Takashi Munemoto

Monohydrocalcite: a promising remediation material for hazardous anions

Abstract The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Arsenate sorption on monohydrocalcite by coprecipitation during transformation to aragonite.

The metastability of monohydrocalcite (CaCO3·H2O: MHC) suggests high reactivity to dissolved trace elements. Using kinetic and isotherm sorption experiments with different reaction times (24h, 48h), As(V) sorption on MHC was examined to elucidate As(V) uptake by MHC. Although the MHC was transformed to aragonite with time, the MHC in higher As(V) loading conditions was able to persist longer than in lower loading conditions. Actually, As(V) uptake was negligible for samples in which the MHC remained. However, remarkable uptake of As(V) was observed for samples in which a complete transformation of MHC to aragonite occurred. Results of kinetic study confirmed that the timing of the MHC transformation coincided perfectly with that of As(V) removal from the solution. XAFS measurements showed that the local structure of As after the MHC transformation was almost identical to that of As in the As(V) coprecipitated aragonite. Sorption behavior of As(V) during the transformation is explainable theoretically by the substitution of As(V) into the aragonite structure. The distribution coefficient and (apparent) maximum sorption capacity of As(V) sorption on MHC after 48h at low-to-moderate As(V) concentrations are 500L/kg and 25μmol/g, respectively, which are much higher than those of simple adsorption of As(V) on calcite.