Revisiting Models of Cd, Cu, Pb and Zn Adsorption onto Fe Oxides

Michael Komáreka, J. Antelob, J. Feinc and C. M. Koretskyd

a Department of Environmental Geosciences, Czech University of Life Sciences Prague, Czech Republic

b Technological Research Institute, University of Santiago de Compostela, Spain

c Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, USA

d Department of Geosciences, Western Michigan University, USA

komarek@fzp.czu.cz

A generic hydrous Fe oxide surface is often used in surface complexation modeling (SCM) for predicting metal behavior in aqueous and soil environments. However, this approach may lead to incorrect results because there are many different naturally-occurring Fe(III) (oxyhydr)oxide mineral phases in the environment, each exhibiting distinct adsorption characteristics. We provide a simple and unified workflow for obtaining the adsorption parameters (DLM and CD-MUSIC), which are readily implementable into widely used geochemical codes, such as Visual MINTEQ, MINEQL+, and ORCHESTRA. The parameters were obtained enabling quantification of metal adsorption onto a range of Fe(III) oxides (goethite, hematite, lepidocrocite, maghemite) in various aqueous environments. The dataset of SCM parameters characterize the adsorption of selected divalent metals (Cd, Cu, Pb, Zn) at varying metal concentrations and ionic strengths. In general, the CD-MUSIC model provides better fits to the observed metal adsorption data onto the studied Fe oxides than the simpler DLM. However, the CD-MUSIC fits were based on more fitting parameters (multiple surface complexes, electrostatic parameters, etc.) and the DLM approach aimed to be as simple and consistent as possible for all the studied Fe(III) oxides and metals. Nevertheless, both modeling approaches provide a useful and viable option that should result in better predictions of metal speciation in the environment than the ‘generic’ Fe oxide model.

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