-A microcosm experiment was carried out in order to test the effect of the herbicide metolachlor on river periphytic diatoms and to find potential diatom bioindicators of contamination. Effects were investigated at different biological organization levels (biofilm, diatom community, population and individual levels). The colonization of glass substrates by natural biofilm in artificial streams did not vary quantitatively between control and contaminated conditions (5 and 30 mg.L x1 ). However, non-parametric multivariate analysis of variance revealed a significant difference between contaminated and control diatom communities with regard to species composition. The difference was due to the greater development of probably tolerant species in the presence of the herbicide (e.g., Planothidium frequentissimum, Planothidium lanceolatum, Amphora montana, Surirella brebissonii and Nitzschia gracilis). An increase in the occurrence of abnormal forms was observed in relation to metolachlor concentration. In particular, up to 8% of the frustules of the species Surirella angusta exhibited prominent deformities. Monospecific acute toxicity tests were then performed on two species to estimate toxicity parameters based on growth inhibition. These tests also confirmed the teratogenic effect of the herbicide on S. angusta. This study shows that low concentrations of metolachlor in natural streams may significantly alter diatom community structure and that abnormal diatom forms should be taken into account in water contamination assessment.
In this work, the effects of matrix interferences on the analytical performance of a new multiresidue method based on off-line solid phase extraction followed by reversed-phase liquid chromatographic separation and electrospray triple quadrupole mass spectrometric detection were investigated. This technique allows the simultaneous determination of 30 triazines, phenylureas and chloroacetanilides, extracted from freshwaters, in 40 minutes. Quantifications were performed with the use of appropriate internal standards (i.e. atrazine D5, diuron D6 and metolachlor D6). The limits of quantification were from 1 to 32 ng L(-1) for the triazines, from 5 to 59 ng L(-1) for the phenylureas and from 13 to 54 ng L(-1) for the chloroacetanilides. The matrix effects were studied by spiking various waters (i.e. tap, river, pond and sea waters) with the chemicals of interest. The results showed that the samples with the highest conductivity (i.e. seawater) and the most abundant dissolved organic matter content (i.e. pond water) exhibited important matrix effects with signal suppressions and high imprecision, respectively. These matrix effects were strongly minimized by performing appropriate internal standardizations. Afterward, this analytical method was applied for analyzing environmental samples from either river or estuarine waters and for monitoring herbicide input in a freshwater-seawater interface.
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