Mechanistic Investigation of Non-Ideal Sorption Behavior in Natural Organic Matter. 1. Vapor Phase Equilibrium

Abstract

Results from an experimental and modeling investigation of the influence of thermodynamic properties of highly purified natural organic matter (NOM) on observed equilibrium sorption/desorption behaviors of vapor phase trichloroethylene (TCE) is presented. Identification of glass transition (T(g)) behavior in Leonardite humic acid and Organosolv lignin enabled evaluation of equilibrium and nonequilibrium sorption behavior in glassy and rubbery NOM. Specific differences in vapor phase equilibrium behavior in NOM above and below their T(g) were identified. In the glassy state (below T(g)), sorption of TCE is well-described by micropore models, with enthalpies of sorption characteristic of microporous, glassy macromolecules. Above T(g), sorptive behavior was well-described by Flory-Huggins theory, indicating that the mobility and structural configuration of rubbery NOM materials may be analogous to the characteristic sorption behavior observed in more mobile, rubbery macromolecules, including strong entropic changes during sorption. Results from this work provide further support that, at least for the samples employed in this study, NOM possesses macromolecular characteristics which display sorption behavior similar to synthetic macromolecules-an important assumption in conceptual sorption equilibrium models used in the analysis of the fate and transport of VOCs in the environment.