Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-23T13:02:33.308Z Has data issue: false hasContentIssue false
  • English
  • Français

Concentric zoning patterns in crystallizing (Cd,Ca)CO3 solid solutions from aqueous solutions

Published online by Cambridge University Press:  05 July 2018

Á. Fernández-González ,
M. Prieto ,
A. Putnis  and
S. López-Andrés
Á. Fernández-González
Affiliation:
Departamento de Geología, Universidad de Oviedo, 33005-Oviedo, Spain
M. Prieto
Affiliation:
Departamento de Geología, Universidad de Oviedo, 33005-Oviedo, Spain
A. Putnis
Affiliation:
Institut für Mineralogie, Universität Münster, D-48149 Münster, Germany
S. López-Andrés
Affiliation:
Departamento de Cristalografía y Mineralogίa, Universidad Complutense, 28040-Madrid, Spain
Get access Rights & Permissions [Opens in a new window]

Abstract

Otavite-calcite solid solutions have been synthesized to investigate the factors which control the patterns of compositional zoning. The equilibrium partitioning of otavite between the aqueous and the solid phase can be described by means of a function X CdCO3 (X Cd,aq)eq, which relates the solid mole fraction and the aqueous activity fraction of Cd. According to this function, there is a strong preferential partitioning of Cd towards the solid. A set of experiments starting with parent solutions with different Cd2+/Ca2+ ratios was carried out. In these experiments nucleation takes place at high supersaturations and the Cd2+ and Ca2+ ions tend to be laid down in a ratio which deviates from the equilibrium distribution. Experimental nucleation data can be fitted to a curve X CdCO3 (X Cd,aq)ef of the same functionality as that for equilibrium.

After nucleation, supersaturation decreases as the crystals grow. During this process, substituting ions are not incorporated into the solid in the same stoichiometric proportion as in the aqueous solution. Therefore, crystal and fluid compositions tend to vary as growth proceeds and this evolution is registered as a compositional zoning. The curves X CdCO3 (X Cd,aq)eq and X CdCO3 (X Cd,aq)ef confine the reaction path corresponding to the growth process. Here, these curves are used to account for the observed zoning patterns.

Keywords

solid solutionotavitecalcitecrystal growthzoningoscillatory zoning
Type
Research Article
Information
Mineralogical Magazine , Volume 63 , Issue 3 , June 1999 , pp. 331 - 343
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1999

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.)

References

Allègre, C.J., Provost, A. and Jaupart, C. (1981) Oscillatory zoning: A pathological case of crystal growth. Nature, 294, 223–8.CrossRefGoogle Scholar
Borodin, V.L., Lyntin, V.I., Ilyukhin, V.V. and Belov, N.V. (1979) Isomorphous calcite-otavite series. Soviet Phys. Dokl., 24, 226–7.Google Scholar
Chang, L.L.Y. and Brice, W.R. (1971) Subsolidus phase relations in the system calcium carbonate-cadmium carbonate. Amer. Mineral., 56, 338–41.Google Scholar
Chiarello, R.P., Sturchio, N.C., Grace, J.D., Geissbuhler, P., Sorensen, L.B., Cheng, L. and Xu, S. (1997) Otavite-calcite solid-solution formation at the calcite-water interface studied in situ by synchrotron X-ray scattering. Geochim. Cosmochim. Acta, 61, 1467–74.CrossRefGoogle Scholar
Davis, J.A., Fuller, C.C. and Cook, A.D. (1987) A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation. Geochim. Cosmochim. Acta, 51, 1477–90.CrossRefGoogle Scholar
Fernández-Díaz, L., Putnis, A., Prieto, M. and Putnis, C. (1996) The role of magnesium in the crystallization of calcite and aragonite in a porous medium. J. Sed. Res., 66, 482–91.Google Scholar
Franke, W., Ittyachen, M.A. and Mohanan Pillai, K. (1979) Scanning electron microscopic studies on different habits of gel grown manganese carbonate crystals. Pramaãna, 13, 293–97.CrossRefGoogle Scholar
Glynn, P.D., Reardon, E.J., Plummer, L.N. and Busenberg, E. (1990) Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems. Geochim. Cosmochim. Acta, 54, 267–82.CrossRefGoogle Scholar
Gray, P. and Scott, S.K. (1990) Chemical Oscillations and Instabilities: Non-linear Chemical Kinetics. Oxford University Press, UK.Google Scholar
Halden, N.M. (1996) Determination of Lyapounov exponents to characterize the oscillatory distribution of trace elements in minerals. Canad. Mineral., 34, 1127–35.Google Scholar
Heijnen, W.M.M. (1985) The morphology of gel grown calcite. Neues Jahrb. Mineral. Mh., 357–71.Google Scholar
Henisch, H.K. (1988) Crystals in Gels and Liesegang Rings. Cambridge University Press, UK.CrossRefGoogle Scholar
Jamtveit, B., Ragnarsdottir, K.V. and Wood, J. (1995) On the origin of zoned grossular-andradite garnets in hydrothermal systems. Eur. J. Mineral., 7, 1399–410.CrossRefGoogle Scholar
Königsberger, E., Hausner, R. and Gamsjäger, H. (1991) Solid-solute phase equilibria in aqueous solution. V: The system CdCO3-CaCO3-H2O. Geochim. Cosmochim. Acta, 55, 3505–14.CrossRefGoogle Scholar
Lippmann, F. (1980) Phase diagrams depicting aqueous solubility of binary carbonate systems. Neues Jahrb. Mineral. Abh., 139, 1–25.Google Scholar
Lloyd, G.E. (1987) Atomic number and crystallographic contrast images with the SEM: A review of backscattered electron techniques. Mineral. Mag., 51, 3–19.CrossRefGoogle Scholar
Nriagu, J.O. (1980) Cadmium in the Environment, Part I. Ecological Cycling. Wiley-Interscience, New York.Google Scholar
Ortoleva, P., Merino, E., Moore, C. and Chadam, J. (1987) Geochemical self-organization I: Reaction-transport feedbacks and modeling approach. Amer. J. Sci., 287, 979–1007.CrossRefGoogle Scholar
Paquette, J. and Reeder, R.J. (1995) Relationships between surface structure, growth mechanism, and trace element incorporation in calcite. Geochim. Cosmochim. Acta, 59, 735–49.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. Acta, 46, 1011–40.CrossRefGoogle Scholar
Prieto, M., García-Ruiz, J.M. and Amorós, J.L. (1981) Growth of calcite crystals with non-singular faces. J. Cryst. Growth, 52, 864–7.CrossRefGoogle Scholar
Prieto, M., Putnis, A. and Fernaández-Díaz, L. (1993) Crystallization of solid solutions from aqueous solutions in a porous medium: zoning in (Ba,Sr)SO4 . Geol. Mag., 130, 289–99.CrossRefGoogle Scholar
Prieto, M., Putnis, A., Fernaández-Díaz, L. and López-Andrés, S. (1994) Metastability in diffusing-reacting systems. J. Cryst. Growth, 142, 225–35.CrossRefGoogle Scholar
Prieto, M., Fernaández-González, A., Putnis, A. and Fernaández-Díaz, S. (1997) Nucleation, growth and zoning phenomena in crystallizing (Ba,Sr)CO3, Ba(SO4,CrO4), (Ba,Sr)SO4, and (Cd,Ca)CO3 solid solutions from aqueous solutions. Geochim. Cosmochim. Acta, 61, 3383–97.CrossRefGoogle Scholar
Putnis, A., Fernaández-Díaz, L. and Prieto, M. (1992) Experimentally produced oscillatory zoning in the (Ba,Sr)SO4 solid solution. Nature, 358, 743–5.CrossRefGoogle Scholar
Putnis, A., Prieto, M. and Fernaández-Díaz, L. (1995) Fluid supersaturation and crystallization in porous media. Geol. Mag., 132, 1–13.CrossRefGoogle Scholar
Reeder, R.J. (1986) Zoning types and their origins in sedimentary carbonate minerals. In Geochemistry of the Earth's Surface (Rodríguez, R. and Tardy, Y., eds). pp. 740–52. Consejo Sup. Invest. Científicas, Centre Nat. Recher. Scientifique.Google Scholar
Reeder, R.J., Fagioly, R.O. and Meyers, W. (1990) Oscillatory zoning of Mn in solution grown calcite crystals. Earth Sci. Rev., 29, 39–46.CrossRefGoogle Scholar
Shore, M. and Fowler, A.D. (1996) Oscillatory zoning in minerals, a common phenomenon. Canad. Mineral., 34, 1111–26.Google Scholar
Stipp, S.L., Hochella, M.F., Parks, G.A. and Leckie, J.O. (1992) Cd2+ uptake by calcite, solid state diffusion, and the formation of solid solution: Interface processes observed with near-surface sensitive techniques (XPS, LEED, and AES). Geochim. Cosmochim. Acta, 56, 1941–54.CrossRefGoogle Scholar
Stipp, S.L., Parks, G.A., Norddstrom, D.K. and Leckie, J.O. (1993) Solubility-product constant and thermodynamic properties for synthetic otavite, CdCO3(s), and aqueous association constants for the Cd(II)-CO2-H2O system. Geochim. Cosmochim. Acta, 57, 2699–713.CrossRefGoogle Scholar
Tesoreiro, A.J. and Pankow, J.F. (1996) Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite. Geochim. Cosmochim. Acta, 60, 1053–63.CrossRefGoogle Scholar
Wang, Y. and Merino, E. (1992) Dynamic model of oscillatory zoning of trace elements in calcite: Double layer, inhibition, and self-organization. Geochim. Cosmochim. Acta, 56, 587–96.CrossRefGoogle Scholar
Zachara, J.M., Cowan, C.E. and Resch, C.T. (1991) Sorption of divalent metals on calcite. Geochim. Cosmochim. Acta, 55, 1549–62.CrossRefGoogle Scholar