Technical Papers
Mar 31, 2012

New Unreacted-Core Model to Predict Pyrrhotite Oxidation in Concrete Dams

Publication: Journal of Materials in Civil Engineering
Volume 25, Issue 3

Abstract

Pyrites and pyrrhotites are the most abundant minerals of the iron sulfide group in nature and may be found in the aggregates used to produce concrete. In the presence of water and oxygen, such compounds generate expansive reactions that may have severe structural damages. This is especially critical in concrete dams, given the large volume of material used and the restrictions in movement imposed by the surroundings. In these cases, the definition of adequate rehabilitation programs depends on the prediction of the expansive reaction evolution and the future behavior of the structure. Although models that describe solid particle–gas reactions may be used with this purpose, none were specifically developed to simulate this phenomenon in dams. This paper introduces a new kinetic model based on the unreacted-core model for pyrrhotite oxidation. The comparison of the results obtained with this new model and with the direct application of the unreacted-core model show significant differences. Following an extensive parametric study, a simplified constitutive equation is proposed to estimate the pyrrhotite oxidation kinetics in concrete dams. The estimations performed with this constitutive equation agree with the experimental data obtained in the tests of different particle sizes.

Get full access to this article

View all available purchase options and get full access to this article.

Acknowledgments

The authors thank the UPC—ENDESA Research contract in the continuing investigation on the kinetics of expansive phenomena (Dam Project), and IBERDROLA for the funding and the support given to this research (Horex Project).

References

Andriolo, R. (2007). “Expansion effects of pyrite in the rock matrix of the Rio Descoberto Dam.” Workshop on Chemical Expansion in Concrete Dams and Hydroelectric Projects, ICOLD Committee on Concrete Dams, Spanish Committee on Concrete for Dams and International Journal on Hydropower & Dams, Granada, Spain.
Araújo, G. S. (2008). “The internal sulfate reaction in concrete dams. A proposed methodology of analysis.” Ph.D. thesis, Polytechnic University of Catalunya, Barcelona, Spain, 194 (in Spanish).
Araújo, G. S., López, C. M., Agulló, L., and Aguado, A. (2005). “Funções de predição das expansões de concreto. Aplicação ao caso de barragens.” VIII CONPAT, Asunción, pp. 71–78 (in Spanish).
Brunetaud, X., Divet, L., and Damidot, D. (2008). “Impact of unrestrained delayed ettringite formation-induced expansion on concrete mechanical properties.” Cem. Concr. Res., 38(11), 1343–1348.
Casanova, I., Agulló, L., and Aguado, A. (1996). “Aggregate expansivity due to sulfide oxidation—I. Reaction system and rate model.” Cem. Concr. Res., 26(7), 993–998.
Castellote, M., and Andrade, C. (2008). “Modelling the carbonation of cementitious matrixes by means of the unreacted-core model, UR-CORE.” Cem. Concr. Res., 38(12), 1374–1384.
Chinchón-Payá, S., Aguado, A., and Chinchon, S. (2011). “Degradation of pyrite and pyrrhotite contained in aggregates and the effect of host rock.” Eng. Geol., 127, 75–80.
Deloye, F. (1989). “Action conjuguée du sofre et des alcalins dans les reactions liant-granulats au sein du béton.” Bulletin des Laboratoires des Ponts et Chaussées, Paris, 161, 41–49 (in French).
Espinós, J., Aguado, A., López, C., Campos, A., and Chinchón-Payá, S. (2010). “Expansion studies for the Paso Nuevo dam.” Proc., 2nd Int. Congress on Dam Maintenance and Rehabilitation, Zaragoza, Spain, 143–152.
Fennemore, G. G., Chad Neller, W., and Andy, D. (1998). “Modeling pyrite oxidation in air environments.” Environ. Sci. Technol., 32(18), 2680–2687.
Fernandes, H. M., and Ramalho, M. F. (2001). “Remediation of acid rock drainage at the Poços de Caldas uranium mining site.” Proc., IMWA Symp. (CD-ROM), 1–8.
Finlayson-Pitts, B. J. E., and Pitts, J. N. (1986). Atmospheric chemistry: Fundamentals and experimental techniques, Wiley, New York.
Guerreiro, M., Fernandez, R., Guerreiro, M. J., and Gómez, G. (1991). “Causes of failure of the Fonsagrada Dam.” 17th ICOLD Congress on Large Dams, 43–64.
Ishida, M., and Wen, Y. C. (1968). “Comparison of kinetic and diffusional models for solid-gas reactions.” AIChE J., 14(2), 311–317.
Kunii, D., and Levenspiel, O. (1991). Fluidization engineering, 2nd Ed., Butterworth-Heinemann, Waltham, MA.
LAB Fit Curve Fitting, V7.2.47 [Computer software]. Universidade Federal de Campina Grande, Paraíba, Brazil.
Levenspiel, O. (1972). Chemical reaction engineering, Wiley, New York.
Lowson, R. T. (1982). “Aqueous oxidation of pyrite by molecular oxygen.” Chem. Rev., 82(5), 461–497.
Martinez Roig, J. M., Aguado, A., Agulló, L., and Vázquez, E. (1991). “Diagnosis of the behavior of the Graus and Tabescán dams.” 7th Int. Congress on Large Dams, Viena, Austria, 603–617.
Mbonimpa, M., Aubertin, M., Dagenais, A.-M., Bussière, B., Julien, M., and Kissiova, M. (2002). “Interpretation of field tests to determine the oxygen diffusion and reaction rate coefficients of tailings and soil covers.” In 55th Canadian Geotechnical Conf. and 3Rd joint IAH-CNC and CGS Groundwater Specialty Conf., Niagara Falls, Ontario, 147–154.
McKibben, M. A., and Barnes, H. L. (1986). “Oxidation of pyrite in low temperature acidic solutions: Rate laws and surface textures.” Geochim. Cosmochim. Acta, 50(7), 1509–1520.
Moradzadeh, A., Ardejani, D. F., Shokri, J. B., Sarkheil1, H., and Osanloo, M. (2007). “A method for coal waste disposal site selection for prevention of environmental impacts.” IMWA Symp. 2007: Water in Mining Environments, R. Cidu and F. Frau, eds., Cagliari, Italy, 239–243.
Nicholson, V. R., Gillham, W. R., and Reardon, J. E. (1989). “Pyrite oxidation in carbonate-buffered solution: 2. Rate control by oxide coating.” Geochim. Cosmochim. Acta, 54(2), 395–402.
Oliveira, I. (2011). “Reacción sulfática interna en presas de hormigón cinética del comportamiento.” Ph.D. thesis, Polytechnic University of Catalunya, Barcelona, Spain (in Spanish).
Oliveira, I., Aguado, A., Chinchón-Paya, S., and Chinchón, S. (2011). “Pyrrhotite oxidation kinetics: Host rock influence and the effect of aggregate size on a concrete.” Int. Congress on the Chemistry of Cement, Madrid, Spain.
Park, J. Y., and Levenspiel, O. (1975). “The crackling core model for the reaction of solid particles.” Chem. Eng. Sci., 30(10), 1207–1214.
Ramachandran, A. P., and Smith, M. J. (1977). “A single-pore model for gas-solid noncatalytic reactions.” AIChE. J., 23(3), 353–361.
Rimstidt, D. J., and Vaughan, J. D. (2003). “Pyrite oxidation: A state-of-the-art assessment of the reaction mechanism.” Geochim. Cosmochim. Acta, 67(5), 873–880.
Tagnit-Hamou, A., Saric-Coric, M., and Rivard, P. (2005). “Internal deterioration of concrete by the oxidation of pyrrhotitic aggregates.” Cem. Concr. Res., 35(1), 99–107.
Taylor, W. F. H., Famy, C., and Scrivener, L. K. (2001). “Delayed ettringite formation.” Cem. Concr. Res., 31(5), 683–693.
Wiersma, C. L., and Rimstidt, J. D. (1984). “Rates of reaction pyrite and marcasite with ferric iron at pH 2.” Geochim. Cosmochim. Acta, 48(1), 85–92.
Yagi, S., and Kunii, D. (1955). Studies on combustion of carbon particles in flames and fluidized beds. Proc. 5th Int. Symp. on Combustion, Van Nostrand Reinhold, New York, 231–244.
Yanful, E. K. (1993). “Oxygen diffusion through soil covers on sulphidic mine tailings.” J. Geotech. Eng., 119(8), 1207–1228.

Information & Authors

Information

Published In

Go to Journal of Materials in Civil Engineering
Journal of Materials in Civil Engineering
Volume 25Issue 3March 2013
Pages: 372 - 381

History

Received: Nov 29, 2011
Accepted: Mar 29, 2012
Published online: Mar 31, 2012
Discussion open until: Aug 31, 2012
Published in print: Mar 1, 2013

Permissions

Request permissions for this article.

Authors

Affiliations

Izelman Oliveira, Ph.D. [email protected]
Civil Engineering, Dept. of Construction Engineering, Universitat Politècnica de Catalunya, Jordi Girona Salgado, 1-3, 08034, Barcelona, Spain (corresponding author). E-mail: [email protected]
Sergio H. P. Cavalaro
Lecturer Professor, Dept. of Construction Engineering, Universitat Politècnica de Catalunya, Jordi Girona Salgado, 1-3, 08034, Barcelona, Spain.
Antonio Aguado
Full Professor, Dept. of Construction Engineering, Universitat Politècnica de Catalunya, Jordi Girona Salgado, 1-3, 08034, Barcelona, Spain.

Metrics & Citations

Metrics

Citations

Download citation

If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.

Cited by

View Options

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Get Access

Access content

Please select your options to get access

Log in/Register Log in via your institution (Shibboleth)
ASCE Members: Please log in to see member pricing

Purchase

Save for later Information on ASCE Library Cards
ASCE Library Cards let you download journal articles, proceedings papers, and available book chapters across the entire ASCE Library platform. ASCE Library Cards remain active for 24 months or until all downloads are used. Note: This content will be debited as one download at time of checkout.

Terms of Use: ASCE Library Cards are for individual, personal use only. Reselling, republishing, or forwarding the materials to libraries or reading rooms is prohibited.
ASCE Library Card (5 downloads)
$105.00
Add to cart
ASCE Library Card (20 downloads)
$280.00
Add to cart
Buy Single Article
$35.00
Add to cart

Media

Figures

Other

Tables

Share

Share

Copy the content Link

Share with email

Email a colleague

Share