Pi-pi interactions may play a role in association of aromatic compounds with natural organic substances. Complexation in aqueous solvents was studied between the pi donor, phenanthrene (PHEN), and model pi-acceptor species (quinones and N-heteroaromatic cations) that represent certain functional units of humic substances. Charge-transfer bands in the UV and ring-current shifts in the proton nuclear magnetic resonance (NMR) spectrum confirmed the face-to-face, pi-pi donor-acceptor nature of the bond. Complexation constants were obtained by the solubility enhancement method; solubility enhancements up to 2500 were found. Ruled out as predominant causes of solubility enhancement were monomer desolvation (i.e., "hydrophobic" effects), partitioning into micelles, pi-cation interactions, and pi-hydrogen bonding. Acceptor self-stacking and formation of higher-stoichiometry acceptor-donor complexes had to be considered in evaluating donor-acceptor equilibria in some cases. The affinity of acceptor for PHEN followed the order of increasing pi-acceptor strength and varied strongly with the degree of ring overlap with PHEN. Complexation between PHEN and the free solution faces of an acceptor was less favorable than intercalation of PHEN between two acceptor units in a stack. A positive hydrophobic effect on complexation was evident in water mixtures with acetone or methanol and found to correlate with the number of faces of PHEN requiring desolvation to form the complex. When hydrophobic effects are subtracted out, the pi-pi complex actually becomes favored as the solvent water content and polarity decline. The results suggest that phenanthrene, and by implication other donor aromatic compounds, are capable of forming pi-pi interactions with appropriate humic fragments.

Abstract---Small-angle X-ray scattering (SAXS), adsorption and nuclear magnetic resonance (NMR) techniques were used to determine the fractal dimensions (D) of 3 natural reference clays: 1) a kaolinite (KGa-2); 2) a hectorite (SHCa-1), and 3) a Ca-montmorillonite (STx-1). The surfaces of these clays were found to be fractal with D values close to 2.0. This is consistent with the common description of clay mineral surfaces as smooth and planar. Some surface irregularities were observed for hectorite and Camontmorillonite as a result of impurities in the materials. The SAXS method generated comparable D values for KGa-2 and STx-1. These results are supported by scanning electron microscopy (SEM). The SAXS and adsorption methods were found to probe the surface irregularities of the clays while the nuclear magnetic resonance (NMR) technique seems to reflect the mass distribution of certain sites in the material. Since the surface nature of clays is responsible for their reactivity in natural systems, SAXS and adsorption techniques would be the methods of choice for their fractal characterization. Due to its wider applicable characterization size-range, the SAXS method appears to be better suited for the determination of the fractal dimensions of clay minerals.

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Photodegradation of [(14)C]-chlorantraniliprole (CLAP) and [(14)C]-cyantraniliprole (CNAP) was investigated in sterile buffer solutions, in natural water, and on soil surfaces. Both compounds displayed rapid degradation in aqueous buffers when exposed to light at concentrations which could result from direct overspray to a shallow water body. While the main products observed had analogous structures, a substantial difference was noted in the rate of degradation of the two compounds despite minimal differences in their structures. Transformations observed were primarily intramolecular rearrangements and degradations resulting from addition of hydroxyl radicals leading to molecular cleavage. Some of the degradation products were transient, and several degradates had isomeric molecular compositions. The sequence of transformations was established definitively with the help of kinetics modeling. Utility of kinetics analysis in verification of the proposed pathways is illustrated.

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