No abstract

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.

Interdisciplinary studies on aquatic environments and cross-validation of laboratory vs. field results will likely increase the need for simultaneous use of large-and small-scale ultrafiltration systems. In this study, a comparison of two ultrafiltration systems differing in scale (PrepScale and PelliconXL, Millipore; membrane areas 0.54 m 2 and 0.005 m 2 , respectively), was made for the cut-offs 3 and 300 kDa. Large systems are useful for their high permeate throughput, while small systems are necessary when the amount of sample is limited. The ability of PrepScale and PelliconXL systems to provide comparable results for organic carbon fractionation was studied for polysaccharide solutions and natural freshwaters. In the latter, the colloidal proportions of different trace metals (V, Cr, Mn, Co, Ni, Cu, Sb, and U) were also determined. Although the colloidal proportions obtained with PelliconXL 3 kDa were sometimes slightly higher than with PrepScale 3 kDa (principally for DOC and U in natural waters), Mann-Whitney statistical test showed no significant difference in the overall fractionation properties of the two systems. Our observations show that reaching high concentration factors lead to a strong modification of colloids size distribution in the range 50-2,000 nm and thus low concentration factors are preferable to preserve the colloid integrity.