Hostname: page-component-848d4c4894-2xdlg Total loading time: 0 Render date: 2024-07-01T13:23:23.378Z Has data issue: false hasContentIssue false

Assessing the Effect of Dissolved Organic Ligands on Mineral Dissolution Rates: an Example from Calcite Dissolution

Published online by Cambridge University Press:  03 September 2012

Teri DeMaio
Affiliation:
Department of Geology, Temple University, Philadelphia, PA 19122U.S.A.
D. E. Grandstaff
Affiliation:
Department of Geology, Temple University, Philadelphia, PA 19122U.S.A.
Get access

Abstract

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or “protect” the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation.

To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22°C in Na-Ca-HCO3-Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 μm) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (< 50 μM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid.

Type
Research Article
Copyright
Copyright © Materials Research Society 1997

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

REFERENCES

1. Rogers, R. D., Hamilton, M. A., Veen, R. H., and McConnell, J. W. in Scientific Basis for Nuclear Waste Management XIX, edited by Murphy, W. M. and Knecht, D. A. (Materials Research Society, Pittsburgh, 1996), pp. 475482.Google Scholar
2. Chave, K.E., Science 148, 1723 (1965).Google Scholar
3. Thomas, M. M. and Longo, J. M., in Water-Rock Interaction V (Orkustofnun, Reykjavik, 1986), pp. 573576.Google Scholar
4. Teng, H. and Grandstaff, D. E., in Scientific Basis for Nuclear Waste Management XIX, edited by Murphy, W. M. and Knecht, D. A. (Materials Research Society, Pittsburgh, 1996), pp. 249256.Google Scholar
5. Welch, S. A. and Ullman, W. J., in Water-Rock Interaction, edited by Kharaka, Y. K. and Maest, A. S. (Balkema, Rotterdam, 1992), pp. 127132.Google Scholar
6. Grandstaff, D. E., in Rates of Chemical Weathering of Rocks and Minerals, edited by Colman, S. M. and Dethier, D. P. (Academic Press, New York, 1986), pp. 4160.Google Scholar
7. Chou, L., Garrels, R. M., and Wollast, R., Chemical Geology 78, 269 (1986).Google Scholar
8. Berner, R. A. and Morse, J. W., Am. Jour. Science 274, 108, (1974).Google Scholar
9. Sjoberg, E. L. and Rickard, D. T., Geochim. Cosmochim. Acta 48, 485 (1984).Google Scholar
10. Plummer, L. N. and Wigley, T. M. L., Geology 40, 191 (1976).Google Scholar
11. Ball, J. W. and Norstrom, D. K., Users manual for WATEQ4F, with revised thermodynamic data base and test cases for calculating speciation of major, trace, and redox elements in natural waters. U.S. Geol. Survey Open-File Report, 91–183 (1991).Google Scholar
12. Sillén, L. G. and Martell, A. E., Stability Constants (The Chemical Society, London, 1964).Google Scholar
13. Stumm, W. and Morgan, J. J., Aquatic Chemistry (Wiley Interscience, New York, 1996)Google Scholar
14. Maclnnis, I. N. and Brantley, S. L., Geology 56, 1113 (1992).Google Scholar