Limitations of Integrative Passive Samplers as a Tool for the Quantification of Pharmaceuticals in the Environment - A Critical Review with the Latest Innovations.

This review starts with a presentation of the theory of kinetic uptake by passive sampling (PS), which is traditionally used to distinguish between integrative and equilibrium samplers. Demonstrated limitations of this model for the passive sampling of pharmaceuticals from water were presented. Most notably, the contribution of the protective membrane in the resistance to mass transfer of lipophilic analytes and the well documented effect of external parameters on sampling rates contributed to the greatest uncertainty in PS application. The diffusion gradient in thin layer (DGT) technique seems to reduce the effect of external parameters (e.g., flow rate) to some degree. The laboratory-determined integrative uptake periods over defined sampler deployments was compared, and the discrepancy found suggests that the most popular Polar Organic Chemical Integrative Sampler (POCIS) could in some cases utilized as an equilibrium sampler. This assertion is supported by own calculations for three pharmaceuticals with extremely different lipophilic characters. Finally, the reasons performance reference compounds (PRCs) are not recommended for the reduction in uncertainty of the TWAC found by adsorptive samplers were presented. It was concluded that techniques of passive sampling of pharmaceuticals need a new uptake model to fit the current situation.