Spectroscopic study of dinitrophenol herbicide sorption on smectite

Sorption of two dinitrophenolic herbicides, 4,6-dinitro-ocresol (DNOC) and 4,6-dinitro-2-sec-butylphenol (DINOSEB) to smectite was studied using FTIR, HPLC, and quantum chemical methods. The high affinity of DNOC and DINOSEB for smectite surfaces was attributed to site-specific interactions with exchangeable cations and nonspecific van der Waals interactions with the siloxane surface. The positions of the ν(NO) and ν(NO) vibrational modes were perturbed by the exchangeable cations with similar changes occurring for both alkali and alkaline earth cations as a function of ionic potential. The cation-induced changes to the vibrational bands of the NO groups indicate that exchangeable metal cations are coordinated to -NO groups. Quantum chemical methods predicted a red-shift ofthe ν(NO) band and a corresponding blue-shift of the ν(NO) modes, as was observed experimentally. The nature of the smectite surface itself did not strongly influence the vibrational modes of sorbed DNOC or DINOSEB on the basis of a comparison of DNOC sorbed to three different smectites (K-SWy-2, K-SAz-1, and K-SHCa-1). FTIR spectra of DNOC and DINOSEB sorbed to a K-SWy-2 smectite were studied quantitatively using a modified form of Beer's law. The FTIR-derived sorption isotherm of DNOC sorbed to K-SWy-2 was in good agreement with the isotherm derived from HPLC measurements. The molar absorptivity value of DNOC sorbed to K-SWy-2 smectite was 1.43 × 107 cm/mol in good agreement with literature values for nitroaromatics (average value of 1.72 × 107 ± 0.3 cm/mol). On the basis of this value, the limit of detection using the FTIR method of ∼5 μg g was determined. These two observations (sorption isotherms and molar absorptivity) provide a direct link between the macroscopic sorption results and the FTIR spectra.