Assessing sequestration of selected polycyclic aromatic hydrocarbons by use of adsorption modeling and temperature-programmed desorption.

Sequestration of phenanthrene and pyrene was investigated in two soils--a sandy soil designated SBS and a silt-loam designated LHS--by combining long-term batch sorption studies with thermal desorption and pyrolysis of amended soil samples. The Polanyi-based adsorption volume and the adsorbed solute mass increased with aging for both soils, thus demonstrating the mechanism for observed sequestration. Despite rigorous thermal analysis, 30-62% (SBS sand) and 8-30% (LHS silt-loam) of phenanthrene could not be recovered after 30-270 days of sorption, with the increase in desorption resistance showing greater significance in SBS sand. For both soils, these values were 20-65% of adsorbed phenanthrene mass. Activation energies estimated from the temperature-programmed desorption (TPD) of sorbed phenanthrene at < or = 375 degrees C were 51-53 kJ/mol, consistent with values derived for desorption of organic compounds from humic materials. The activated first-order model fitting of observed TPD data supports the conclusion that the desorption-resistant fraction of phenanthrene has become sequestered onto condensed organic domains and requires temperatures exceeding 600 degrees C to be released. The work demonstrates the use of thermal analysis in complementing the Polanyi-based adsorption modeling approach for assessing the mechanistic basis for sequestration of organic contaminants in soils.