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A thermodynamic prediction on the stability of the nukundamite + chalcopyrite and bornite + pyrite assemblages

Published online by Cambridge University Press:  05 July 2018

Shoji Kojima
Affiliation:
Institute of Mineralogy, Petrology and Economic Geology, Faculty of Science, Tohoku University, Aoba 980, Sendai, Japan
Teiichi Ueno
Affiliation:
Department of Earth Sciences, Fukuoka University of Education, Munakata 811-41, Fukuoka, Japan

Abstract

A thermodynamic prediction of the Gibbs free energy of formation (ΔGfo) of nukundamite (empirical composition Cu5.5FeS6.5) was made in order to specify whether the nukundamite + chalcopyrite or the bornite + pyrite assemblage is stable in the Cu-Fe-S system. The results of calculations using previously reported data of ΔGfo values of some Cu-Fe-sulphide minerals in equilibrium with nukundamite indicate that the total free energy of the nukundamite + chalcopyrite assemblage is appreciably higher than that of the bornite + pyrite assemblage in the temperature range 250–400°C. This means that nukundamite + chalcopyrite is a metastable assemblage under common ore-forming conditions.

The occurrence of nukundamite is not uncommon in the Fijian kuroko deposits in contrast to the Japanese kuroko deposits. A thermochemical treatment for this phenomenon leads to the interpretation that the black ore containing nukundamite in the Fijian deposit was formed under relatively highsulphidation and low-pH conditions. This suggestion is in good agreement with the present experimental result that the bornite + pyrite assemblage was produced in the temperature range 350–250°C by using near-neutral hydrothermal solutions.

Type
Mineralogy
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1994

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References

Barton, P. B., Jr. and Skinner, B. J. (1979) Sulfide mineral stabilities. In Geochemistry of Hydrothermal Ore Deposits, 2nd edn. (H. L. Barnes, ed.), 278-403, Wiley-Interscience, New York.Google Scholar
Bourcier, W. L. and Barnes, H. L. (1987) Rocking autoclaves for hydrothermal experiments I. Fixed-volume systems. In Hydrothermal Experimental Techniques (G. C. Ulmer and H. L. Barnes, eds.), 189-215, Wiley-Interscience, New York.Google Scholar
Busey, R. H. and Mesmer, R. E. (1978) Thermo-dynamic quantities for the ionization of water in sodium chloride media to 300°C. J. Chem. Eng. Data, 23, 175–6.CrossRefGoogle Scholar
Clark, A. H. (1970) An occurrence of the assemblage, native sulfur-covellite-'Cu5.5FeS6 5', Aucanquil-cha, Chile. Amer. Mineral, 55, 913–8.Google Scholar
Colley, H. and Rice, C. N. (1975) A kuroko-type ore deposit in Fiji. Econ. Geol, 70, 1373–86.CrossRefGoogle Scholar
Craig, J. R. and Barton, P. B., Jr. (1973) Thermo-chemical approximations for sulfosaits. Econ. Geol, 68, 493–506.CrossRefGoogle Scholar
Czamanske, G. K. (1974) The FeS content of sphalerite along the chalcopyrite-pyrite-bornite sulfur fugacity buffer. Econ. Geol, 69, 1328–34.CrossRefGoogle Scholar
Drummond, S. E. (1981) Boiling and mixing of hydrothermal fluid: Chemical effects on mineral precipitation. Unpubl. Ph. D. Thesis, Penn. State Univ., 380 pp.Google Scholar
Eldridge, C. S., Barton, P. B., Jr. and Ohmoto, H. (1983) Mineral textures and their bearing on formation of the kuroko orebodies. Econ. Geol. Mon., 5, 241–81.Google Scholar
Frenzel, G. and Ottemann, J. (1967) Eine Sulfidpar-agenese mit kupferhaltigem Zonarpyrit von Nukundamu/Fiji. Mineral. Deposita, 1, 307—16.Google Scholar
Helgeson, H. C, Kirkham, D. H. and Flowers, G. C. (1981) Theoretical prediction of the thermody-namic behavior of aqueous electrolysis at high pressures and temperatures. IV. Calculation of activity coefficients, and apparent molal and standard and relative partial molal properties to 600°C and 5 kb. Amer. J. Set, 281, 1249–516.Google Scholar
Kajiwara, Y. (1970) Gypsum-anhydrite ores and associated minerals from the Motoyama deposits of the Hanawa mine. In Volcanism and Ore Genesis (T. Tatsumi, ed.), Univ. Tokyo Press, Tokyo, 207-13.Google Scholar
Kojima, S. and Ohmoto, H. (1991) Hydrothermal synthesis of wurtzite and sphalerite at T = 350°-250°C. Mining Geol, 41, 313–27.Google Scholar
Kojima, S. and Sugaki, A. (1985) Phase relations in the Cu-Fe—Zn-S system between 500° and 300°C under hydrothermal conditions. Econ. Geol, 80, 158–71.CrossRefGoogle Scholar
Matsukuma, T. and Horikoshi, E. (1970) Kuroko deposits in Japan, a review. In Volcanism and Ore Genesis (T. Tatsumi, ed.), Univ. Tokyo Press, Tokyo, 153-79.Google Scholar
Merwin, H. E. and Lombard, R. H. (1937) The system Cu-Fe-S. Econ. Geol, 32, 203–84.CrossRefGoogle Scholar
Montoya, J. W. and Hemley, J. J. (1975) Activity relations and stabilities in alkali feldspar and mica alteration reactions. Econ. Geol., 70, 577—83.Google Scholar
Mukaiyama, H. and Izawa, E. (1970) Phase relations in the Cu—Fe—S system: The copper deficient part. In Volcanism and Ore Genesis (T. Tatsumi, ed.), Univ. Tokyo Press, Tokyo, 339-55.Google Scholar
Murowchick, J. B. and Barnes, H. L. (1987) Effects of temperature and degree of supersaturation on pyrite morphology. Amer. Mineral., 11, 1241-50.Google Scholar
Naumov, G. B., Ryzhenko, B. N. and Khodakovsky, I. L. (1974) Handbook of thermodynamic data. U.S. Geol. Survey Rept. USGS-WRD-74-001, 328pp.Google Scholar
Ohmoto, H., Mizukami, M., Drummond, S. E., Eldridge, C. S., Pisutha-Arnond, V. and Lenagh, T. C. (1983) Chemical processes of kuroko formation. Econ. Geol. Mon., 5, 570–604.Google Scholar
Rice, C. M., Atkin, D., Bowles, J. F. W. and Criddle, A. J. (1979) Nukundamite, a new mineral, and idaite. Mineral. Mag., 43, 193–200.CrossRefGoogle Scholar
Robie, R. A., Hemingway, B. S. and Fisher, J. R. (1978) Thermodynamic properties of minerals and related substances at 298.15°K (25°C) and one atmosphere (1.013 bars) and at higher temperatures. U.S. Geol. Surv. Bull., 1452.Google Scholar
Robie, R. A., Wiggins, L. B., Barton, P. B., Jr. and Hemingway, B. S.(1985) Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4). J. Chem. Thermodynamics, 17, 481–8.CrossRefGoogle Scholar
Roseboom, E. H., Jr. and Kullerud, G. (1958) The solidus in the system Cu—Fe—S between 400°C and 800°C. Carnegie Inst. Wash. Year Book, 57, 222–7.Google Scholar
Schneeberg, E. P. (1973) Sulfur fugacity measure-ments with the elecrochemical cell Ag|AgI|Ag2+xS,/s2. Econ. Geol. 68, 507-17.Google Scholar
Shima, H., Ueno, H. and Nakamura, Y. (1982) Synthesis and phase studies on sphalerite solid solution — the systems Cu—Fe-Zn-S and Mn-Fe-Zn—S. Japan. Assoc. Mineral. Petrol. Econ. Geol., Spec. Issue 3, 271-80 (in Japanese).Google Scholar
Shimazaki, Y. (1974) Ore minerals of the kuroko-type deposits. Soc. Mining Geol. Japan, Spec. Issue 5, 311-22.Google Scholar
Sugaki, A., Shima, H., Kitakaze, A. and Harada, H. (1975) Isothermal phase relations in the system Cu-Fe-S under hydrothermal conditions at 35O°C and 300°C. Econ. Geol., 70, 806–23.CrossRefGoogle Scholar
Sugaki, A., Kitakaze, A. and Hayashi, K. (1981) Synthesis of minerals in the Cu-Fe-Bi—S system under hydrothermal condition and their phase relations. Bull. Mineral, 104, 484–95.Google Scholar
Sugaki, A., Kitakaze, A., and Ueno, T. (1982) Hydrothermal syntheses of minerals in the system Cu-Fe-S and their phase equilibrium at 400°C and 500°C. Japan. Assoc. Mineral. Petrol. Econ. Geol, Spec. Issue, 3, 257-69 (in Japanese).Google Scholar
Sugaki, A., Kitakaze, A., and Hayashi, K. (1984) Hydrothermal synthesis and phase relations of the polymetallic system, especially on the Cu-Fe-Bi-S system. In Materials Science of the Earth's Interior (I. Sunagawa, ed.), TERRAPUB, Tokyo, 543-83.Google Scholar
Takahashi, T. and Suga, K. (1974) Geology and ore deposits of the Hanaoka Kuroko belt, Akita Prefecture. Soc. Mining Geol. Japan, Spec. Issue 6, 101-13.Google Scholar
Takeuchi, T., Nambu, M., Suzuki, M. and Okada, K.(1956) Germanium bearing black ores from the Kamikita mine, Aomori Prefecture. Mining Geol, 6, 231–43. (in Japanese).Google Scholar
Toulmin, P.,U.I. and Barton, P. B., Jr. (1964) A thermodynamic study of pyrite and pyrrhotite. Geochim. Cosmochim. Ada, 28, 641—71.Google Scholar
Yamaoka, K. and Asakura, E. (1974) Metallic ore minerals and associated clay minerals from the Kuroko deposits in the Nishi-Aizu district, Fukushima Prefecture, Japan. Soc. Mining Geol. Japan, Spec. Issue 6, 363—70.Google Scholar
Yund, R. A. and Kullerud, G. (1966) Thermal stability of assemblages in the Cu-Fe-S system. J. Petrol, 7, 454–88.CrossRefGoogle Scholar