Spectroscopic Study of Carbaryl Sorption on Smectite from Aqueous Suspension

Sorption of carbaryl (1-naphthyl-N-methyl-carbamate) from aqueous suspension to smectite was studied using Fourier transform infrared (FTIR), high-performance liquid chromatography (HPLC) (for batch sorption), and quantum chemical methods. The amount of carbaryl sorbed was strongly dependent on the surface-charge density of the smectite with more sorption occurring on the two “low” surface-charge density smectites (SHCa-1 and SWy-2) compared to that of the high surface-charge SAz-1 smectite. In addition, the amount of carbaryl sorbed was strongly dependent on the nature of the exchangeable cation and followed the order of Ba ∼ Cs ∼ Ca > Mg ∼ K > Na ∼ Li for SWy-2. A similar trend was found for hectorite (SHCa-1) of Cs > Ba > Ca > K ∼ Mg > Na ∼ Li. Using the shift of the carbonyl stretching band as an indicator of the strength of interaction between carbaryl and the exchangeable cation, the observed order was Mg > Ca > Ba ∼ K > Na > Cs. The position of the carbonyl stretching band shifted to lower wavenumbers with increasing ionic potential of the exchangeable cation. Density functional theory predicted a cation-induced lengthening of the CO bond, resulting from the carbonyl group interacting directly with the exchangeable cation in support of the spectroscopic observations. Further evidence was provided by a concomitant shift in the opposite direction by several vibrational bands in the 1355−1375 cm-1 region assigned to stretching bands of the carbamate N−Ccarbonyl and Oether−Ccarbonyl bonds. These data indicate that carbaryl sorption is due, in part, to site-specific interactions between the carbamate functional group and exchangeable cations, as evidenced by the FTIR data. However, these data suggest that hydrophobic interactions also contribute to the overall amount of carbaryl sorbed. For example, the FTIR data indicated that the weakest interaction occurred when Cs+ was the exchangeable cation. In contrast, the highest amount of carbaryl sorption was observed on Cs-exchanged smectite. Of all the cations studied, Cs has the lowest enthalpy of hydration. It is suggested that this low hydration energy provides the carbaryl with greater access to the hydrophobic regions of the siloxane surface.