High frequency monitoring of pesticides in runoff water to improve understanding of their transport and environmental impacts.

Rainfall-induced peaks in pesticide concentrations can occur rapidly. Low frequency sampling may therefore 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 lacking. High frequency monitoring (2min) of 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 maximum pesticide concentrations were 387µgL-1. Samples from all of the runoff events exceeded the legal limit of 0.1µgL-1 for at least one 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 point and average (time or discharge-weighted) concentrations indicated up to a 30- or 4-fold underestimation of the TU obtained when measuring the maximum concentrations, respectively. This highlights the important role of 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 understanding of pesticide supply and transport.

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.