Passive sampling of polycyclic aromatic hydrocarbons with low-density polyethylene: Equilibration limitations in...

Polyethylene (PE) and other polymers are widely and successfully used as passive samplers for organic pollutants in the environment. This study provides high-resolution experimental data from batch shaking tests on the uptake, reversibility, and linear equilibrium partitioning of polycyclic aromatic hydrocarbons (PAHs) using two different PE sheets of 30 µm and 80 µm thickness. Kinetics for phenanthrene are well described by a mechanistic first-order model with mass transfer limited by an aqueous boundary layer (with a mean thickness of 170 µm). Equilibration in laboratory batch systems during uptake and desorption is very rapid with characteristic times of 1-2 h but this depends on the boundary condition, e.g., the ratio of PE mass to water volume. Therefore, equilibration of PE in other setups, e.g., in soil slurries or sediment suspensions, may take orders of magnitude longer because the boundary condition for PE changes from finite to infinite bath conditions (soil or sediment particles may keep the concentration in water almost constant). Solid precipitates for high molecular weight PAHs explain partition coefficients below expected values because of kinetic limitations in such a system. Nevertheless, passive sampling can be employed safely if such limitations are considered; furthermore, partition coefficients can be estimated accurately by empirical relationships (e.g., within 0.1 log unit) based on molecular weight, octanol/water partition coefficients, or subcooled liquid solubilities.