Influence of organic ligands on Cr desorption from hydroxy-Cr intercalated montmorillonite

Abstract

Retention of metals as hydroxy precipitates on mineral surfaces is an important process maintaining environmental quality. Hydroxy precipitates of Cr(III) are particularly important because appreciable mobilisation of intercalated, hydrolysed Cr from montmorillonite is currently thought to occur only via oxidative dissolution. The present study examines the potential of oxalate, tartrate, and citrate to desorb Cr from both hydroxy-Cr and hydroxy Al–Cr precipitates sorbed to montmorillonite. For all intercalated clays there was an initial very rapid dissolution, followed by a slow but sustained Cr release that more closely followed a parabolic rate law, the latter indicative of transport-controlled dissolution. The initial rapid dissolution persisted longer for the pure Cr clay (∼48 h) than for the coprecipitated Al–Cr clay (∼24 h). At the end of the 30 d reaction, however, most Cr remained sorbed to the montmorillonite in all systems. Citrate, for example, solubilised only ∼10% of the total sorbed Cr from the pure Cr clays. Aluminum presence decreased Cr solubilisation rate due to Al accumulation at the polymer margins. Moreover, Al presence maintained the integrity of the intercalated polymers and prevented c-axis expansion beyond 1.4 nm, thus restricting the supply of organic ligand to the interlayer region. Oxalate, tartrate, and citrate were shown to be effective chelators of sorbed Cr and these ligands may therefore play an important role in the mobilisation and cycling of this metal in soils and sediments.