The interaction of boron with goethite: Experiments and CD–MUSIC modeling

Boron (B) is an essential element for plants and animals growth that interacts with mineral surfaces regulating its bioavailability and mobility in soils, sediments, and natural ecosystems. The interaction with mineral surfaces is quite important because of a narrow range between boron deficiency and toxicity limits. In this study, the interaction of boric acid with goethite (α-FeOOH) was measured in NaNO3 background solution as a function of pH, ionic strength, goethite and boron concentration representing as adsorption edges and isotherms. Boron adsorption edges showed a bell-shaped pattern with maximum adsorption around pH 8.50, whereas adsorption isotherms were rather linear. The adsorption data were successfully described with the CD–MUSIC model in combination with the Extended Stern (ES) model. The charge distribution (CD) of inner-sphere boron surface complexes was calculated from the geometry optimized with molecular orbital calculations applying density functional theory (MO/DFT). The CD modeling suggested dominant binding of boric acid as a trigonal inner-sphere complex with minor contributions of a tetrahedral inner-sphere complex (at high pH) and a trigonal outer-sphere complex (at low pH). The interpretation with the CD model is consistent with the spectroscopic observations.

Research highlights
► The CD–MUSIC model described B adsorption data on goethite in various conditions.
► MO/DFT applied to derive charge distribution values to be used in modeling.
► Boron is mainly adsorbed as a trigonal bidentate inner-sphere complex.
► An outer-sphere and a tetrahedral inner-sphere contribute in overall B adsorption.
► The derived surface speciation is in agreement with the spectroscopic data.