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Knowledge on the bioavailability of trace elements is essential in developing environmental quality standards. The purpose of this study was to explore the relationships between trace elements (in particular Uranium (U)) in sediments, porewater and their bioaccumulation by Chironomus riparius on a uranium mining site and river sediments upstream of the mine. The mobility and speciation of U in sediments was investigated using DGT. Geochemical modelling using CHESS provided insight on sorption behavior of U on ironoxyhydrite (HFO) and aqueous speciation of U. In the upstream site U concentrations found were 0.05 μmol g−1 in surface sediment, 0.84 nmol L−1 in porewater and 2.4 nmol g−1 in Chironomus riparius whereas in the ferrihydrite deposits on the mining sites the concentrations found were up to 9.4 μmol g−1 in surface sediment, 0.37 μmol L−1 in porewater and 0.684 μmol g−1 in in Chironomus riparius. Despite the large differences in concentrations of U between the two sites, sediment to dissolved partitioning coefficients, bioconcentration factor (BCF) and biota sediment accumulation factors (BSAF) were very comparable. In the upstream sediment binding of U to organic matter controls sorption and aqueous speciation of U, whereas in the HFO rich sediments, sorption on HFO and the formation of HFO colloids are the determining factors. The low BSAF factors and high BCF factors indicate that the bioaccumulation is due to uptake from the dissolved phase. The DGT probes with different binding resins provide information on the colloidal nature and lability of the dissolved U species. Image 1 • Bioaccumulation of U in mining sediments and an upstream site was investigated. • Low BSAF and high BCF at both sites were observed. • Sorption of U on ironoxyhydrite and organic matter control speciation and bioavailability. • DGT provides information on colloidal fraction and labile U-species. [ABSTRACT FROM AUTHOR]