In situ monitoring of the diurnal cycling of dynamic metal species in a stream under contrasting photobenthic biofilm activity and hydrological conditions.

The diurnal evolution of the dynamic fraction, i.e., the potentially bioavailable fraction, of Cd, Cu, and Pb in a small river impacted by mining and smelting waste was studied in situ, under contrasting biofilm activity and hydrological conditions, using an automated voltammetric analyzer. The in situ, near real-time measurements revealed persistent dynamic metal species diurnal cycles. These cycles were affected mainly by the biochemical conditions rather than hydrological conditions. The data obtained from the in situ measurements, coupled with complementary laboratory analyses, revealed that various processes control the diurnal dynamic metal species cycles in the studied site; the trends of the diurnal cycles of the dynamic metal species can be different from those observed for the dissolved metal species measured in filtered samples. Moreover, the dynamic fraction of a given cationic metal can show diurnal cycles with opposite trends depending on the environmental conditions. All these findings highlight the interest and importance of automated, continuous measurements of specific relevant environmental metal fractions, compared to punctual weekly or monthly traditional sampling strategies of total dissolved metal analysis, to allow more appropriate water quality control and reliable assessment of metal ecotoxicological impact.