Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: Accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 μm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients KDOC were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.