Evaluation of affinity constants of Cu, Cd, Ca and H for active soil surfaces for a solid phase-controlled soil ligand model

Julien Rachou; Sébastien Sauvé

doi:10.1071/EN07093

RESEARCH ARTICLE

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Evaluation of affinity constants of Cu, Cd, Ca and H for active soil surfaces for a solid phase-controlled soil ligand model

Julien Rachou ^A and Sébastien Sauvé ^A ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry, Université de Montréal, PO Box 6128 Downtown, Montréal, QC, H3C 3J7, Canada.

^B Corresponding author. Emial: sebastien.sauve@umontreal.ca

Environmental Chemistry 5(2) 150-160 https://doi.org/10.1071/EN07093
Submitted: 8 December 2007 Accepted: 4 March 2008 Published: 17 April 2008

Environmental context. The speciation of metals in soils is controlled by the equilibrium between the solid and aqueous phases and by several parameters such as pH and total metal concentrations. The integration of affinity constants between several cations and active soil surfaces of different soils in the chemical equilibrium modelling software MINEQL+ allows a good evaluation of the chemical speciation of the metals.

Abstract. A new approach, derived from the concept of the biotic ligand model, was used for the determination of the affinity constants of Ca, Cu, Cd and H to the active surfaces of different kinds of soils. This approach allowed us to obtain consistent data and to integrate these values in the chemical equilibrium modelling software MINEQL+ and eventually into a solid phase-controlled soil ligand model. This could then very easily be transformed into a terrestrial biotic ligand model by adding constants for biological components. We obtained the chemical speciation of the metals of interest by integrating the initial characteristics of the soil (pH; cation exchange capacity, CEC; total metal concentrations in soil extracts; ionic strength; and CO₂ pressure). Comparison of the predicted and measured values of free Cu²⁺ is excellent using soil-specific affinity constants as well as average values. The average affinity constants between the active soil surfaces (S) and the target cations are log K_Ca–S = –0.84 (±0.01), log K_Cu–S = 5.3 (±0.1), log K_Cd–S = 4.4 (±0.2) and log K_H–S = 4.1 (±0.2). External soils have been used to validate the conceptual model and the results show a very good correlation between the predicted and the measured free Cu (pCu) except for an acidic soil (pH < 5.2), highlighting the importance of integrating Al into the model.

Additional keywords: contaminated soils, soil chemistry modelling, terrestrial biotic ligand model, TBLM.

Acknowledgements

The authors gratefully acknowledge the support of the Natural Sciences and Engineering Research Council Metals in the Human Environment (NSERC-MITHE) research network. A complete list of sponsors is available at www.mithe-rn.org.

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