sakai et al. (1970) and Sato (1973). This REE pattern could be explained in terms of the mixing of hydrothermal solution and cold seawater and low degree of seawater/hydrothermal solution mixing ratio (Shikazono et al., 1983). 

Sverjensky (1984) calculated the dependency of Eu +/Eu + in hydrothermal solution on /oj (oxygen fugacity), pH and temperature. According to his calculations and assuming temperature, pH and /oj for epidote-stage alteration of basalt and Kuroko ores (Shikazono, 1976), divalent Eu is considered to be dominant in the rocks and hydrothermal solution. Thus, it is reasonable to consider that Eu in the rocks was removed to hydrothermal solution under the relatively reduced condition more easily than the other REE which are all tiivalent state in hydrothermal solution. Thus, it is hkely that Eu is enriched in epidote-rich altered volcanic rocks. Probably Eu was taken up by the rocks from Eu-enriched hydrothermal solution which was generated by seawater-volcanic rock interaction at relatively low water/rock ratio. 

Positive Eu anomaly is observed for hydrothermal solution issuing from the hydrothermal vent on the seawater at East Pacific Rise (Bence, 1983 Michard et al., 1983 Michard and AlbarMe, 1986). Guichard et al. (1979) have shown that the continental hydrothermal barites have a positive Eu anomaly, indicating a relatively reduced environment. Graf (1977) has shown that massive sulfide deposits and associated rocks from the Bathurst-Newcastle district. New Brunswick have positive Eu anomalies. These data are compatible with positive Eu anomaly of altered basaltic rocks, ferruginous chert and Kuroko ores in Kuroko mine area having positive Eu anomaly and strongly support that Eu is present as divalent state in hydrothermal solution responsible for the hydrothermal alteration and Kuroko mineralization. 

At the stage of Kuroko mineralization, evolved reacted seawater enriched in Eu, Ca, and Sr formed at low seawater/rock ratio (ca. 1 by mass) and at relatively reduced condition (Eu +/Eu + greater than 1). Selective leaching of Eu, Ca and Sr occurred from the dacitic rocks underlying the Kuroko ores. The hydrothermal solution enriched... 

The REE study indicates that the concentrations of REE, particularly Eu and Ce in altered rocks and ore minerals are useful indicators of oxidation state, intensity of discharging hydrothermal solution and evolutionary stage of submarine hydrothermal activity. 

The precipitation of anhydrite from hydrothermal solutions has been studied extensively by various workers (e.g., Marshall et al., 1964a,b). The salinity of the inclu-... 

Figure 1.49. Change of the strontium content and Sr/ Sr ratio of Kuroko anhydrite during the deposition and dissolution due to the mixing of hot ascending solution and cold solution (normal seawater) (Shikazono et al., 1983). R mixing ratio (in weight) = S.W./(S.W.+H.S.) in which S.W. and H.S. are seawater and hydrothermal solution, respectively. Open triangle Fukazawa deposits. Solid triangle Hanawa deposits. Open square Wanibuchi deposits. Solid square Shakanai deposits. Concentration of Ca, Sr " " and SO of H.S. are assumed to be 1,(XX) ppm, 1 ppm, and 10 mol/kg H2O, respectively. Concentrations of Ca, Sr " and SO of S.W. are taken to be 412 ppm, 8 ppm, and 2,712 ppm. Temperatures of H.S. and S.W. are assumed to be 350°C and 5°C (Shikazono et al., 1983).

Sato (1973) and Ohmoto et al. (1983) calculated the amounts of sulfides precipitated due to the mixing of ascending hydrothermal solution and cold seawater. Their calculations showed that the calculated ratios of the amounts of minerals precipitated are generally consistent with those in Kuroko ore deposits. 

If hydrothermal solution in which H2S is dominant aqueous sulfur species and SO is free mixed with cold seawater in which high amounts of SO are contained. 

The behavior of silica and barite precipitation from the hydrothermal solution which mixes with cold seawater above and below the seafloor based on the thermochemical equilibrium model and coupled fluid flow-precipitation kinetics model is described below. 

It is thought that the precipitation of amorphous silica is caused by conductive cooling from the hydrothermal solution which flows laterally in the chimney (Herzig et al., 1988). 

Solubilities of quartz and amorphous silica in aqueous solutions increase with increasing of temperature (Holland and Malinin, 1979). Solubility of barite depends on salinity and temperature (Blount, 1977). The solubility of barite in hydrothermal solution having more than 1 molal NaCl concentration increases with increasing temperature, while a solubility maximum exists in the solution with NaCl concentration less than ca. 0.2 molal (Blount, 1977). 

Barite precipitation highly depends on SO and Ba " concentrations in the fluids. That means that the mixing ratio of hydrothermal solution and seawater is also an important factor for the precipitation of barite, together with the factors mentioned above. 

Chemical composition of hydrothermal solution experimentally interacted with rocks... 

Origin of ore fluids is constrained by (1) chemical compositions of ore fluids estimated by thermochemical calculations (section 1.3.2) and by fluid inclusion analyses, (2) isotopic compositions of ore fluids estimated by the analyses of minerals and fluid inclusions (section 1.3.3), (3) seawater-rock interaction experiments, (4) computer calculations on the seawater-rock interaction, and (5) comparison of chemical features of Kuroko ore fluids with those of present-day hydrothermal solutions venting from seafloor (section 2.3). 

Several factors such as Cl concentration, water/rock ratio and temperature are important in controlling the chemical composition of the hydrothermal solution interacted with the rocks. For example, water/rock ratio affects the alteration mineralogy (Mottl and Holland, 1978 Seyfried and Mottl, 1982 Shikazono, 1984). For example, at low water/rock ratio, epidote is stable, while chlorite at high water/rock ratio (Shikazono, 1984 Shikazono and Kawahata, 1987). 

In Fig. 1.59 the relationship between temperature and concentration of elements (Zn, Ba) at constant Cl concentration which is equal to that of seawater obtained by the experimental studies and analytical data on natural hydrothermal solution (geothermal water) are shown. It is seen that the concentrations of base-metal elements (Zn, Fe, Mn, Cu, Pb) and Ba increase with increasing of temperature. Concentrations of these... 

Figure 1.56. Relationship between the zinc and Cl concentration in geothermal waters and hydrothermal solution experimentally interacted with rocks (Shikazono, 1988c).

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