A distributed reactivity model for sorption by soils and sediments. 14. Characterization and modeling of phenanthrene desorption rates.

Rates and extents of phenanthrene desorption were studied for more than 250 days as functions of sorbent type, initial loading level, and aging. Apparent first-order desorption rate constants for the slowly desorbing fraction were found to (i) range from 0.00086 to 0.148 days-1 for geosorbents that contain geologically mature kerogen and less rigid humic-type soil organic matter, respectively, (ii) decrease by as much as an order of magnitude with decreasing initial sorbed solid-phase phenanthrene concentration, (iii) decrease by a factor of 2 with increasing aging time for a humic topsoil but remain unaffected by aging time beyond 3 months for a shale, and (iv) be 1-2 orders of magnitude lower than rate constants for the rapidly desorbing phenanthrene fractions for any given contaminated sample. Six models were used to fit the desorption rate data. Biphasic diffusion and biphasic first-order models with three fitting parameters possess broad utility and are potentially useful in a variety of environmental applications. Disadvantages of a five-parameter triphasic first-order desorption model, a two-parameter gamma-function model, and a one- or two-parameter pore diffusion model are also discussed.