Soil & Water Res., 2007, 2(4):135-140 | DOI: 10.17221/2110-SWR

Thermodynamics of copper desorption from soils as affected by citrate and succinateOriginal Paper

Elsayed A. Elkhatib, A. M. Mahdy, N. H. Barakat
Department of Soil and Water Science, College of Agriculture, Elchatby, Alexandria University, Alexandria, Egypt

Desorption of Cu and low molecular weight dissolved organics are the primary factors that impact fate and transport of Cu in soils. To improve predictions of the toxicity and threat from Cu contaminated soil, it is critical that time-dependent desorption behaviour be understood. In this paper, the effect of organic ligands citrate and succinate on the kinetics of Cu desorption from contaminated soils varying widely in soil characteristics was investigated at three different temperatures. The results showed that the first order equation adequately described the kinetics of Cu desorption from clay and sandy soils under isothermal conditions. The reaction rate constant (kd) values of the first order kinetic equation for Cu desorption increased consistently with temperature, indicating faster release of Cu at higher temperatures. The Cu desorption rate from the studied soils at all three temperatures was as follows: citric > succinic. The Eavalues indicates that Cu desorption from the studied soils in the presence of two organic ligands is a diffusion controlled reaction. The negative values of ΔH* suggest that the desorption reactions are not energy consuming process. The higher negative values of (ΔH*) for Cu desorption from the studied soils in the presence of succinic ligand indicate that the heat energy required to overcome the Cu desorption barrier was greater than that for Cu desorption in the presence of citric ligand. Computation of the free energy of activation (ΔG*) yielded values ranging for 87 to 87.9 kJ/mol. The largest value represents ΔG* for Cu desorption for clay soil in the presence of succinic acid while the lowest value represents ΔG* for Cu desorption for sandy soil in the presence of citric acid. The information in this study is quite necessary to construct full functioning models that will help scientists to better understand mobility and bioavailability of metals in soils.

Keywords: kinetics; thermodynamic parameters; low molecular weight organic acids

Published: December 31, 2007  Show citation

ACS AIP APA ASA Harvard Chicago Chicago Notes IEEE ISO690 MLA NLM Turabian Vancouver
Elkhatib EA, Mahdy AM, Barakat NH. Thermodynamics of copper desorption from soils as affected by citrate and succinate. Soil & Water Res. 2007;2(4):135-140. doi: 10.17221/2110-SWR.
Download citation

References

  1. Ainsworth C.C., Pilon J.L., Gassman P.L, Van Der Sluys W.G. (1994): Cobalt, Cd and Pb sorption to hydrous iron oxide: residence time effect. Soil Science Society of America Journal, 58: 1615-1623. Go to original source...
  2. Atwood J.D. (1997): Inorganic and Organometallic Reaction Mechanisms. 2nd Ed. Wiley-VCH Verlag GmbH & Co, Town.
  3. Black C.A. (1965): Methods of Soil Analysis. Part 1. Agronomy. Vol. 9, American Society of Agronomy, Madison. Go to original source...
  4. Chaignon V., Sanchez Neira I., Herrmann P., Jaillard B., Hinsinger P. (2003): Copper bioavailability and extractability as related to chemical properties of contaminated soils from a vine-growing area. Environmental Pollution, 123: 229-238. Go to original source... Go to PubMed...
  5. Chen Y.X., Lin Q., Luo Y.M., He Y.F., Zhen S.J., Yu Y.L., Tian G.M., Wong M.H. (2003): The role of citric acid on the phytoremediation of heavy metal contaminated soil. Chemosphere, 50: 807-811. Go to original source... Go to PubMed...
  6. Collins R.N., Merrington G., McLaughlin M.J., Morel J.L. (2003) Organic ligand and pH effects on isotopically exchangeable cadmium in polluted soils. Soil Science Society of America Journal, 67: 112-121. Go to original source...
  7. Daniels F., Alberty R.A. (1975): Physical Chemistry. Jon Wiley, New York.
  8. Elkhatib E.A., Eishebiny G.M., Balba A.M. (1992): Comparison of four equations to describe the kinetics of Pb desorption from soils. Zeitschrift für Pflanzenernahrung und Bodenkunde, 155: 285-291. Go to original source...
  9. Elkhatib E.A., El Shebiny O.M., Elsubriuti G.M., Balba A.M. (1993): Thermodynamics of lead sorption and desorption in soils. Zeitschrift für Pflanzenernahrung und Bodenkunde, 156: 461-465. Go to original source...
  10. Impelliteri C.A., Saxe J.K., Cochran M., Jassen C.M., Allen H.E. (2003): Predicting the bioavailability of copper and zinc in soils: Modeling the partitioning of potentially bioavailable copper and zinc from soil solid to soil solution. Environmental Toxicology and Chemistry, 22: 1380-1386. Go to original source... Go to PubMed...
  11. Jencks W.P. (1969): Catalysis in Chemistry and Enzymology. McGraw-Hill, New York.
  12. Laidler K.J. (1965): Chemical Kinetics. 2nd Ed., McGrawHill, New York.
  13. Naidu R., Harter R.D. (1998): Effect of different organic ligands on cadmium sorption by and extractability from soils. Soil Science Society of America Journal, 62: 644-650. Go to original source...
  14. Nelson D.W., Sommers L.E. (1982): Total carbon, organic carbon and organic matter. In: Page A.L., Miller R.H., Keeney D.R. (eds): Methods of Soil Analysis. American Society of Agronomy, Madison, 539-549. Go to original source...
  15. Saeki K., Kunito T., Oyaizu H., Matsumoto S. (2002): Relationships between bacterial tolerance levels and forms of copper and zinc in soils. Journal of Environmental Quality, 31: 1570-1575. Go to original source... Go to PubMed...
  16. SAS Institute (1996). SAS Release 6.12. SAS Institute, Cary.
  17. Scheckel K.G., Sparks D.L. (2001): Temperature effects on nickel sorption kinetics at the mineral-water interface. Soil Science Society of America Journal, 65: 719-728. Go to original source...
  18. Serjeant E.P., Dempsey B. (1979): Ionization Constants of Organic Acids in Aqueous Solutions. Pergamon, Oxford.
  19. Sparks D.L. (1995): Environmental Soil Chemistry. Academic Press, San Diego. Go to original source...
  20. Stewart M.A., Jardine P.M., Benett M.O., Mebehoun T.L., Hyder L.K., Mckay L.D. (2003): Influence of soil geochemical and physical properties on sorption and bioaccumulation of chromium (111). Journal of Environmental Quality, 32: 129-137. Go to original source... Go to PubMed...
  21. Thomas G.W. (1982): Exchangeable cations. In: Page A.L., Miller R.H., Keeney D.R. (eds): Methods of Soil Analysis. American Society of Agronomy, Madison, 159-165. Go to original source...

This is an open access article distributed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY NC 4.0), which permits non-comercial use, distribution, and reproduction in any medium, provided the original publication is properly cited. No use, distribution or reproduction is permitted which does not comply with these terms.