Pesticides applied onto agricultural fields are frequently found in adjacent rivers. To what extent and along which pathways they are transported is influenced by intrinsic pesticide properties such as sorption and degradation. In the environment, incomplete degradation of pesticides leads to the formation of transformation products (TPs), which may differ from the parent compounds regarding their intrinsic fate characteristics. Thus, the export processes of TPs in catchments and streams may also be different. In order to test this hypothesis, we extended a distributed hydrological model by the fate and behaviour of pesticides and transformation products and applied it to a small, well-monitored headwater catchment in Switzerland. The successful model evaluation of three pesticides and their TPs at three sampling locations in the catchment enabled us to estimate the quantity of contributing processes for pollutant export. Since all TPs were more mobile than their parent compounds (PCs), they exhibited larger fractions of export via subsurface pathways. However, besides freshly applied pesticides, subsurface export was found to be influenced by residues of former applications. Export along preferential flow pathways was less dependent on substance fate characteristics than soil matrix export, but total soil water flow to tile drains increased more due to preferential flow for stronger sorbing substances. Our results indicate that runoff generation by matrix flow to tile drains gained importance towards the end of the modelling period whereas the contributions from fast surface runoff and preferential flow decreased. Accordingly, TPs were to a large extent exported under different hydrological conditions than their PCs, due to their delayed formation and longer half-lives. Thus, not only their different intrinsic characteristics but also their delayed formation could be responsible for the fact that TPs generally took different pathways than their PCs. We suggest that these results should be considered in risk assessment for the export of agricultural chemicals to adjacent rivers and that models should be extended to include both PCs and TPs.

Fluorotelomer precursors in soil constitute a reservoir for perfluoroalkyl acids (PFAAs) in the environment. In the present study, precursor degradation and transfer rates of seven fluorotelomer precursors and F-53B (chlorinated polyfluoroalkyl ether sulfonates) were investigated in pot experiments with maize plants (Zea mays L.). The degradation of fluorotelomer precursors to perfluoroalkyl carboxylic acids (PFCAs) and their uptake spectra corresponded to those of fluorotelomer alcohol (FTOH) in terms of the number of perfluorinated carbon atoms. Short-chain PFCAs were translocated into the shoots (in descending order perfluoropentanoic, perfluorobutanoic, and perfluorohexanoic acid), whereas long-chain PFCAs mainly remained in the soil. In particular, fluorotelomer phosphate diesters (diPAPs) were retained in the soil and showed the highest degradation potential including evidence of α-oxidative processes. F-53B did not degrade to PFAAs and its constituents were mainly detected in the roots with minor uptake into the shoots. The results demonstrate the important role of precursors as an entry pathway for PFCAs into the food chain.

Transformation products (TP) of pesticides are found everywhere in the aquatic environment. Their dynamic formation and subsequent transport from agricultural fields to adjacent water bodies can be estimated by using environmental fate models, which is done in the registration process for plant protection products in the European Union. In this study, peer-reviewed applications of such models, the model complexity and their structure are documented and analysed. In total, 20 publications of 10 models – eight leaching models (GLEAMS, MACRO, RZWQM2, PEARL, PRZM, Pelmo, LEACHM, HYDRUS 1-D) and two catchment scale models (Zin-AgriTra, FRM) – were identified. The reviewed models greatly differ in their process complexity regarding the formation rate and the formation pathways of TPs.The major reason given for models failing to reproduce sampled TP concentrations in case studies was an erroneous substance transport, especially missing preferential flow simulation in soil. However, the contribution of TP formation processes to simulation uncertainty was not analysed at all in most of the studies. By comparing the structure of existing models, the state of knowledge on TP fate and requirements of TP fate assessment, the following recommendations were drawn: i) It is suggested that the models should be updated to reflect the current state of knowledge in process research, especially more complex transformation schemes and the formation of different TPs in different compartments, which was not included in most of the models. ii) Even though there are pesticide parent compound fate models at the catchment scale with a temporal resolution of one day, none of these models is able to simulate TP fate. Such models would enable scientists and authorities to estimate the environmental fate of TPs at the larger catchment scale or the regional scale. iii) To get over the assessment of the huge number of TPs formed in the environment, an integration of Quantitative Structure Properties Relationship models predicting TP fate characteristics, TP pathway prediction models and environmental fate models is suggested. This would allow for a largely automated and comprehensive assessment of the fate of a pesticide parent compound and all its TPs for regulatory purposes.