Elodie Maillard

Removal of pesticide mixtures in a stormwater wetland collecting runoff from a vineyard catchment

Wetlands can collect contaminated runoff from agricultural catchments and retain dissolved and particle-laden pesticides. However, knowledge about the capacity and functioning of wetland systems with respect to the removal of pesticides is very limited. Here we show that stormwater wetlands can efficiently remove pesticides in runoff from vineyard catchments during the period of pesticide application, although flow and hydrochemical conditions of the wetland largely vary over time. During the entire agricultural season, the inflowing load of nine fungicides, six herbicides, one insecticide and four degradation products was 8.039g whereas the outflowing load was 2.181g. Removal rates of dissolved loads by the wetland ranged from 39% (simazine) to 100% (cymoxanil, gluphosinate, kresoxim methyl and terbuthylazine). Dimethomorph, diuron, glyphosate, metalaxyl and tetraconazole were more efficiently removed in spring than in summer. More than 88% of the input mass of suspended solids was retained, underscoring the capability of the wetland to trap pesticide-laden particles via sedimentation. Only the insecticide flufenoxuron was frequently detected in the wetland sediments. Our results demonstrate that stormwater wetlands can efficiently remove pesticide mixtures in agricultural runoff during critical periods of pesticide application, although fluctuations in the runoff regime and hydrochemical characteristics can affect the removal rates of individual pesticides.

Transport and attenuation of dissolved glyphosate and AMPA in a stormwater wetland.

Glyphosate is an herbicide used widely and increasingly since the early 1990s in production of many crops and in urban areas. However, knowledge on the transport of glyphosate and its degradation to aminomethylphosphonic acid (AMPA) in ecosystems receiving urban or agricultural runoff is lacking. Here we show that transport and attenuation of runoff-associated glyphosate and AMPA in a stormwater wetland differ and largely vary over time. Dissolved concentrations and loads of glyphosate and AMPA in a wetland receiving runoff from a vineyard catchment were assessed during three consecutive seasons of glyphosate use (March to June 2009, 2010 and 2011). The load removal of glyphosate and AMPA by the wetland gradually varied yearly from 75% to 99%. However, glyphosate and AMPA were not detected in the wetland sediment, which emphasises that sorption on the wetland vegetation, which increased over time, and biodegradation were prevailing attenuation processes. The relative load of AMPA as a percentage of total glyphosate increased in the wetland and ranged from 0% to 100%, which indicates the variability of glyphosate degradation via the AMPA pathway. Our results demonstrate that transport and degradation of glyphosate in stormwater wetlands can largely change over time, mainly depending on the characteristics of the runoff event and the wetland vegetation. We anticipate our results to be a starting point for considering degradation products of runoff-associated pesticides during their transfer in wetlands, in particular when using stormwater wetlands as a management practice targeting pesticide attenuation.

Bacterial communities in batch and continuous-flow wetlands treating the herbicide S-metolachlor

Knowledge of wetland bacterial communities in the context of pesticide contamination and hydrological regime is scarce. We investigated the bacterial composition in constructed wetlands receiving Mercantor Gold(®) contaminated water (960 g L(-1) of the herbicide S-metolachlor, >80% of the S-enantiomer) operated under continuous-flow or batch modes to evaluate the impact of the hydraulic regime. In the continuous-flow wetland, S-metolachlor mass removal was >40%, whereas in the batch wetland, almost complete removal of S-metolachlor (93-97%) was observed. Detection of ethanesulfonic and oxanilic acid degradation products further indicated S-metolachlor biodegradation in the two wetlands. The dominant bacterial populations were characterised by terminal restriction fragment length polymorphism (T-RFLP) and 454 pyrosequencing. The bacterial profiles evolved during the first 35 days of the experiment, starting from a composition similar to that of inlet water, with the use of nitrate and to a lesser extent sulphate and manganese as terminal electron acceptors for microbial metabolism. Proteobacteria were the most abundant phylum, with Beta-, Alpha- and Gammaproteobacteria representing 26%, 19% and 17% respectively of total bacterial abundance. Bacterial composition in wetland water changed gradually over time in continuous-flow wetland and more abruptly in the batch wetland. Differences in overall bacterial water structure in the two systems were modest but significant (p=0.008), and S-metolachlor, nitrate, and total inorganic carbon concentrations correlated with changes in the bacterial profiles. Together, the results highlight that bacterial composition profiles and their dynamics may be used as bioindicators of herbicide exposure and hydraulic disturbances in wetland systems.

Using compound-specific isotope analysis to assess the degradation of chloroacetanilide herbicides in lab-scale wetlands

Compound-specific isotope analysis (CSIA) is a promising tool to study the environmental fate of a wide range of contaminants including pesticides. In this study, a novel CSIA method was developed to analyse the stable carbon isotope signatures of widely used chloroacetanilide herbicides. The developed method was applied in combination with herbicide concentration and hydrochemical analyses to investigate in situ biodegradation of metolachlor, acetochlor and alachlor during their transport in lab-scale wetlands. Two distinct redox zones were identified in the wetlands. Oxic conditions prevailed close to the inlet of the four wetlands (oxygen concentration of 212±24μM), and anoxic conditions (oxygen concentrations of 28±41μM) prevailed towards the outlet, where dissipation of herbicides mainly occurred. Removal of acetochlor and alachlor from inlet to outlet of wetlands was 56% and 51%, whereas metolachlor was more persistent (23% of load dissipation). CSIA of chloroacetanilides at the inlet and outlet of the wetlands revealed carbon isotope fractionation of alachlor (εbulk=-2.0±0.3‰) and acetochlor (εbulk=-3.4±0.5‰), indicating that biodegradation contributes to the dissipation of both herbicides. This study is a first step towards the application of CSIA to evaluate the transport and degradation of chloroacetanilide herbicides in the environment.

Pesticide mass budget in a stormwater wetland.

Wetlands are reactive landscape zones that provide ecosystem services, including the improvement of water quality. Field studies distinguishing pesticide degradation from retention to evaluate the sink and source functions of wetlands are scarce. This study evaluated based on a complete mass budget the partitioning, retention, and degradation of 12 pesticides in water, suspended solids, sediments, and organisms in a wetland receiving contaminated runoff. The mass budget showed the following: (i) dissolved pesticides accounted for 95% of the total load entering the wetland and the pesticide partitioning between the dissolved phase and the suspended solids varied according to the molecules, (ii) pesticides accumulated primarily in the <250 μm bed sediments during spring and late summer, and (iii) the hydrological regime or the incoming pesticide loads did not influence the pesticide dissipation, which varied according to the molecules and the wetland biogeochemical conditions. The vegetation enhanced the pesticide degradation during the vegetative phase and the pesticides were released during plant senescence. The dithiocarbamates were degraded under oxic conditions in spring, whereas glyphosate and aminomethylphosphonic acid (AMPA) degradation occurred under reducing conditions during the summer. The complete pesticide mass budget indicates the versatility of the pesticide sink and source functions of wetland systems.

Degradation of chloroacetanilide herbicides and bacterial community composition in lab-scale wetlands

Degradation of chloroacetanilide herbicides rac-metolachlor, acetochlor, and alachlor, as well as associated bacterial populations, were evaluated in vertical upflow wetland columns using a combination of hydrochemical and herbicide analyses, and DNA-based approaches. Mass dissipation of chloroacetanilides, continuously supplied at 1.8-1.9 μM for 112 days, mainly occurred in the rhizosphere zone under nitrate and sulphate-reducing conditions, and averaged 61±14%, 52±12% and 29±19% for acetochlor, alachlor and rac-metolachlor, respectively. Metolachlor enantiomer fractions of 0.494±0.009 in the oxic zone and 0.480±0.005 in the rhizosphere zone indicated preferential biodegradation of the S-enantiomer. Chloroacetanilide ethane sulfonic acid and oxanilic acid degradates were detected at low concentrations only (0.5 nM), suggesting extensive degradation and the operation of yet unknown pathways for chloroacetanilide degradation. Hydrochemical parameters and oxygen concentration were major drivers of bacterial composition, whereas exposure to chloroacetanilides had no detectable impact. Taken together, the results underline the importance of anaerobic degradation of chloroacetanilides in wetlands, and highlight the potential of complementary chemical and biological approaches to characterise processes involved in the environmental dissipation of chloroacetanilides.

Dissipation of hydrological tracers and the herbicide S-metolachlor in batch and continuous-flow wetlands

Pesticide dissipation in wetland systems with regard to hydrological conditions and operational modes is poorly known. Here, we investigated in artificial wetlands the impact of batch versus continuous-flow modes on the dissipation of the chiral herbicide S-metolachlor (S-MET) and hydrological tracers (bromide, uranine and sulforhodamine B). The wetlands received water contaminated with the commercial formulation Mercantor Gold(®) (960 g L(-1) of S-MET, 87% of the S-enantiomer). The tracer mass budget revealed that plant uptake, sorption, photo- and presumably biodegradation were prominent under batch mode (i.e. characterized by alternating oxic-anoxic conditions), in agreement with large dissipation of S-MET (90%) under batch mode. Degradation was the main dissipation pathway of S-MET in the wetlands. The degradate metolachlor oxanilic acid (MOXA) mainly formed under batch mode, whereas metolachlor ethanesulfonic acid (MESA) prevailed under continuous-flow mode, suggesting distinct degradation pathways in each wetland. R-enantiomer was preferentially degraded under batch mode, which indicated enantioselective biodegradation. The release of MESA and MOXA by the wetlands as well as the potential persistence of S-MET compared to R-MET under both oxic and anoxic conditions may be relevant for groundwater and ecotoxicological risk assessment. This study shows the effect of batch versus continuous modes on pollutant dissipation in wetlands, and that alternate biogeochemical conditions under batch mode enhance S-MET biodegradation.

Removal of dissolved pesticide mixtures by a stormwater wetland receiving runoff from a vineyard catchment: an inter-annual comparison

Wetlands can collect contaminated runoff from agricultural catchments and have intrinsic physical, chemical and biological retention and removal processes useful for mitigating pesticides. However, knowledge about the ability of stormwater wetlands to mitigate pesticide mixtures in runoff is currently very limited. We show here that stormwater wetlands that primarily serve for flood protection can also be effective tools for reducing concentrations and removing loads of runoff-related pesticides and some of their degradation products into downstream aquatic ecosystems. Dissolved concentrations and loads of seven fungicides, six herbicides and four degradation products in runoff from a vineyard catchment were continuously recorded at the inlet and the outlet of the stormwater wetland during two successive periods of pesticide application (April to June). Reduction of pesticide concentrations by the wetland ranged from 50% (simazine) to 100% (azoxystrobin, cymoxanil, cyprodinil, gluphosinate, terbuthylazine...