Effects of aged sorption on pesticide leaching to groundwater simulated with PEARL

Leaching to groundwater is an important element of the regulatory risk assessment of pesticides in western countries. Including aged sorption in this assessment is relevant because there is ample evidence of this process and because it leads to a decrease in simulated leaching. This work assesses the likely magnitude of this decrease for four groundwater scenarios used for regulatory purpose in the EU (from the UK, Portugal, Austria and Greece) and for ranges of aged-sorption parameters and substance properties using the PEARL model. Three aged-sorption parameters sets were derived from literature, representing approximately 5th, 50th and 95th percentile cases for the magnitude of the effect of aged sorption on leaching concentrations (called S, M and L, respectively). The selection of these percentile cases was based only on the f_NE parameter (i.e. the ratio of the aged sorption and the equilibrium sorption coefficients) because leaching was much more affected by the uncertainty in this parameter than by the uncertainty in the desorption rate coefficient of these sites (k_d). For the UK scenario, the annual flux concentration of pesticide leaching at 1m depth decreased by typically a factor of 5, 30 and >1000 for the S, M and L parameter sets, respectively. This decrease by a factor of 30 for the M parameter set appeared to be approximately valid also for the other three scenarios. Decreasing the Freundlich exponent N from 0.9 into 0.7 for the M parameter set, increased this factor of 30 into a factor of typically 1000, considering all four scenarios. The aged-sorption sites were close to their equilibrium conditions during the leaching simulations for two of the four scenarios (for all substances considered and the M parameter set), but this was not the case for the other two scenarios.