To what extent can the biogeochemical cycling of mercury modulate the measurement of dissolved mercury in surface freshwaters by passive sampling?

Mercury (Hg) is a pollutant of global concern owing to its great toxicity even at very low concentrations. Its toxicity depends on its chemical forms evidencing the importance to study its speciation. Dissolved Hg (Hg(d)) and methylmercury (MeHg(d)) monitoring in surface freshwaters represents a great challenge because of their very low concentrations and substantial temporal variability at different timescales. The Hg(d) temporal variability depends on the environmental conditions such as the hydrology, water temperature, redox potential (Eh), and solar photo cycle. Passive samplers represent an alternative to improve the assessment of Hg(d) and MeHg(d) concentrations in surface freshwaters by integrating their temporal variability. An original sampling strategy was designed to assess the relevance of 3-mercaptopropyl DGT (Diffusive Gradient in Thin films) to integrate in situ the temporal variations of labile Hg (Hg(DGT)) and MeHg (MeHg(DGT)) concentrations. This strategy was implemented on two rivers to study the dynamics of Hg(d), Hg(DGT), MeHg(d) and MeHg(DGT) at diurnal and annual timescales. We evidenced that Hg(DGT) and MeHg(DGT) concentrations were generally consistent with discrete sampling measurements of Hg(d) and MeHg(d) in dynamic surface freshwaters. However, Hg(DGT) concentrations were overestimated (2-16 times higher) in case of low flow or low water depth, low suspended particulate matter (SPM) concentrations and elevated daily photoperiod. The most probable hypothesis is that such conditions promoted Hg0 production, and resulted in Hg0 uptake by DGT. Thus, attention should be paid when interpreting Hg(DGT) concentrations in surface freshwaters in environmental conditions that could promote Hg0 production.

The impact of dam flushing event on dissolved trace elements concentrations: Coupling integrative passive sampling and discrete monitoring.

Sediments accumulation in reservoirs induces water storage capacities reduction and flood risks increases rendering dam flushing or dredging events compulsory for security reasons. Short transient events like dam flushing monitoring is still a great challenge because the suspended sediments and contaminants concentrations increases could occur over only few hours/days and cover tens of kilometres. Since 1942, 21 dam flushing events have been performed on the Upper Rhône River (from Lake Geneva in Switzerland to Lyon in France) in order to evacuate accumulated sediments behind the Verbois dam (Switzerland). We designed an original sampling strategy to assess the 2016 dam flushing event consequences on the spatio-temporal dynamics of dissolved trace elements concentration and to reveal how passive sampling monitoring (Diffusive Gradient in Thin films, DGT) could improve this evaluation. Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, As and Hg dissolved concentrations were monitored by discrete and passive sampling at 3 stations over 160 km downstream the Verbois dam. Since dissolved Fe, Cu, Cd, Cr, Pb, Zn and Hg concentrations did not show great variations during the flushing event, the DGT efficiency was not fully demonstrated for these elements. In contrast, a sharp increase of Mn, Ni, Co and As dissolved concentrations (up to 22 times) was recorded, resulting mainly from a release from resuspended sediment. The dissolved As increase was mainly caused by reduced arsenic (AsIII) increase, even monitored 160 km downstream the Verbois dam. The DGT measurements were highly representative of trace elements concentrations and As speciation dynamics in comparison with discrete sampling. Although relatively high dispersion was highlighted for some elements DGT measurements during the flushing event, we showed that DGTs are robust and powerful time-integrative tools to monitor many trace elements more efficiently than discrete sampling during a short transient event on a large spatial scale.