Variability in goethite surface site density: evidence from proton and carbonate sorption

Goethite is a representative iron oxide in natural environments due to its abundance and thermodynamic stability and may be responsible for many surface-mediated processes, including ion retention and mobility in aqueous settings. A large variability in morphologies and specific surface areas of goethite crystals exists but little work has been done to compare surface reactivity between them. The present work offers experimental evidence for the existence of an inverse relationship between sorption capacity for protons and carbonate ions and specific surface area of goethite for three synthetic goethite preparations spanning surface area differences by a factor of 2. An explanation for this was found by assuming a variable reactive site density between preparations in direct relationship to their sorption capacity based on congruency of carbonate sorption computed on a per-site basis. Previous evidence of maximum sorption capacities supports this explanation, and site density ratios between the goethites studied here were obtained. Triple layer surface complexation modeling was successful in describing adsorption data for all goethite preparations using equal stoichiometries. A new formulation of standard state for activities of surface species based on a 1.0 mole fraction of sites on the solid allowed transformation of the conventional molar concentration-based affinity constants to values based on site occupancy. In this fashion, by applying the appropriate site density ratios, a single set of affinity constant values was found that described accurately the adsorption data for all preparations.