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Recently, a new sampling device combining active and passive sampling (APS) was developed for the measurement of time-averaged concentrations of metal species and both polar and non-polar organic contaminants in water. By coupling a diffusion cell (loaded with a set of sorbents selective for different substances) with a small pump and a flow meter, the APS device is able to perform in situ measurements that are independent of the hydrodynamic conditions in the exposure medium. In the present study, the diffusion layer thickness (δ) at the sorbent/solution interface within the diffusion cell was characterised under controlled flow conditions. Laboratory tests indicated that, in the range of flow rates investigated, the average diffusion layer thickness ( δ ¯) varied from ∼60 to ∼110 μm, depending on the type of substance measured and the position of the sorbent with respect to the flow direction. Due to its ability to maintain an approximately constant δ ¯ , good to excellent agreement was found between measurements performed with the APS device in non-complexing media and concentrations measured in discrete water samples for all the substances investigated. These results suggest that the APS device could overcome issues affecting the quantitative interpretation of measurements by conventional passive sampling devices and serve as a useful tool for simultaneously monitoring a wide range of contaminants in water. • Accumulation is predicted from the aqueous diffusion layer thickness. • Controlled flow enabled accurate estimates of aqueous contaminant concentrations. • Excellent agreement was found with conventional sampling methods. [ABSTRACT FROM AUTHOR]