Hostname: page-component-78c5997874-lj6df Total loading time: 0 Render date: 2024-11-10T11:02:48.046Z Has data issue: false hasContentIssue false
  • English
  • Français

The formation of rhodochrosite–smithsonite (MnCO3–ZnCO3) solid-solutions at 5°C

Published online by Cambridge University Press:  05 July 2018

Michael E. Böttcher
Michael E. Böttcher*
Affiliation:
Geochemical Institute, Georg-August-University, Goldschmidtstr.1, D-37077 Göttingen, Germany
Get access Rights & Permissions [Opens in a new window]

Abstract

MnxZn(1−x)CO3 solid-solutions were prepared at 5°C by precipitation from metal-bearing bicarbonate solutions. The solids were identified by X-ray powder diffraction and infrared spectroscopy. Zn2+ ions substitute extensively for Mn2+ ions in the crystal lattice of anhydrous rhombohedral carbonates. Throughout the 24 h during which the experiments were conducted, the aqueous solutions remained undersaturated with respect to pure oxides, sulphates, hydroxides and hydroxysulphates. The solutions, however, were supersaturated with MnxZn(1−x)CO3 of any given composition. Besides the anhydrous rhombohedral carbonates, Zn4(OH)2(CO3)3·4H2O was precipitated from an aqueous solution with initially high Zn2+ concentration. The negative logarithm of the solubility product of Zn4(OH)2(CO3)3·4H2O was estimated theoretically to be 43.9 (25°C). Remaining saturation with respect to Zn4(OH)2(CO3)3·4H2O was calculated accordingly. The suggestion is made that hydrated zinc hydroxycarbonate is metastable under the experimental conditions used here, but that it should transform into anhydrous carbonates.

Keywords

rhodochrositesmithsonitesolid-solutionszinc hydroxycarbonatesynthesis
Type
Mineralogy
Information
Mineralogical Magazine , Volume 59 , Issue 396 , September 1995 , pp. 481 - 488
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1995

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

*

Present address: Institute of Chemistry and Biology of the Marine Environment (ICBM), Microbiogeochemistry, Carl von Ossietzky University, P.O. Box 2503, D-26111 Oldenburg, Germany

References

Ball, J.W., Nordstrom, D.K. and Zachmann, D.W. (1987) WATEQ-4F-A personal computer Fortran translation of the geochemical model WATEQ2 with revised data base. U.S. Geol. Sum. Open-File Rep. 87-50.Google Scholar
Birch, W.D. (1986) Zinc-manganese carbonates from Broken Hill, New South Wales. Mineral. Mag., 50, 49–53.CrossRefGoogle Scholar
Bottcher, M.E. (1993) Experimental investigations of metal-enrichment reactions from aqueous solutions with relevance to ore deposits, with special regard to the formation of rhodochrosite (MnC03) (in German). Dr.rer.nat. thesis, Georg-August-University, Gottingen.Google Scholar
Bottcher, M.E. and Usdowski, E. (1990) An estimation of dissociation constants for Mn(II) complexes in aqueous solutions up to 300°C. Z. Phys. Chem. N.F., 167, 81–6.CrossRefGoogle Scholar
Bottcher, M.E., Gehlken, P.-L., Birch, W.D., Usdowski, E. and Hoefs, J. (1993) The rhodochrosite-smithsonite solid-solution series from Broken Hill (NSW), Australia: Geochemical and infrared spec-trosopic investigations. Neues Jahrb. Mineral., Mh., 352-62.Google Scholar
Bottcher, M.E., Gehlken, P.-L., and Usdowski, E. (1992) Infrared spectroscopic investigations of the calcite-rhodochrosite and parts of the calcite-magnesite mineral series. Contrib. Mineral. Petrol., 109, 304–6.CrossRefGoogle Scholar
Effenberger, H., Mereiter, K. and Zemann, J. (1981) Crystal structure refinements of magnesite, calcite, rhodochrosite, siderite, smithsonite and dolomite, with discussion of some aspects of the stereochemistry of calcite-type carbonates. Z. Kristall., 156, 233–43.Google Scholar
Feitknecht, W. and Oswald, H.R. (1966) Uber die Hydoxidcarbonate des Zinks. Helv. Chim. Ada, 49, 335–43.Google Scholar
Glynn, P.D. and Reardon, E.J. (1990) Solid-solution aqueous-solution equilibria: Thermodynamic theory and representation. Amer. J. Sci., 290, 164–201.CrossRefGoogle Scholar
Jambor, J.L. (1964) Studies of basic copper and zinc carbonates: I. Synthetic zinc carbonates and their relationship to hydrozincite. Can. Mineral., 8, 92–108.Google Scholar
Johnson, J.W., Oelkers, E.H. and Helgeson, H.C. (1992) SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0° to 1000°C. Comp. Geosci, 18, 899–947.CrossRefGoogle Scholar
Kaushansky, P. and Yariv, S. (1986) The interactions between calcite particles and aqueous solutions of magnesium, barium and zinc chlorides. Appl. Geochem., 1, 607–18.CrossRefGoogle Scholar
Kharaka, Y.K., Gunter, W.D., Aggarwal, P.K., Perkins, B.H. and DeBraal, J.D. (1988) SOLMINEQ.88: A computer program for geochemical modelling of water—rock interactions. U.S. Geol. Surv. Wat.-Res. Inv. Rep., 88-4227.Google Scholar
Konigsberger, E., Hausner, R. and Gamsjager, H. (1991) Solid-solute phase equilibria in aqueous solutions. V. The system CdCO3-CaCO3-CO2-H2O. Geochim. Cosmochim. Ada, 55, 3505–14.CrossRefGoogle Scholar
Kraut, K. (1897) Kohlensaures Zinkoxyd. anorg. Chem., 13, 1–15.CrossRefGoogle Scholar
La Iglesia, A. and Felix, J.F. (1994) Estimation of thermodynamic properties of mineral carbonates at high and low temperatures from the sum of the polyhedral contributions. Geochim. Cosmochim. Acta, 58, 3983–91.CrossRefGoogle Scholar
Lesht, D. and Bauman, J.E. (1978) Thermodynamics of the manganese(II) bicarbonate system. Inorg. Chem., 17, 3332–4.CrossRefGoogle Scholar
Lorens, R.B. (1981) Sr, Cd, Mn and Co distribution coefficients in calcite as a function of precipitation rate. Geochim. Cosmochim. Ada, 45, 553–61.CrossRefGoogle Scholar
Mann, A.W. and Deutscher, R.L. (1980) Solution geochemistry of lead and zinc in water containing carbonate, sulphate and chloride ions. Chem. Geol, 29, 293–311.CrossRefGoogle Scholar
Plummer, L.N. and Busenberg, E. (1982) The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0° and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O. Geochim. Cosmochim. Ada, 46, 1011–40.CrossRefGoogle Scholar
Ryan, M.R.. and Bauman, J.E. (1978) Thermodynamics of the zinc bicarbonate system. Inorg. Chem., 17, 3329–32.CrossRefGoogle Scholar
Schindler, P.W. (1967) Heterogeneous equilibria involving oxides, hydroxides, carbonates, and hydroxide carbonates. In Equilibrium Concepts in Natural Water Systems Stumm, W. (ed.). Adv. Chem. Ser., ACS, 67, 196–221.CrossRefGoogle Scholar
Schindler, P., Reinert, M. and Gamsjager, H. (1969) Zur Thermodynamik der Metallcarbonate. 3. Loslich-keitskonstanten und Freie Bildungsenthalpien von ZnCO3 und Zn5(OH)6(CO3)2 bei 25°C. Helv. Chim. Ada, 52, 2327–32.CrossRefGoogle Scholar
Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Harlow, I., Bailey, S.M., Churney, K.L. and Nuttall, R.L. (1982) The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C] and C2 organic substances in SI units. J. Phys. Chem. Ref. Data, 11 Suppl. 2.Google Scholar
Wiwchar, B.W., Perkins, B.H. and Gunter, W.D. (1988) Solmineq.88 PC/Shell, user manual (Alberta Res. Counc. (ed.)).Google Scholar
Zachara, J.M., Kittrick, J.A., Dake, L.S. and Harshi, J.B. (1989) Solubility and surface spectroscopy of zinc precipitates on calcite. Geochim. Cosmochim. Ada, 53, 9–19.CrossRefGoogle Scholar