Predicting ion adsorption onto the iron hydroxide goethite in single and multi-solute systems
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Surface complexation models (SCMs) have proven to be a useful tool in predicting ion adsorption at the mineral – water interface. In particular, previous research has shown that the Diffuse Layer Model (DLM), Constant Capacitance Model (CCM), and Triple Layer Model (TLM), are all capable of predicting ion adsorption in relatively simple single solute systems. To better simulate the environmental conditions experienced by groundwater sources present in the Earth’s subsurface, experimental adsorption studies have been conducted for more complex multi-solute systems. Under these conditions, SCMs have not proven to be reliable in consistently predicting ion adsorption behavior for the adsorbates of interest. This inability of these SCMs to predict ion adsorption for more complex, multi-solute systems is thought to stem from the variable site density (NS) values utilized in these models. In this research, a methodology was developed for characterizing mineral surface heterogeneity that allows for the different site density values predicted from crystallography, microscopic imaging, tritium exchange, surface saturation data, and surface charging data to all be explained using a single unified theory. This methodology was applied to a goethite mineral sample used in performing batch adsorption studies in single and bi-solute systems with Cd(II), Pb(II), and Se(IV). The adsorption behavior of these adsorbates onto the goethite sample was successfully predicted using the Charge Distribution Multi-Site Complexation (CD-MUSIC) Model and surface complexes consistent with spectroscopic data and computational molecular modeling simulations. A second, separate modeling study was performed using CD-MUSIC to predict Hg(II) adsorption onto different goethite samples of varying size and crystal morphology in single and multi-solute systems. In this study, site density values were predicted for the mineral samples studied utilizing a linear relationship observed for goethite between specific surface area and proton reactive site density. The CD-MUSIC model proved successful in predicting Hg(II) adsorption over all conditions studied while employing only surface complexes consistent with molecular scale analyses. In addition, a novel method for quantifying carbonate’s presence in experimental systems was developed.