Chalcopyrite dissolution rate law from pH 1 to 3

Authors

  • P. ACERO CTJA and IDAEA Institute of Environmental Assessment and Water Research - CSIC. C/ Jordi Girona 18-26, 08034 Barcelona, Spain Petrology and Geochemistry Area, Earth Sciences Department, University of Zaragoza. C/ Pedro Cerbuna 12, 50009 Zaragoza, Spain.
  • J. CAMA CTJA and IDAEA Institute of Environmental Assessment and Water Research - CSICc/ Jordi Girona 18-26, 08034 Barcelona, Spain
  • C. AYORA CTJA and IDAEA Institute of Environmental Assessment and Water Research - CSIC. C/ Jordi Girona 18-26, 08034 Barcelona, Spain
  • M.P. ASTA CTJA and IDAEA Institute of Environmental Assessment and Water Research - CSIC. C/ Jordi Girona 18-26, 08034 Barcelona, Spain

DOI:

https://doi.org/10.1344/105.000001444

Keywords:

Acid Mine Drainage, Kinetics, Flow-through, Sulfides

Abstract

Chalcopyrite dissolution kinetics in the pH range of 1 to 3 were studied by means of long-term flow-through experiments to obtain a dissolution rate law which can be coupled with reactive transport models to forecast Acid Rock Drainage. In the range of conditions under study, the rate of chalcopyrite dissolution is only slightly dependent on hydrogen ion activity, increasing with decreasing pH. The steady-state dissolution rates obtained in the present study were combined with earlier results presented by Acero et al. (2007a) to obtain the following expression for chalcopyrite dissolution rate law: where Rchalcopyrite is the chalcopyrite dissolution rate (mol m-2 s-1), aH+ is the activity of hydrogen ion in solution, R is the gas constant (kJ mol-1 K-1) and T is the temperature (K). This expression can applied through a wide range of environmental conditions similar to the ones found in systems affected by acid drainage. In agreement with earlier chalcopyrite kinetic studies, iron was released to solution preferentially over copper and sulfur, compared with the stoichiometry of the pristine mineral. Consistently, XPS examination of the samples showed that reacted surfaces were enriched in sulfur and copper (relative to iron) compared with the initial, pristine chalcopyrite surface. However, this surface layer does not exert any passivating effect on chalcolpyrite dissolution and the kinetics of the overall process in the long term seems to be surface-controlled.

References

Acero, P., Cama, J., Ayora, C., 2007a. Kinetics of chalcopyrite dissolution at pH 3. European Journal of Mineralogy, 19(2), 173-182.

Acero, P., Cama, J., Ayora, C., 2007b. Sphalerite dissolution kinetics in acidic environment. Applied Geochemistry, 22(9), 1872-1883.

Acero, P., Cama, J., Ayora, C., 2007c. Rate law for galena dissolution in acidic environment. Chemical Geology, 245, 219-229.

Adebayo, A., Ipinmoroti, K., Ajayi, O., 2003. Dissolution kinetics of chalcopyrite with hydrogen peroxide in sulphuric acid medium. Chemical and Biochemical Engineering Quarterly, 17(3), 213-218.

Almodóvar, G., Sáez, R., Pons, J., Maestre, A., Toscano, M., Pascual, E., 1998. Geology and genesis of the Aznalcóllar massive sulphide deposits, Iberian Pyrite Belt, Spain. Mineralum Deposita, 33(1-2), 111-136.

Antonijevic, M., Bogdanovic, G., 2004. Investigation of the leaching of chalcopyritic ore in acidic solutions. Hydrometallurgy, 73(3-4), 245-256.

Antonijevic, M., Jankovic, Z., Dimitrijevic, M., 2004. Kinetics of chalcopyrite dissolution by hydrogen peroxide in sulphuric acid. Hydrometallurgy, 71(3-4), 329-334.

Aydogan, S., Ucar, G., Canbazoglu, M., 2006. Dissolution kinetics of chalcopyrite in acidic potassium dichromate solution. Hydrometallurgy, 81(1), 45-51.

Barrante, J., 1974. Applied Mathematics for Physical Chemistry. Prentice-Hall, New Jersey, Englewood Cliffs, 173 pp.

Biegler, T., Horne, M., 1985. The electrochemistry of surface oxidation of chalcopyrite. Journal of the Electrochemical Society, 132(6), 1363-1369.

Brunauer, S., Emmet, P., Teller, E., 1938. Adsorption of gases in multimolecular layers. Journal of the American Chemical Society, 60, 309-319.

Buckley, A., Woods, R., 1984. An X-Ray Photoelectron Spectroscopy study of the oxidation of chalcopyrite. Australian Journal of Chemistry, 37(12), 2403-2413.

Cama, J., Acero, P., 2005. Dissolution of minor sulphides present in a pyritic sludge at pH 3 and 25ºC. Geologica Acta, 3, 15-26.

Cama, J., Acero, P., Ayora, C., Lobo, A., 2005. Galena surface reactivity at acidic pH and 25 ºC based on flow-through and in situ AFM experiments. Chemical Geology, 214(3-4), 309-330.

Çolak, S., Alkan, M., Kocakerim, M., 1987. Dissolution kinetics of chalcopyrite containing pyrite in water saturated with chlorine. Hydrometallurgy, 18(2), 183-193.

De Giudici, G., Zuddas, P., 2001. In situ investigation of galena dissolution in oxygen saturated solution: Evolution of surface features and kinetic rate. Geochimica et Cosmochimica Acta, 65(9), 1381-1389.

Devi, N., Madhuchhanda, M., Rao, K., Rath, P., Paramguru, R., 2000. Oxidation of chalcopyrite in the presence of manganese dioxide in hydrochloric acid medium. Hydrometallurgy, 57(1), 57-76.

Domènech, C., de Pablo, J., Ayora, C., 2002. Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain). Chemical Geology, 190(1-4), 339-353.

Dutrizac, J., 1981. The dissolution of Chalcopyrite in FerricSulfate and Ferric-Chloride Media. Metallurgical Transactions B-Process Metallurgy, 12(2), 371-378.

Dutrizac, J., 1990. Elemental sulfur formation during the ferricchloride leaching of chalcopyrite. Hydrometallurgy, 23(2-3),

-176.

Fairthorne, G., Fornasiero, D., Ralston, J., 1997. Effect of oxidation on the collectorless flotation of chalcopyrite. International Journal of Mineral Processing, 49(1-2), 31-48.

Farquhar, M., Wincott, P., Wogelius, R., Vaughan, D., 2003. Electrochemical oxidation of the chalcopyrite surface: an XPS and AFM study in solution at pH 4. Applied Surface Science, 218(1-4), 34-43.

Hackl, R., Dreisinger, D., Peters, E., King, J., 1995. Passivation of Chalcopyrite during oxidative leaching in sulfate media. Hydrometallurgy, 39(1-3), 25-48.

Harmer, S.L., Thomas, J.E., Fornasiero, D., Gerson, A. R., 2006. The evolution of surface layers formed during chalcopyrite leaching. Geochimica et Cosmochimica Acta, 70(17), 4392-4402.

Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M., 2000. A model for ferrous-promoted chalcopyrite leaching. Hydrometallurgy, 57(1), 31-38.

Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M., 2001. Enhancement of chalcopyrite leaching by ferrous ions in acidic ferric sulfate solutions. Hydrometallurgy, 60(3), 185-197.

Holliday, R., Richmond, W., 1990. An electrochemical study of the oxidation of chalcopyrite in acidic solution. Journal of Electroanalytical Chemistry, 288(1-2), 83-98.

Janzen, M., Nicholson, R., Scharer, J., 2000. Pyrrhotite reaction kinetics: Reaction rates for oxidation by oxygen, ferric iron, and for nonoxidative dissolution. Geochimica et Cosmochimica Acta, 64(9), 1511-1522.

Klauber, C., 2003. Fracture-induced reconstruction of a chalcopyrite (CuFeS2) surface. Surface and Interface Analysis, 35(5), 415-428.

Klauber, C., Parker, A., van Bronswijk, W., Watling, H., 2001. Sulphur speciation of leached chalcopyrite surfaces as determined by X-ray photoelectron spectroscopy. International Journal of Mineral Processing, 62(1-4), 65-94.

Lasaga, A., Soler, J., Ganor, J., Burch, T., Nagy, K., 1994. Chemical weathering rate laws and global geochemical cycles. Geochimica et Cosmochimica Acta, 58(10), 2361-2386.

Lochmann, J., Pedlik, M., 1995. Kinetic anomalies of dissolution of sphalerite in ferric sulfate solution. Hydrometallurgy, 37(1), 89-96.

Lu, Z., Jeffrey, M., Lawson, F., 2000. The effect of chloride ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy, 56(2), 189-202.

Mikhlin, Y., Tomashevich, Y., Asanov, I., Okotrub, A., Varnek, V., Vyalikh, D., 2004. Spectroscopic and electrochemical characterization of the surface layers of chalcopyrite (CuFeS2) reacted in acidic solutions. Applied Surface Science, 225(1-4), 395-409.

Munoz, P., Miller, J., Wadsworth, M., 1979. Reaction-mechanism for the acid ferric sulfate leaching of chalcopyrite. Metallurgical Transactions B-Process Metallurgy, 10(2), 149-158.

Nordstrom, D., 2000. Aqueous Redox Chemistry and the Behavior of Iron in Acid Mine Waters. In: Wilkin, R.D., Ford, R. (eds.). Proceedings of the Workshop on Monitoring Oxidation-Reduction Processes for Ground-water Restoration. Enviromental Protection Agency, EPA/600/R-02/002, 43-47.

Palmer, B., Nebo, C., Rau, M., Fuerstenau, M., 1981. Rate phenomena involved in the dissolution of chalcopyrite in chloride-bearing lixiviants. Metallurgical Transactions BProcess Metallurgy, 12(3), 595-601.

Parker, A., Paul, R., Power, G., 1981. Electrochemistry of the oxidative leaching of copper from chalcopyrite. Journal of Electroanalytical Chemistry, 118(FEB), 305-316.

Parkhurst, D., 1995. User’s guide to PHREEQC: A computer program for speciation, reaction path, advective-transport, and inverse geochemical calculations. U.S. Geological Survey, Water-Resources Investigations Report 95-4227, 143 pp.

Price, D., Warren, G., 1986. The influence of silver ion on the electrochemical response of chalcopyrite and other sulfide electrodes in sulfuric-acid. Hydrometallurgy, 15(3), 303-324.

Rimstidt, J., Chermak, J., Gagen, P., 1994. Rates of reaction of galena, sphalerite, chalcopyrite and arsenopyrite with Fe(III) in acidic solutions. In: Alpers, C.N., Blowes, D.W. (eds.). Environmental geochemistry of sulfide oxidation. American Chemical Symposium, Series 550, Washington DC, 2-13.

Rosso, K., Vaughan, D.J., 2006. Reactivity of Sulfide Mineral Surfaces. In: Vaughan, D.J. (ed.). Sulfide Mineralogy and Geochemistry. Reviews in Mineralogy and Geochemistry (61), Mineralogical Society of America, Chantilly, Virginia, 557-607.

Salmon, S.U., Malmström, M.E., 2006. Quantification of mineral dissolution rates and applicability of rate laws: Laboratory studies of mill tailings. Applied Geochemistry, 21(2), 269-288.

Scharer, J., Nicholson, R., Halbert, B., Snodgrass, W., 1994. A computer program to assess acid generation in pyritic tailings. In: Alpers, C.N., Blowes, D.W. (eds.). Environmental geochemistry of sulfide oxidation. American Chemical Symposium Series 550, Washington DC, 132-152.

Todd, E., Sherman, D., Purton, J., 2003. Surface oxidation of chalcopyrite (CuFeS2) under ambient atmospheric and aqueous (pH 2-10) conditions: Cu, Fe L- and OK-edge X-ray spectroscopy. Geochimica et Cosmochimica Acta, 67(12), 2137-2146.

Velásquez, P., Leinen, D., Pascual, J., Ramos-Barrado, J. R., Grez, P., Gómez, H., Schrebler, R., Del Río, R., Córdova, R., 2005. A chemical, morphological, and electrochemical (XPS, SEM/EDX, CV, and EIS) analysis of electrochemically modified electrode surfaces of natural chalcopyrite (CuFeS2) and pyrite (FeS2) in alkaline solutions. Journal of Physical Chemistry B, 109(11), 4977-4988.

Weisener, C., Smart, R., Gerson, A., 2003. Kinetics and mechanisms of the leaching of low Fe sphalerite. Geochimica et Cosmochimica Acta, 67(5), 823-830.

Weisener, C., Smart, R., Gerson, A., 2004. A comparison of the kinetics and mechanism of acid leaching of sphalerite containing low and high concentrations of iron. International Journal of Mineral Processing, 74(1-4), 239-249.

Published

2009-01-11

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