Abstract
Water scarcity in the Mediterranean area has increased the number of intermittent rivers. Recently, hyporheic zones (HZ) of intermittent rivers have gained attention since a substantial part of the stream's natural purification capacity is located within these zones. Thus, understanding the flow dynamics in HZs is crucial for gaining insights into the degradation of organic micropollutants. A lab-scale study using column experiments was conducted in an attempt to elucidate the environmental processes accounting for the biodegradation capacity of the HZ under flow intermittency. A mixture of six compounds including pesticides (chloranthraniliprole, fluopyram and trifloxystrobin) and pharmaceuticals (venlafaxine, amisulpride and paroxetine) spiked at 1 μg/L level was used for degradation kinetic studies and at 1 mg/L for transformation products identification using suspect/non-target liquid chromatography high-resolution mass spectrometry approaches. The experiments lasted 60 days, divided into two 14-day phases: one before and one after a 5-week desiccation period. Bacterial community was charaterized by high-throughput DNA sequencing. The results suggested that intermittent flows stimulated the biodegradation of three compounds namely fluopyram, trifloxystrobin and venlafaxine, showing a large range of biodegradation profiles in batch water/sediment testing system according to OECD 308 tests. Biodegradation rate enhancement was ascribed to the occurrence of additional transformation routes after the desiccation period of river sediment, with the formation of new transformation products reported for the first time in the present work. 16S rDNA sequencing revealed that the desiccation period favored the growth of nitrifying and denitrifying bacteria which could partially explain the emergence of the new transformation pathways and most specifically those leading to N-oxide derivatives. Identification of transformation products also revealed that reductive transformation routes were relevant for this study, being dehydrogenation, dehalogenation, ether bond cleavage and sulfone reduction into sulphide important reactions. These results suggest that the intermittent flow conditions can influence the HZ biodegradation capacity.