Flow conditions influence diuron toxicokinetics and toxicodynamics in freshwater biofilms.

Biofilms are considered as good bioindicators of contamination by means of their capacity to react quickly to xenobiotics exposure, and their pivotal role in sustaining the aquatic trophic web. The exchanges of dissolved substances between water column and biofilm can be modulated by flow velocity. This study deals with toxicokinetic (transfer mechanisms) and toxicodynamic (effects) modelling of pesticides under two contrasted flow conditions. Diuron was used to run a 2-h kinetic study on mature biofilms in river channels. Two flow conditions were considered (⋘1 cm·s-1: lentic environments such as ponds, 2 cm·s-1: lotic environments such as watercourses). Three concentrations were tested in order to estimate contamination levels in biofilms: 0, 5 (environmentally relevant concentration) and 50 (to determine the concentration effect) µg·L-1. The effect of the above-mentioned factors was also assessed on biofilms photosynthesis inhibition. For successive sampling times between 0 and 2 h, the raw biofilms and EPS tightly bound to cells plus microorganisms (T-EPS-M), were physically separated and analysed for diuron accumulation and structural and functional microbial descriptors. Diuron amounts accumulated in biofilm increased with increasing diuron exposure. Biofilms accumulated higher amounts of diuron at the lower flow velocity compared to high flow for raw biofilms, while accumulation in the T-EPS-M fraction was similar between flow conditions. Consequently, both flow velocity and diuron exposure had an influence on diuron bioaccumulation and distribution. Photosynthesis inhibition over time was directly linked to the exposure concentration of diuron recorded in the T-EPS-M fraction. These results suggest that flow causes a loss of organic matter in biofilms, decreasing the total accumulation of diuron, especially within diffusible EPS. As pesticide distribution in biofilm is a major factor in the onset of toxicity, the novel fractioning method presented here will improve further toxicokinetic and toxicodynamic studies dealing with biofilms exposed to organic toxicants.

Hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry for acidic herbicides and metabolites analysis in fresh water.

Theoretical papers and environmental applications of hydrophilic interaction liquid chromatography (HILIC) have been published for a wide range of analytes, but to our knowledge, no study focused on acidic herbicides (e.g., triketones, phenoxy acids, sulfonylurea, and acidic metabolites of chloroacetanilides). Matrix effects are the main obstacle to natural sample analysis by liquid chromatography coupled with tandem mass spectrometry (MS) via an electrospray ionization (ESI) interface. Therefore, we paid particular attention on limiting interference by (i) adapting the emerging HILIC technique, which is generally considered more sensitive than conventional reversed phase liquid chromatography and (ii) optimizing the solid phase extraction (SPE) step using a design of experiment. A rapid and reliable off line SPE-HILIC-ESI-MS/MS method was thus developed for the quantification of acidic herbicides in fresh water, with limits of quantifications (LOQs) ranging from 5 to 22 ng L(-1). Then, the analysis of freshwater samples highlighted the robustness of the method, and the importance of the chloroacetanilides metabolites among the studied analytes.