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Cation– Bonding

A New Perspective on the Sorption of Polycyclic Aromatic Hydrocarbons to Mineral Surfaces

^a Department of Geology and Geophysics, Texas A&M University, College Station, TX 77843
^b School of the Environment, Clemson University, Clemson, SC 29634-0919
^c Present address: Connecticut Agricultural Experiment Station, 123 Huntington Street, New Haven, CT 06504

View larger version (22K): [in a new window]   Fig. 1. Deuterium nuclear magnetic resonance (2H NMR) spectra of d2–dichloromethane (CD2Cl2), d6–benzene (C6D6), d8–toluene (C6D5CD3) and d2–water (D2O) contained at natural abundance in aqueous suspensions of Na–montmorillonite at pH 3.0 and 9.0 (1:200 clay to solution mass ratio, 0.01 M NaCl): (a) d2–dichloromethane (downfield-shifted) at pH 3; (b) d2–dichloromethane at pH 9; (c) d6–benzene (downfield-shifted) at pH 3; (d) d6–benzene at pH 9; (e) d8–toluene at pH 3 (C6D5– as the most downfield-shifted driblet corresponding to and ß deuterium; CD3– as the most upfield-shifted); and (f) d8–toluene at pH 9 (quadrupolar splitting observed for deuterium of C6D5– moiety).

View larger version (13K): [in a new window]   Fig. 2. Proposed interactions for orientations of d2–dichloromethane (CD2Cl2) and d6–benzene (C6D6) at the clay interface: (a) charge–dipole interaction, (b) H-bonding, (c) cation– interaction, and (d) H-bonding.

View larger version (25K): [in a new window]   Fig. 3. Apparent distribution coefficients (Kd) for sorption of naphthalene and/or pyrene to minerals saturated by different cations: (a) naphthalene/silica gels (pore sizes of 60 and 150 Å), (b) pyrene/silica gels (pore sizes of 60 and 150 Å), and (c) pyrene/kaolinite (kaol), and pyrene/vermiculite (verm) (Na-kaol, Cs-kaol, Na-verm, and Cs-verm data from Grimaldi [1999]).

View larger version (28K): [in a new window]   Fig. 4. Amount sorbed (q) vs. equilibrium concentration (Ce) for sorption and/or desorption of phenanthrene (PHEN) and 1,2,4,5-tetrachlorobenzene (TrCB) with reference montmorillonite. The solid lines represent the fit of the Freundlich model to the sorption data using weighted nonlinear regression. The dashed line is a smoothed spline through the sorption data points.