Pesticides in groundwater at a national scale (France): Impact of regulations, molecular properties, uses, hydrogeology and climatic conditions

Highlights: • Data on groundwater quality at national scale were analysed for >20 years. • Changes in regulations have short- and medium-term impact on groundwater quality. • The climatic context is at least as important as the use and properties of pesticides. • Rapid transfer of pesticides can occur whatever the lithology of the aquifer. • Triazines and acetochlor are still detected despite banned application. Contaminants in groundwater are a major issue worldwide. Temporal trends of such occurrences in French groundwaters were evaluated for several active substances of pesticides belonging to different chemical classes, to identify key factors explaining groundwater contamination. Our study relied on exploitation of a French national database (ADES, created in the mid-1990s and remarkable for the available data, including over 88 million analyses). Temporal changes in the frequency of exceeding a reference value of 0.1 μg/L for several substances were determined at yearly and monthly scales. Such trends were examined by distinguishing different periods according to changes in regulations (new approval, withdrawal, or dose reduction), and were combined with data on effective rainfall as a proxy for groundwater recharge, on aquifer lithology, and on sales of active substances as a proxy for actual applications. A review of monthly data shows that a rapid transfer of pesticides with contrasting physico-chemical properties can occur after application in many aquifers, regardless of their lithology. For substances such as metolachlor, showing a sharp increase in sales, a clear relationship exists between quantities sold and frequency of exceeding the reference value. For other active substances, such as isoproturon or chlortoluron, frequencies of exceedance are governed by both sales and effective rainfall. Finally, the occurrence of active substances in groundwater several years after their withdrawal from the market is explained by at least three major mechanisms: the transfer time from soil into groundwater, processes of remobilization from soil and/or unsaturated zone, and no or low degradation in the saturated zone. While these processes are well documented for atrazine and different types of aquifers, they can be virtually unknown for other active substances.