PMID: 11352030May 16, 2001Paper

Detailed sorption isotherms of polar and apolar compounds in a high-organic soil

Environmental Science & Technology
G Xia, Joseph J Pignatello


Sorption isotherms of 13 apolar liquids and solids and polar solids-six in unprecedented detail-are used to evaluate a polymer-based model for natural organic matter. While all isotherms are nonlinear, the "running" Freundlich exponent n varies markedly with concentration. The isotherms show linear-scale inflection consistent with the presence of flexible (deformable) porosity as predicted by the glassy polymer-based Extended Dual-Mode Model (EDMM). The EDMM assumes dissolution and hole-filling domains in the organic solid, with provision for sorbate-caused plasticization of the solid and "melting" of the holes. Features of the EDMM are illustrated for chlorinated benzenes in poly(vinyl chloride). The solutes fall into categories of "hard" (aliphatics and 2,4-dichlorophenol) and "soft" (chlorinated benzenes, 2-chloronitrobenzene) according to their ability to plasticize organic matter. Comparison of domain coefficients at infinite dilution reveals that organic solutes have a modestly greater affinity for holes than dissolution sites (by 0.1-0.6 log unit), as expected by the polymer model. Sorption of CHCl3 shows time-dependent hysteresis diminished at high concentrations by the plasticizing effect. Sorption of CHCl3 also shows ...Continue Reading


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