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Woodchip bioreactors have gained popularity in many countries as a conservation practice for reducing nitrate load to freshwater. However, current methods for assessing their performance may be inadequate when nitrate removal rates (RR) are determined from low-frequency (e.g., weekly) concurrent sampling at the inlet and outlet. We hypothesised that high-frequency monitoring data at multiple locations can help improve the accuracy of quantifying nitrate removal performance, enhance the understanding of processes occurring within a bioreactor, and therefore improve the design practice for bioreactors. Accordingly, the objectives of this study were to compare RRs calculated using high- and low-frequency sampling and assess the spatiotemporal variability of the nitrate removal within a bioreactor to unravel the processes occurring within a bioreactor. For two drainage seasons, we monitored nitrate concentrations at 21 locations on an hourly or two-hourly basis within a pilot-scale woodchip bioreactor in Tatuanui, New Zealand. A novel method was developed to account for the variable lag time between entry and exit of a parcel of sampled drainage water. Our results showed that this method not only enabled lag time to be accounted for but also helped quantify volumetric inefficiencies (e.g., dead zone) within the bioreactor. The average RR calculated using this method was significantly higher than the average RR calculated using conventional low-frequency methods. The average RRs of each of the quarter sections within the bioreactor were found to be different. 1-D transport modelling confirmed the effect of nitrate loading on the removal process as nitrate reduction followed Michaelis-Menten (MM) kinetics. These results demonstrate that high-frequency temporal and spatial monitoring of nitrate concentrations in the field allows improved description of bioreactor performance and better understanding of processes occurring within woodchip bioreactors. Thus, insights gained from this study can be used to optimise the design of future field bioreactors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

The denitrification capacity of wetlands, riparian zones, and aquifers in glacial outwash areas is well documented, but little or no information exists for volcanic profiles, particularly those containing relict organic matter contained in or on top of paleosols (old soils buried by volcanic deposits) below the groundwater table. Relict carbon contained in these layers could provide the necessary electrons to fuel heterotrophic denitrification. To the best of our knowledge, this is the first study investigating the denitrification capacity in both the unsaturated and saturated zone of volcanic profiles. Samples from three profile types with differing organic matter distribution were amended with N-enriched nitrate (NO-) and incubated in the laboratory under anaerobic conditions. Dinitrogen (N) dominated the N gas fluxes; averaged across all samples, it accounted for 96% of the total N (nitrous oxide [NO] and N) gas fluxes. Dinitrogen fluxes were generally highest in the A horizon samples (4.1-6.2 nmol N g h), but substantial fluxes were also observed in some paleosol layers (up to 0.72 nmol N g h). A significant correlation ( < 0.001) was found between the concentration of extractable dissolved organic carbon and the total N gas flux produced in samples from below the A horizon, suggesting that heterotrophic denitrification was the dominant NO attenuation process in this study. Extrapolation of lab-derived denitrification capacities to field conditions suggests that the denitrification capacity of profiles containing relict soil organic matter in the saturated zone exceeds the estimated N leaching from the root zone., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)