Hydrogeological characteristics influencing the occurrence of pesticides and pesticide metabolites in groundwater across the Republic of Ireland.

Pesticide contamination of water is a potential environmental issue which may impact the quality of drinking water. The full extent of pesticide contamination is not fully understood due to complex fate pathways in the subsurface. Groundwater pesticide occurrence was investigated at seven agricultural sites in different hydrogeological settings to identify where pesticide occurrence dominated in temperate maritime climatic conditions. In Ireland, six cereal dominated sites in the South East and one grassland site in the West were investigated. Soil and subsoils varied from acid brown earths with high permeability to clay and silt rich tills with lower permeability. Over a 2year monitoring period, 730 samples were collected from a network of dedicated wells and springs across the seven sites. Multi-nested piezometers were installed in intergranular, fissured and karstic type aquifers to target shallow, transition and deeper groundwaters. Several springs were also sampled and the network included a confined aquifer. Groundwater was analysed for nine pesticide active ingredients and eight metabolites. Mecoprop and 2,4-D were the most frequently detected active ingredients above the instrument detection limit, accounting for 36% and 26% of the 730 samples collected and analysed. Phenoxyacetic acid was the most frequently detected and widespread metabolite found in 39% of samples collected at all seven sites. Where the European Union drinking water standard of 0.1μg/L was exceeded, metabolites accounted for the majority of exceedances with 3,5-dichlorobenzoic acid (DBA) and phenoxyacetic acid (PAC) dominating. Highest detections were encountered in sites with well drained soils underlain by gravel and limestone aquifers and within gravel lenses in lower permeability subsoil. Across the seven sites pesticide detections were mostly associated with metabolites and the environmental impact of many of these is unknown as they have received little attention in groundwater previously.