The achievement of good chemical status: an impossible mission for local water managers?

The European Water Framework Directive (2000) required to achieve good ecological and chemical status in surface waters of the EU Member States in 2015. For pesticides, this means ensuring that concentrations in rivers do not exceed 0.1 g/L per molecule and 0.5 g/L for the sum of the concentrations of the different molecules found. At national scale, EcoPhyto plan (2008) aimed to reduce pesticide use by 50% within 10. This plan has been revised and postponed to 2025 as observed pesticide use is varying between years and concentrations in river did not decrease as expected. Although vineyards cover a small percentage of agricultural land surfaces, they contribute to 20% of national pesticide use. The presence of pesticides in rivers surrounding wine territories is therefore a current environmental concern. Thus, the recovery of the water quality requires local action programs to reduce pesticide contamination in rivers. The Layon catchment comprises 13% of vineyard. It is therefore subject to an action program led by the local water committee: the SAGE Layon-Aubance-Louet. Its goal is to ensure pesticide concentrations are reduced to 1 g/L in 2018 and 0.5 g/L in 2027. In this context, one of the actions of the SAGE, with the assistance of the University of Angers, addresses the study of peaks in pesticide concentrations during runoff events in a small catchment covered by vineyards. Between 2009 and 2016, one of the two farmers has converted to organic farming with consequent decreases in pesticides input to the case study which thus complied with the EcoPhyto objectives. Results demonstrate first a peak intensity of pesticides in runoff waters in relation with the date of application with a decrease of concentrations during time after the treatment and second a relation between peaks of SPM and pesticides. Transfer of pesticides in this catchment is strongly linked to runoff. Thus, even if the increase of grass surface within vineyard improves the soil stability and decreases erosion sensitivity, it is not sufficient to stop all transfer of pesticides. Following the results of this study, neither the objectives of national policies to reduce by half the pesticide use nor the local objectives to decrease partially the un-weeded surface of vineyards would permit to achieve good chemical status, as confirmed by the current state of the water quality of the Layon river monitored by local water managers. Thus, in the continuation of all its efforts

Multiresidue determination of 256 pesticides in lavandin essential oil by LC/ESI/sSRM: advantages and drawbacks of a sampling method involving evaporation under nitrogen

The determination of 256 multiclass pesticides in lavandin essential oil has been performed by liquid chromatography–electrospray ionization tandem mass spectrometry using the scheduled selected reaction monitoring mode available on a quadrupole-linear ion trap mass spectrometer. With the aim of improving the limits of quantification (LOQs) of the target molecules, a sampling step based on evaporation of the essential oil under a nitrogen flow assisted by controlled heating was tested. The LOQs determined in this case were compared with the values obtained with the classic dilution preparation method. With sampling by dilution, 247 pesticides were detected and quantified at low concentration, with 74 % of the pesticides having LOQs of 10 μg L-1 or less. With the evaporation method, a global improvement of the LOQs was observed, with lower LOQs for 92 active substances and LOQs of 10 μg L-1 or less for 82.8 % of the pesticides. Almost twice as many active substances had an LOQ of 1 μg L-1 or less when the evaporation method was used. Some pesticides exhibited poor recovery or high variance caused by volatilization or degradation during the evaporation step. This behavior was evidenced by the case of thiophanate-methyl, which is degraded to carbendazim. Figure Sampling method by dilution or evaporation in the multiresidue determination of pesticides in essential oils by LC/M

Revue des principales méthodes d’identification des sources de pollutions fécales des eaux et coquillages

Les contaminations fécales des eaux et des coquillages induisent des risques pour la santé humaine et des pertes économiques liées, entre autres, aux interdictions de baignade et à la fermeture des zones de conchyliculture. La réduction des apports à l’origine de cette contamination est facilitée par une identification précise des sources (humaines ou animales) qui peut aussi servir à hié rarchiser les mesures à adopter en cas de besoin. De nombreux marqueurs ont été proposés à ce titre durant les deux dernières décennies. Ils correspondent :-à des micro-organismes (bactéries, virus ou bactériophages) mis en évidence par des approaches culturales, biochimiques ou moléculaires; -à des molécules chimiques présentes naturellement dans les fèces ou associées à l’une des sources de pollution; -et à la mise en évidence de cellules spécifiques de l’hôte dissimulées dans les matières fécales. Cet article présente ces différentes methods d’identification des sources de contaminations fécales en décrivant leur utilisation et la nature des résultats qu’elles permettent d’obtenir. Le principal corollaire de cette revue bibliographique est qu’il semble nécessaire de coupler différents marqueurs pour pouvoir identifier les sources

Multiresidue Analysis of Multiclass Pesticides in Lavandin Essential Oil by LC/MS/MS Using the Scheduled Selected Reaction Monitoring Mode

In this paper we describe the development of the first multiclass pesticide residue method applied to essential oils. A total of 70 pesticides covering a wide range of polarity and currently used on essential oil crops have been included in the method. The procedure consists of a 10-fold dilution of lavandin essential oil followed by a direct injection analysis by liquid chromatography/tandem mass spectrometry. The system used is an API 4000 QTrap equipped with an electrospray ionization interface and operating in scheduled selected reaction monitoring acquisition mode. Matrix effects were evaluated by comparing the slopes of matrix-matched and solvent-based calibration curves. Weak signal suppression or enhancement (<20%) was observed for most of the compounds. Method sensitivity was determined statistically by the injection of five matrix-matched calibration curves with the distribution’s normality and the variance’s homogeneity checked before establishment of a suitable regression model. Limits of detection (LODs) and quantification (LOQs) were then determined using the blank standard’s deviation and the slope of the mean curve. The analytical method has been validated for 67 of the 70 pesticides and meets the following LOQs: ≤1 μg/L for 9 pesticides, ≤5 μg/L for 44, ≤10 μg/L for 9, and ≤20 μg/L for

Effect of thiamethoxam on cockroach locomotor activity is associated with its metabolite clothianidin

BACKGROUND: In the present study, the effect of thiamethoxam and clothianidin on the locomotor activity of American cockroach, Periplaneta americana (L.), was evaluated. Because it has been proposed that thiamethoxam is metabolised to clothianidin, high-performance liquid chromatography coupled with mass spectrometry was used to evaluate the amount of clothianidin on thiamethoxam-treated cockroaches. RESULTS: One hour after neonicotinoid treatment, the time spent in the open-field-like apparatus significantly increased, suggesting a decrease in locomotor activity. The percentage of cockroaches displaying locomotor activity was significantly reduced 1 h after haemolymph application of 1 nmol g(-1) neonicotinoid, while no significant effect was found after topical and oral administration. However, at 24 and 48 h, all neonicotinoids were able to reduce locomotor activity, depending on their concentrations and the way they were applied. Interestingly, it was found that thiamethoxam was converted to clothianidin 1 h after application, but the amount of clothianidin did not rise proportionately to thiamethoxam, especially after oral administration. CONCLUSION: The data suggest that the effect of thiamethoxam on cockroach locomotor activity is due in part to clothianidin action because (1) thiamethoxam levels remained persistent 48 h after application and (2) the amount of clothianidin in cockroach tissues was consistent with the toxicity of thiamethoxam

High frequency monitoring of pesticides in runoff water from a vineyard: ecotoxicological and hysteresis pattern analysis

Rainfall-induced peaks in pesticide concentrations can occur rapidly; therefore, low frequency sampling may largely underestimate maximum pesticide concentrations and fluxes. Detailed storm-based sampling of pesticide concentrations in runoff water to better predict pesticide sources, transport pathways and toxicity within the headwater catchments is actually lacking. High frequency monitoring (2 min) of dissolved concentrations and loads for seven pesticides (Dimetomorph, Fluopicolide, Glyphosate, Iprovalicarb, Tebuconazole, Tetraconazole and Triadimenol) and one degradation product (AMPA) were assessed for 20 runoff events from 2009 to 2012 at the outlet of a vineyard catchment in the Layon catchment in France. The pesticide concentrations reached 387 g/L. All of the runoff events exceeded the mandated acceptable concentrations of 0.1 g/L for each pesticide (European directive 2013/39/EC). High resolution sampling used to detect the peak pesticide levels revealed that Toxic Units (TU) for algae, invertebrates and fish often exceeded the European Uniform principles (25%). The instantaneous and average (time or discharge-weighted) concentrations indicated an up to 30- or 4-fold underestimation of the TU obtained when measuring the maximum concentrations, respectively, highlighting the important role of the sampling methods for assessing peak exposure. High resolution sampling combined with concentration-discharge hysteresis analyses revealed that clockwise responses were predominant (52%), indicating that Hortonian runoff is the prevailing surface runoff trigger mechanism in the study catchment. The hysteresis patterns for suspended solids and pesticides were highly dynamic and storm- and chemical-dependent. Intense rainfall events induced stronger C-Q hysteresis (magnitude). This study provides new insights into the complexity of pesticide dynamics in runoff water and highlights the ability of hysteresis analysis to improve the understanding of pesticide supply and transport

Modalités de transferts de pesticides dans un petit bassin versant viticole du Layon

Date du colloque&nbsp;: 2012</p