Degradation of seven pesticides and two metabolites before and during aquifer storage transfer and recovery operation

Degradation of 7 common pesticides (bentazon, boscalid, chloridazon, fluopyram, flutolanil, imidacloprid, and methoxyfenozide) and 2 metabolites of chloridazon (desphenyl-chloridazon, and methyl-desphenyl-chloridazon) was studied in an anoxic and brackish sandy aquifer before and during Aquifer Storage Transfer and Recovery (ASTR) operation. Fresh tile drainage water was injected and stored for later re-use as irrigation water. We hypothesized that electron acceptors (O₂, NO₃), dissolved organic carbon (∼24.7 mg/L), nutrients (NO₃: ∼14.1 mg/L, NH₄: ∼0.13 mg/L, PO₄: ∼5.2 mg/L), and biodegrading bacteria in tile drainage water could stimulate degradation of the pesticides and metabolites (ranging between 0.013 and 10.8 μg/L) introduced in the aquifer. Pesticide degradation was studied at 6 depths in the aquifer using push-pull tests lasting ±18 days before the onset of ASTR operation. Degradation was too limited to quantify and/or could not be assessed because of the potential occurrence of pesticide retardation. Utilizing push-pull tests to obtain degradation constants should only be considered in future studies for non-retarding pesticides with relative low half-lives (here <20 days). During ASTR operation, pesticide degradation was studied at the same depths during 3 storage periods equally spread over 1.5 years of ASTR operation. Overall, trends of degradation were observed, although with relatively high half-lives of at least 53 days. Microbial adaptation of the aquifer and/or bioaugmentation by the injected biodegrading bacteria did not result in enhanced degradation during consecutive storage periods. Operational monitoring data over longer periods and distances yielded half-lives of at least 141 days. The slow degradation mostly agrees with previous studies. The injected tile drainage water composition did therefore not notably stimulate pesticide degradation. The relatively persistent behavior of the studied pesticides/metabolites implies that ASTR abstracted water will have generally high pesticide concentrations, and non-abstracted water may form a contamination risk for the surrounding native brackish groundwater.