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This study aimed to optimize organo-clay formulations for reduction of leaching of the herbicides alachlor, metolachlor, and norflurazon, which include a phenyl ring in the structure. The adsorbed amounts of herbicides increased severalfold when montmorillonite was preadsorbed by an organic cation; benzyltrimethylammonium (BTMA) was more effective than benzyltriethylammonium (BTEA). Fourier transform infrared studies indicated interactions between alachlor molecules and adsorbed BTMA. The adsorption affinity of the herbicides increased with BTEA loading up to the cation exchange capacity (CEC) of montmorillonite but reached a maximum at a BTMA loading of 5/8 of the CEC. The enhanced adsorbed amounts of herbicides are mainly due to interactions between the phenyl rings of herbicide molecules and organic cations, which are favored with the smaller cation, BTMA. BTMA preadsorbed on the clay up to the CEC forms a fraction (14-18%) of charged dimers so that less phenyl rings are available for interacting with herbicide molecules. This effect is small for preloading by BTEA, so that the amounts adsorbed increase with the degree of preloading. Thus, optimization of claybased herbicide formulations requires a selection of structurally compatible organic cations preadsorbed on the clay at optimal coverage.

Engineering of clay nanocomposite materials by modification of their surfaces can enable the control of retention, transport, and persistence of toxic chemicals in the geosystem. The properties and interactions of clay nanocomposites have been widely studied, but little information exists on their microstructure at a range of scale extending down to atomic dimensions. The pairing of Na-montmorillonite clay with organic cations as well as with the herbicide fluridone, chosen as a model for an organic pollutant, was studied. Three organic cations were selected: hexadecyltrimethylammonium, benzyltrimethylammonium, and benzyltriethylammonium at 0%, 60%, and 100% of cation exchange capacity (CEC) loadings. A detailed microstructural analysis of the organo-clay nanocomposites and of the fluridone nanocomposites was undertaken by high-resolution transmission electron microscopy (HRTEM) and X-ray energy-dispersive spectroscopy (EDS). Morphological observations and chemical analyses were performed simultaneously on the same sample. The combined HRTEM and EDS measurements strongly suggest (a) heterogeneous local intercalation of the organic cations manifested by a range in the measured d001 spacing, implying random expansion of the clay layered structure with increased loading of the organic cations; (b) intercalation within the external layers, which is thoroughly influenced by local defect microstructure and/or edge availability of the montmorillonite nanoparticles as well as by the molecular structure of the intercalating organic cation. Additional intercalation of fluridone molecules did not affect the structure (d001 spacing) of the organo-clay nanocomposites.

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