Contrasting distribution of REE and yttrium among particulate, colloidal and dissolved fractions during low and high flows in peri-urban and agricultural river systems.

Understanding the possible consequences of anthropogenic activities on REY environmental fate and adverse effects on biota requires a detailed knowledge of their distribution between the particulate, colloidal and dissolved fractions. Such information is practically non-existent for peri-urban rivers having heavily populated basins and suffering from direct impacts from various human activities. The present study compared the distribution of REY among the particulate (>1000 nm), coarse colloidal (1000 nm - 220 nm), small colloidal (220 nm - 10 kDa) and dissolved (<10 kDa) water fractions in two peri-urban river basins having contrasted land uses (agricultural vs urban/industrial) under low and high flow conditions. Regardless of hydrological conditions, most of the REY were in the particulate fraction for both catchments. These results suggest erosion of soils as the main source of particulate REY in the two rivers, although a Nd anomaly of industrial origin occurred in the particulate and coarse colloidal fractions of the industrialized river basin. During low flow, the REY patterns of the dissolved fraction displayed marked Gd and Eu anomalies and a fractionation between Light REY and Heavy REY. Both characteristics reflect the influence of wastewater treatment plant effluents on the dissolved REY patterns in the two rivers. During high flow, the dissolved fraction acquired a less fractionated, more natural Light REY and Middle REY pattern, including much lower Gd and Eu positive anomalies. The REY fractionation of the coarse colloidal fraction was close to the particulate, while small colloids were depleted in Light REY and more similar to the dissolved fraction. These different patterns suggest a difference in the nature of REY bearing phases between the two colloidal fractions. The available results collectively show that a complete understanding of REY environmental fate and anomalies cannot be achieved from the sole study of filterable water fractions (typically <0.45 µm).

Effect of natural organic matter on thallium and silver speciation.

Natural organic matter (NOM) is known to play an important role in the transport and binding of trace metal elements in aquatic and soil systems. Thallium is a pollutant for which the extent of the role played by NOM is poorly known. Consequently, this study investigates thallium(I) and its complexation to a purified humic substance as proxy for NOM. Experiments were performed with the Donnan Membrane Technique to separate, for the first time, the free Tl+ ion from its complexed form in the bulk solution. Various pH and concentrations were investigated at constant ionic strength and constant NOM proxy concentrations in solution. Experimental results were described with NICA-Donnan model. Thallium complexation was compared to silver complexation using literature data and using the same NICA-Donnan formalism. Parameters for these two cations (Tl+ and Ag+) are reported in this article, for the first time. Results display low thallium complexation to the NOM proxy while silver competes with divalent cations for the NOM binding sites. Calculated speciation for dissolved thallium highlights the dominance of free thallium (Tl+) in solution whereas Tl-NOM complexes contribute roughly 15% to total Tl(I) species in river and lake type waters. Similar results are obtained for soil solutions, Tl-bound to NOM < 30% of total, from UK soils with different land use and geochemistry.