Effects of Myo-inositol Hexakisphosphate on Zn(II) Sorption on γ-Alumina: A Mechanistic Study

Abstract

Myo-inositol hexakisphosphate (IHP), a most common organic phosphorus in many soils, can strongly interact with aluminum (Al) oxides and influence the fate of metal ions. In this study, the effects of presorbed IHP on γ-Al2O3 (γ-alumina) surfaces on Zn(II) sorption were investigated in batch experiments using a combination of powder X-ray diffraction (XRD), in situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), 31P and 27Al solid-state nuclear magnetic resonance spectroscopies (NMR), and Zn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS). The results of the batch experiments show that the presorption of IHP increases the sorption density of Zn(II) on γ-Al2O3 surfaces. The XRD data indicate that the presorption of IHP hinders the formation of Zn–Al layered double hydroxide (LDH) precipitates by raising the critical concentration of Zn(II) required to precipitate the complex. Solid-state NMR spectra further suggest that the chemical environment and speciation of IHP presorbed change, i.e., from inner-sphere surface complexes to ternary surface complexes and to zinc phytate precipitates (Zn-IHP) with the increase in Zn(II) concentration or pH. Linear combination fittings (LCFs) of the EXAFS spectra indicate that the proportion of Zn(II) in binary or ternary surface complexes decreases and that in Zn–Al LDH increases with increasing concentration of Zn(II) at pH 7. Furthermore, the order at which IHP and Zn are added in the reaction can influence the cosorption mechanism. At pH 7, more binary or ternary Zn surface complexes and Zn-IHP form, and less Zn–Al LDH precipitates form if Zn is added first. These results demonstrate that both the timing and concentration of IHP and divalent metals have sweeping influences on their solubility and speciation and these intricacies need to be taken into consideration toward predicting their fates in the environment.