Do pesticides degrade in surface water receiving runoff from agricultural catchments? Combining passive samplers (POCIS) and compound-specific isotope analysis.

Pesticides lead to surface water pollution and ecotoxicological effects on aquatic biota. Novel strategies are required to evaluate the contribution of degradation to the overall pesticide dissipation in surface waters. Here, we combined polar organic chemical integrative samplers (POCIS) with compound-specific isotope analysis (CSIA) to trace in situ pesticide degradation in artificial ponds and agricultural streams. The application of pesticide CSIA to surface waters is currently restricted due to environmental concentrations in the low µg.L-1 range, requiring processing of large water volumes. A series of laboratory experiments showed that POCIS enables preconcentration and accurate recording of the carbon isotope signatures (δ13C) of common pesticides under simulated surface water conditions and for various scenarios. Commercial and in-house POCIS did not significantly (Δδ13C < 1 %) change the δ13C of pesticides during uptake, extraction, and δ13C measurements of pesticides, independently of the pesticide concentrations (1-10 µg.L-1) or the flow speeds (6 or 14 cm.s-1). However, simulated rainfall events of pesticide runoff affected the δ13C of pesticides in POCIS. In-house POCIS coupled with CSIA of pesticides were also tested under different field conditions, including three flow-through and off-stream ponds and one stream receiving pesticides from agricultural catchments. The POCIS-CSIA method enabled to determine whether degradation of S-metolachlor and dimethomorph mainly occurred in agricultural soil or surface waters. Comparison of δ13C of S-metolachlor in POCIS deployed in a stream with δ13C of S-metolachlor in commercial formulations suggested runoff of fresh S-metolachlor in the midstream sampling site, which was not recorded in grab samples. Altogether, our study highlights that the POCIS-CSIA approach represents a unique opportunity to evaluate the contribution of degradation to the overall dissipation of pesticides in surface waters.

Electrochemical analysis of a microbial electrochemical snorkel in laboratory and constructed wetlands.

Microbial electrochemical snorkel (MES) is a short-circuited microbial fuel cell applicable to water treatment that does not produce energy but requires lower cost for its implementation. Few reports have already described its water treatment capabilities but no deeper electrochemical analysis were yet performed. We tested various materials (iron, stainless steel and porous graphite) and configurations of snorkel in order to better understand the rules that will control in a wetland the mixed potential of this self-powered system. We designed a model snorkel that was studied in laboratory and on the field. We confirmed the development of MES by identifying anodic and cathodic parts, by measuring the current between them and by analyzing microbial ecology in laboratory and field experiments. An important application is denitrification of surface water. Here we discuss the influence of nitrate on its electrochemical response and denitrification performances. Introducing nitrate caused the increase of the mixed potential of MES and of current at a potential value relatively more positive than for nitrate-reducing biocathodes described in the literature. The major criteria for promoting application of MES in artificial wetland dedicated to mitigation of non-point source nitrate pollution from agricultural water are considered.

High denitrification potential but low nitrous oxide emission in a constructed wetland treating nitrate-polluted agricultural run-off.

Constructed wetlands (CW) can efficiently remove nitrogen from polluted agricultural run-off, however, a potential caveat is nitrous oxide (N2O), a harmful greenhouse gas and stratospheric ozone depleter. During five sampling campaigns, we measured N2O fluxes from a 0.53 ha off-stream CW treating nitrate-rich water from the intensively fertilized watershed in Rampillon, France, using automated chambers with a quantum cascade laser system, and manual chambers. Sediment samples were analysed for potential N2 flux using the HeO2 incubation method. Both inlet nitrate (NO3-) concentrations and N2O emission varied significantly between the seasons. In the Autumn and Winter inlet concentrations were about 11 mg NO3--N L-1, and < 6.5 mg NO3--N L-1 in the Spring and Summer. N2O emission was highest in the Autumn (mean ± standard error: 9.7 ± 0.2 µg N m-2 h-1) and lowest in the Summer (wet period: 0.2 ± 0.3 µg N m-2 h-1). The CW was a very weak source of N2O emitting 0.32 kg N2O-N ha-1 yr-1 and removing around 938 kg NO3--N ha-1 yr-1, the ratio of N2O-N emitted to NO3--N removed was 0.033%. The automated and manual chambers gave similar results. From the potential N2O formation in the sediment, only 9% was emitted to the atmosphere, the average N2 N 2O ratio was high: 89:1 for N2-Npotential: N2O-Npotential and 1353:1 for N2-Npotential: N2O-Nemitted. These results indicate complete denitrification. The focused principal component analysis showed strong positive correlation between the gaseous N2O fluxes and the following environmental factors: NO3--N concentrations in inlet water, streamflow, and nitrate reduction rate. Water temperature, TOC and DOC in the water and hydraulic residence time showed negative correlations with N2O emissions. Shallow off-stream CWs such as Rampillon may have good nitrate removal capacity with low N2O emissions.

Denitrifying bio-cathodes developed from constructed wetland sediments exhibit electroactive nitrate reducing biofilms dominated by the genera Azoarcus and Pontibacter.

To limit the nitrate contamination of ground and surface water, stimulation of denitrification by electrochemical approach is an innovative way to be explored. Two nitrate reducing bio-cathodes were developed under constant polarization (-0.5 V vs SCE) using sediments and water from a constructed wetland (Rampillon, Seine-et-Marne, France). The bio-cathodes responded to nitrate addition on chronoamperometry through an increase of the reductive current. The denitrification efficiency of the pilots increased by 47% compared to the negative controls without electrodes after polarization. 16S rRNA gene sequencing of the biofilms and sediments evidenced the significant and discriminating presence of the Azoarcus and Pontibacter genera in the biofilms from biocathodes active for nitrate reduction. Our study shows the possibility to promote the development of efficient Azoarcus-dominated biocathodes from freshwater sediment to enhance nitrate removal from surface waters.

Dynamics and mitigation of six pesticides in a "Wet" forest buffer zone.

Pesticide pollution is one of the main current threats on water quality. This paper presents the potential and functioning principles of a "Wet" forest buffer zone for reducing concentrations and loads of glyphosate, isoproturon, metazachlor, azoxystrobin, epoxiconazole, and cyproconazole. A tracer injection experiment was conducted in the field in a forest buffer zone at Bray (France). A fine time-scale sampling enabled to illustrate that interactions between pesticides and forest buffer substrates (soil and organic-rich litter layer), had a retarding effect on molecule transfer. Low concentrations were observed for all pesticides at the forest buffer outlet thus demonstrating the efficiency of "Wet" forest buffer zone for pesticide dissipation. Pesticide masses injected in the forest buffer inlet directly determined concentration peaks observed at the outlet. Rapid and partially reversible adsorption was likely the major process affecting pesticide transfer for short retention times (a few hours to a few days). Remobilization of metazachlor, isoproturon, desmethylisoproturon, and AMPA was observed when non-contaminated water flows passed through the forest buffer. Our data suggest that pesticide sorption properties alone could not explain the complex reaction mechanisms that affected pesticide transfer in the forest buffer. Nevertheless, the thick layer of organic matter litter on the top of the forest soil was a key parameter, which enhanced partially reversible sorption of pesticide, thus retarded their transfer, decreased concentration peaks, and likely increased degradation of the pesticides. Consequently, to limit pesticide pollution transported by surface water, the use of already existing forest areas as buffer zones should be equally considered as the most commonly implemented grass buffer strips.

Pesticide contamination interception strategy and removal efficiency in forest buffer and artificial wetland in a tile-drained agricultural watershed.

Pesticide pollution is a major threat to aquatic ecosystems that can be mitigated through complementary actions including buffer zones (BZs). This paper discusses the results of 3 yr of field-scale monitoring of the concentration and load transfer of 16 pesticides out of a tile-drained catchment (Bray, France) and their reduction through two BZ: an artificial wetland (AW) and a forest buffer (FB). Typically, the highest concentrations were measured in the first flows following pesticide applications or resuming after periods of low or no flow. An open/close water management strategy was implemented to operate the parallel BZ based on pesticide applications by the farmer. The strategy was efficient in intercepting molecules whose highest concentrations occurred during the first flows following application. Inlet vs. outlet pesticide load reductions ranged from 45% to 96% (AW) and from -32% to 100% (FB) depending on the pesticide molecule and the hydrological year. Partly reversible adsorption was a dominant process explaining pesticide removal; whereas, degradation occurred for sufficiently long water retention time. Apart from the least sorbing molecules (e.g., isoproturon), BZ can partially remove pesticide pollution.