Redox and size speciation of chromium in rivers contaminated with tannery wastewater was carried out to provide insight into its transport and removal mechanisms. Total chromium was determined with Inductively Coupled Plasma‐Mass Spectrometry and Cr (VI) with Catalytic Adsorption Stripping Voltammetry. For the size speciation, particles were retained with a cartridge filter (cut‐off 1.2 μm) and the total filterable fraction was further fractionated with Tangential Flow Filtration to determine the concentrations of chromium associated with the High Molecular Weight Colloidal (HMWC), Low Molecular Weight Colloidal (LMWC) and Truly Dissolved (TD) fractions. Two fluvial systems of similar sizes, but located in contrasting climatic zones, were selected for comparison: the Sebou‐Fez system in Morocco and Dunajec River‐Czorsztyn Reservoir system in Poland. Particulate Cr dominated in the Sebou‐Fez system (about 90 %); while in the Dunajec‐Czorsztyn system, it represented only 17–53 % of the total chromium in raw water. Still, the partition coefficients [Kd] were of the same magnitude. Chromium (III) was the only form detected in Sebou‐Fez, whereas in Dunajec‐Czorsztyn Cr (VI) was also present with its proportion increasing downstream from the input of tannery wastewater due to the preferential removal of Cr (III). In the filtered water in Morocco a large fraction of Cr occurred in the HMWC fraction (50–70 %) at the two most contaminated sites, while the LMWC and TD forms prevailed at the non‐contaminated sites in the Sebou River. At a very high concentration, in the water in the proximity of tanneries (well above the theoretical saturation level) Cr precipitated as polynuclear Cr‐hydroxide. In Dunajec‐Czorsztyn, the partition of Cr (III) was approximately equal between the HMWC, LMWC and TD fractions, in contrast to Cr (VI) which occurred almost exclusively in the TD fraction. In both systems, Cr (III) was rapidly removed from the water to the sediments. The confluence of the Sebou with the Fez and the Czorsztyn reservoir trapped efficiently Cr (III) preventing its spreading over long distances. Cr (VI) showed conservative behavior and bypassed the Czorsztyn Reservoir. This study provides a first set of data on the partitioning of Cr (III) and Cr (VI) between the particulate, the colloidal and truly dissolved fractions in fluvial systems contaminated with tannery effluents. It also suggests that, in these systems, truly dissolved Cr (III) can be adequately modeled from the total filterable concentrations.
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