A difficult coexistence: Resolving the iron-induced nitrification delay in groundwater filters.

Rapid sand filters (RSF) are an established and widely applied technology for the removal of dissolved iron (Fe2+) and ammonium (NH4+) among other contaminants in groundwater treatment. Most often, biological NH4+oxidation is spatially delayed and starts only upon complete Fe2+ depletion. However, the mechanism(s) responsible for the inhibition of NH4+oxidation by Fe2+ or its oxidation (by)products remains elusive, hindering further process control and optimization. We used batch assays, lab-scale columns, and full-scale filter characterizations to resolve the individual impact of the main Fe2+ oxidizing mechanisms and the resulting products on biological NH4+ oxidation. modeling of the obtained datasets allowed to quantitatively assess the hydraulic implications of Fe2+ oxidation. Dissolved Fe2+ and the reactive oxygen species formed as byproducts during Fe2+ oxidation had no direct effect on ammonia oxidation. The Fe3+ oxides on the sand grain coating, commonly assumed to be the main cause for inhibited ammonia oxidation, seemed instead to enhance it. modeling allowed to exclude mass transfer limitations induced by accumulation of iron flocs and consequent filter clogging as the cause for delayed ammonia oxidation. We unequivocally identify the inhibition of NH4+oxidizing organisms by the Fe3+ flocs generated during Fe2+ oxidation as the main cause for the commonly observed spatial delay in ammonia oxidation. The addition of Fe3+ flocs inhibited NH4+oxidation both in batch and column tests, and the removal of Fe3+ flocs by backwashing completely re-established the NH4+removal capacity, suggesting that the inhibition is reversible. In conclusion, our findings not only identify the iron form that causes the inhibition, albeit the biological mechanism remains to be identified, but also highlight the ecological importance of iron cycling in nitrifying environments.

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.

Denitrification kinetics during aquifer storage and recovery of drainage water from agricultural land.

An aquifer storage transfer and recovery (ASTR) system was studied in which tile drainage water (TDW) was injected with relatively high NO3 (about 14 mg/L) concentrations originating from fertilizers. Here we present the evolution of denitrification kinetics at 6 different depths in the aquifer before, and during ASTR operation. First-order denitrification rate constants increased over time before and during the first days of ASTR operation, likely due to microbial adaptation of the native bacterial community and/or bioaugmentation of the aquifer by denitrifying bacteria present in injected TDW. Push-pull tests were performed in the native aquifer before ASTR operation. Obtained first-order denitrification rate constants were negligible (0.00-0.03 d-1) at the start, but increased to 0.17-0.83 d-1 after a lag-phase of about 6 days. During the first days of ASTR operation in autumn 2019, the arrival of injected TDW was studied at 2.5 m distance from the injection well. First-order denitrification rate constants increased again over time (maximum >1 d-1). Three storage periods without injection were monitored in winter 2019, fall 2020, and spring 2021 during ASTR operation. First-order rate constants ranged between 0.12 and 0.61 d-1. Denitrification coupled to pyrite oxidation occurred at all depths, but other oxidation processes were indicated as well. NO3 concentration trends resembled Monod kinetics but were fitted also to a first-order decay rate model to facilitate comparison. Rate constants during the storage periods were substantially lower than during injection, probably due to a reduction in the exchange rate between aquifer solid phases and injected water during the stagnant conditions. Denitrification rate constants deviated maximally a factor 5 over time and depth for all in-situ measurement approaches after the lag-phase. The combination of these in-situ approaches enabled to obtain more detailed insights in the evolution of denitrification kinetics during AS(T)R.

Removal of bacterial plant pathogens in columns filled with quartz and natural sediments under anoxic and oxygenated conditions.

Irrigation with surface water carrying plant pathogens poses a risk for agriculture. Managed aquifer recharge enhances fresh water availability while simultaneously it may reduce the risk of plant diseases by removal of pathogens during aquifer passage. We compared the transport of three plant pathogenic bacteria with Escherichia coli WR1 as reference strain in saturated laboratory column experiments filled with quartz sand, or sandy aquifer sediments. E. coli showed the highest removal, followed by Pectobacterium carotovorum, Dickeya solani and Ralstonia solanacearum. Bacterial and non-reactive tracer breakthrough curves were fitted with Hydrus-1D and compared with colloid filtration theory (CFT). Bacterial attachment to fine and medium aquifer sand under anoxic conditions was highest with attachment rates of max. katt1 = 765 day-1 and 355 day-1, respectively. Attachment was the least to quartz sand under oxic conditions (katt1 = 61 day-1). In CFT, sticking efficiencies were higher in aquifer than in quartz sand but there was no differentiation between fine and medium aquifer sand. Overall removal ranged between < 6.8 log10 m-1 in quartz and up to 40 log10 m-1 in fine aquifer sand. Oxygenation of the anoxic aquifer sediments for two weeks with oxic influent water decreased the removal. The results highlight the potential of natural sand filtration to sufficiently remove plant pathogenic bacteria during aquifer storage.

Intra aquifer variations in pesticide sorption during a field injection experiment.

A field injection experiment was performed in an anoxic sandy aquifer over 6 days to assess sorption characteristics of 7 commonly applied pesticides in agriculture and 2 frequently detected metabolites. Pesticide use changed considerably in the last decades, and there is insufficient knowledge of the fate of currently used pesticides in aquifers. Injected water arrival was monitored at 6 depth intervals of 1 m ranging from 11.4 to 32.2 m-below surface level with varying organic carbon contents (0.057-0.91%d.w.) to examine intra-aquifer variations in sorption. Observed pesticide concentrations were fit using a non-linear least squares routine to an advection-dispersion equation, from which retardation factors (R) were obtained. Pesticide degradation did not significantly influence the simulated R during the experiment. We observed that bentazon and cycloxydim were most mobile with R < 1.1 at all depths. Desphenyl chloridazon, methyl desphenyl chloridazon, and imidacloprid were, on average, less mobile, with maximum R of 1.5. Boscalid, chloridazon, fluopyram, and flutolanil showed a larger range of R, and R > 2.0 were observed in the shallowest part of the aquifer. Largest R were observed at the top of the aquifer and decreased with depth. Koc values varied similarly, which indicates that sorption is not only influenced by sedimentary organic matter (SOM) content but also by its sorption reactivity. Obtained sorption parameters were substantially lower than reported in a widely used pesticide sorption database, which suggests that sorption parameters are influenced by methodological differences and variations in the sorption reactivity of SOM. The large intra-aquifer variations in pesticide sorption highlights that aquifer heterogeneity should be considered in groundwater risk assessments.