title: Model verification of thermal programmed desorption-mass spectrometry for estimation of release energy values for polycyclic aromatic hydrocarbons on mineral sorbents.
abstract: The physical availability of organic compounds in soil and sediment strongly influences their bioavailability and toxicity. Previous work has indicated that physical availability changes throughout the processes of aging and treatment and that it can be linked to the energy required to release the compound from its sorbent matrix, with a higher energy indicating a more tightly bound compound. This study focused on determining release energy values for various mineral geosorbents (glass beads, sand, and kaolin) contaminated with a 16 polycyclic aromatic hydrocarbon (PAH) mixture. The sorbents were analyzed using thermal program desorption/mass spectrometry (TPD/MS) and the release energy values were calculated from the resulting thermograms utilizing a nonlinear fit of the analytical solution to a simplified version of the Polanyi-Wigner equation. This solution method resulted in a series of combinations of values for the pre-exponential factor (v) and release energy (E) that produced desorption rate curves with similar errors when fit to actual data sets. These combinations can be viewed as an error surface, which clearly shows a valley of minimum error values spanning the range of both E and v. This indicates that this method may not provide a unique set of E- and v-values and suggests that the simplified version of the Polanyi-Wigner equation cannot be used to determine release energy based on TPD data alone.
authors.affiliation: Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, Indiana 46556, USA.
authors.forename: Sara I
authors.initials: SI
authors.lastname: Nicholl
authors.forename: Jeffrey W
authors.initials: JW
authors.lastname: Talley
authors.forename: Stephan
authors.initials: S
authors.lastname: Silliman
mesh_terms: D000327:Adsorption; D005898:Glass / Q000737:chemistry*; D006358:Hot Temperature; D007616:Kaolin / Q000737:chemistry; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods*; D008956:Models, Chemical; D017711:Nonlinear Dynamics; D011084:Polycyclic Aromatic Hydrocarbons / Q000032:analysis* / Q000737:chemistry; D012822:Silicon Dioxide / Q000737:chemistry; D012989:Soil Pollutants / Q000032:analysis*
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D012989:Soil Pollutants; D007616:Kaolin; D012822:Silicon Dioxide