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.

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.

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.

Fungicides transport in runoff from vineyard plot and catchment: contribution of non-target areas.

Surface runoff and erosion during the course of rainfall events are major processes of pesticides transport from agricultural land to aquatic ecosystem. These processes are generally evaluated either at the plot or the catchment scale. Here, we compared at both scales the transport and partitioning in runoff water of two widely used fungicides, i.e., kresoxim-methyl (KM) and cyazofamid (CY). The objective was to evaluate the relationship between fungicides runoff from the plot and from the vineyard catchment. The results show that seasonal exports for KM and CY at the catchment were larger than those obtained at the plot. This underlines that non-target areas within the catchment largely contribute to the overall load of runoff-associated fungicides. Estimations show that 85 and 62 % of the loads observed for KM and CY at the catchment outlet cannot be explained by the vineyard plots. However, the partitioning of KM and CY between three fractions, i.e., the suspended solids (>0.7 µm) and two dissolved fractions (i.e., between 0.22 and 0.7 µm and <0.22 µm) in runoff water was similar at both scales. KM was predominantly detected below 0.22 µm, whereas CY was mainly detected in the fraction between 0.22 and 0.7 µm. Although KM and CY have similar physicochemical properties and are expected to behave similarly, our results show that their partitioning between two fractions of the dissolved phase differs largely. It is concluded that combined observations of pesticide runoff at both the catchment and the plot scales enable to evaluate the sources areas of pesticide off-site transport.

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.

Seasonal changes of macroinvertebrate communities in a stormwater wetland collecting pesticide runoff from a vineyard catchment (Alsace, France).

Agricultural land use may influence macroinvertebrate communities by way of pesticide contamination associated with agricultural runoff. However, information about the relation between runoff-related pesticides and communities of benthic macroinvertebrates in stormwater wetland that receive agricultural runoff does not currently exist. Here we show changes in macroinvertebrates communities of a stormwater wetland that collects pesticide-contaminated runoff from a vineyard catchment. Sixteen runoff-associated pesticides, including the insecticide flufenoxuron, were continuously quantified at the inlet of the stormwater wetland from April to September (period of pesticide application). In parallel, benthic macroinvertebrate communities, pesticide concentrations, and physicochemical parameters in the wetland were assessed twice a month. Twenty-eight contaminated runoffs ranging from 1.1 to 114 m3 entered the wetland during the study period. Flufenoxuron concentrations in runoff-suspended solids ranged from 1.5 to 18.5 µg kg(-1) and reached 6 µg kg(-1) in the wetland sediments. However, flufenoxuron could not be detected in water. The density, diversity, and abundance of macroinvertebrates largely varied over time. Redundancy and formal concept analyses showed that concentrations of flufenoxuron, vegetation cover, and flow conditions significantly determine the community structures of stormwater wetland macroinvertebrates. This study shows that flow conditions, vegetation cover, and runoff-related pesticides jointly affect communities of benthic macroinvertebrates in stormwater wetlands.

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.