Induction of crystallization of calcium oxalate dihydrate in micellar solutions of anionic surfactants

Calcium oxalate dihydrate (CaC2O4 center dot (2+x)H2O; COD; x < or = 0.5) does not readily crystallize from electrolytic solutions but appears as a component in crystalluria. In this paper, we review in vitro studies on the factors responsible for its nucleation and growth with special attention given to the role of surfactants. The following surfactants were tested: dodecyl ammonium chloride (cationic), octaethylene mono-hexadecylether (non-ionic), sodium dodecyl sulfate (SDS, anionic), dioctyl sulphosuccinate (AOT, anionic), and sodium cholate (NaC, anionic). The cationic and some of the anionic surfactants (SDS, AOT) induced different habit modifications of growing calcium oxalate crystals by preferential adsorption at different crystal faces. In addition, the anionic surfactants effectively induced crystallization of COD at the expense of COM, the proportion of COD in the precipitates abruptly increasing above a critical surfactant concentration, close to, but not necessarily identical with the respective CMC. A mechanism is proposed, whereby crystallization of COD in the presence of surfactants is a consequence of the inhibition of COM by preferential adsorption of surfactant hemimicelles (two-dimensional surface aggregates) at the surfaces of growing crystals.