Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France).

A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.

Sensitivity of freshwater periphytic diatoms to agricultural herbicides.

The biomonitoring of pesticide pollution in streams and rivers using algae such as diatoms remains difficult. The responses of diatom communities to toxic stress in stream water are disturbed by the variations of environmental parameters. In this study, periphytic algae collected in situ were exposed under controlled conditions to two major herbicides used in French agriculture (isoproturon and s-metolachlor). Three exposure regimes were tested: 5 and 30 microg L(-1) for 6 days and 30 microg L(-1) for 3 days followed by a recovery period of 3 days. The algal biomasses were assessed from pigment concentrations (chlorophyll a and c) and from live cell density. The highest concentration (30 microg L(-1)) of isoproturon inhibited the biomass increase statistically significantly. In periphyton exposed to 5 and 30 microg L(-1) of s-metolachlor, chlorophyll c concentration and live cell density were also statistically significantly lower than in the control. Periphyton left to recover after reduced exposure duration (3 days) showed higher growth rates after treatment with s-metolachlor than with isoproturon. Taxonomic identifications showed that species like Melosira varians, Nitzschia dissipata and Cocconeis placentula were not affected by the herbicide exposure. Other species like Eolimna minima and Navicula reichardtiana were more sensitive. Studying diatoms according to their trophic mode showed that facultative heterotroph species were statistically significantly favoured by isoproturon exposure at the highest concentration. Results obtained with s-metolachlor exposure showed a disturbance of cell multiplication rather than that of photosynthesis. These results suggest that photosynthesis inhibitors like isoproturon favour species able to survive when the autotroph mode is inhibited.

Investigation of the matrix effects on a HPLC-ESI-MS/MS method and application for monitoring triazine, phenylurea and chloroacetanilide concentrations in fresh and estuarine waters.

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.