A study on the mechanism of Ca2+ adsorption on TiO2 and Fe2O3 with the usage of calcium ion-selective electrode.

The paper presents the quantitative characterization of the solid/water interface applying both experimental and theoretical approaches for the system of TiO2 (mixture of anatase and rutile) and Fe2O3 (maghemite) with calcium ions in the pH function. The aim of the study was also to find a bonding mechanism between Ca2+ and metal oxides surface based on the calculations from the surface complexation modeling code (GEOSURF by Sahai and Sverjensky, 1998). In order to obtain adsorption edges, a calcium ion-selective electrode (Ca-ISE) was applied for determination of Ca2+ concentration in the suspensions. The results of both the Ca-ISE and parallel spectrophotometric determination were similar. The adsorption data showed that TiO2 exhibited stronger calcium binding than Fe2O3 at pH > 8. Using 2-pK TLM (triple-layer model) it was demonstrated that mechanism of the calcium adsorption onto the metal oxides surface involved different reactions. In the case of TiO2 it involved formation of >SO-_CaOH+ predominately on the ß-plane and at pH > 9 also on the 0-plane. In the case of Fe2O3 one could observe the existence of (>SO-)2_Ca2+ on the ß-plane in the whole studied pH range. At pH above 7 the tetranuclear complexes (>SOH)2(>SO-)2_Ca(OH)+ were found, and at pH > 9 also >SO-_CaOH+ could be observed. On the other hand, the analysis of the ζ-potential data suggested the absence of the tetra-species on the maghemite surface. The study indicated that the properly validated calcium ion-selective electrode can be an attractive instrument for monitoring Ca2+ adsorption on metal oxides in the environment.

Electrophoretic and potentiometric signatures of multistage CaCO3 nucleation.

HYPOTHESIS: Calcium carbonate nucleation is often a complex and multistep process that is difficult to follow in situ. The time-resolved electrochemical and electrophoretic methods can provide a new insight into the nucleation pathway. EXPERIMENTS: Here, we used a combination of speciation calculations with time-resolved electrophoretic and potentiometric methods to monitor calcium carbonate precipitation from a slightly supersaturated solution. FINDINGS: After an initial mixing period of three minutes in which metastable CaCO3 phases may have nucleated and subsequently dissolved due to locally-high supersaturations, bulk solution pH and Ca2+ concentrations stabilize before decreasing in tandem with the precipitation of a CaCO3 phase. After an hour, the precipitate is dominated by calcite that grows at the expense of dissolving vaterite. The time-dependent electrokinetic potential shows analogous signatures of multistage nucleation process: initial rapid changes in ζ-potential are followed by much slower equilibration starting about one hour after reagents are mixed. The changes in ζ-potential, solution pH, saturation indexes, and particle morphology are consistent with vaterite to calcite transformation via dissolution of the former and recrystallization of the latter. These findings highlight the potential use of ζ-potential measurements for monitoring polymorphic transformations of carbonate phases in-situ.