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Recent developments in analytics using infrared spectroscopy have enabled us to identify the adsorption mechanism at interfaces, but such methods are applicable only for simple systems. In this study, the preferential adsorption of phosphate on binary goethite and maghaemite was investigated. As a result, monodentate and bidentate complexes were the major complexes on goethite and maghaemite, respectively. A shrinking effect in goethite and a swelling effect in maghaemite were identified, and environmental perturbations caused a significant decrease in the integrated absorbance of phosphate complexes on maghaemite, while no effect was observed on goethite, which implies that different adsorption mechanisms were involved. Based on the results, a bridging complex was proposed, and the swelling effect is explained by the negatively charged maghaemite surface resulting from the bidentate complex. The isolation of phosphate by the shrinking effect explains the low phosphate bioavailability in the soil environment, while the colloidal properties of the bidentate complex on maghaemite are the reason for colloidal mobilization. To the best of our knowledge, this study not only addresses the shrinking and swelling properties of iron (hydr)oxide nanoparticles but also demonstrates preferential adsorption on binary sorbents using in situ ATR-FTIR for the first time.

The structural configuration of arsenate on iron (hydr)oxide determines its leachability and bioavailability in the soil environment. It is important to understand how the stability of iron hydroxide and the structural configuration of arsenate complexes vary in response to changes in environmental conditions. Therefore, we investigated the effects of drying, pH and surface loadings on the stability of goethite and the structural configuration of arsenate through batch experiments and TEM and XAS measurements with DFT calculation. As a result, we observed no significant transformation of goethite under most conditions, but TEM confirmed the partial formation of bernalite in the presence of arsenate at a pH of 10, and the bernalite showed 2.18 times higher arsenate sorption than the goethite. The linear combination fitting of the EXAFS spectra with DFT calculations revealed that tridentate and bidentate complexes were dominant under low surface loading and pH conditions in the sedimented samples, while monodentate complexes were abundant under high surface loading and pH conditions. Based on our results, we conclude that the formation of arsenic-rich colloids could account for mobilization in the soil environment, and the density of available sorption sites combined with the concentration of solute could cause the change in structural configuration.