Flow analysis and hydraulic performance of denitrifying bioreactors under different carbon dosing treatments.

Denitrifying bioreactors are an effective approach for removing nitrate from a variety of non-point wastewater sources, including agricultural tile drainage. However, compared to alternate mitigation approaches such as constructed wetlands, nitrate removal in bioreactors may decline with time and low temperature, resulting in poor long-term nitrate removal rates. To address the low nitrate removal rates in bioreactors, the addition of an external carbon source has been found to be an effective method for enhancing and maintaining nitrate removal rates. While carbon dosing has led to a significant improvement in nitrate removal, some of the possible adverse effects of carbon dosing, such as clogging and reduction in hydraulic efficiency, remain unknown and need to be investigated. Using observations from both field and mesocosm trials, we compared the hydraulic performance of bioreactors with and without carbon dosing. The pilot-scale field bioreactor (58 m3 total woodchip volume, 25 m3 saturated volume, referred to as field bioreactor in this work) treated drainage water from a paddock of a dairy farm. The bioreactor received an exogenous carbon dose of 8% methanol (v/v) at 10 mL min-1 and 5 mL min-1 in the 2020 and 2021 drainage seasons, respectively. The field bioreactor had a statistically higher hydraulic conductivity in 2018 when not carbon-dosed of 4601 m day-1, reducing to 1600 m day-1 in 2021 which was the second year of carbon dosing. Field observations could not establish whether the addition of liquid carbon could affect the bioreactor's internal hydraulics performance, such as actual hydraulic retention time (AHRT), despite a significant decline in hydraulic conductivity in the field bioreactor. Separate experiments on replicated bioreactor mesocosms were conducted to investigate the effects of carbon dosing on the internal hydraulic parameters of bioreactors. These mesocosm bioreactors had previously been used to study the long-term effects of methanol dosing on bioreactor performance, such as nitrate removal under steady-state conditions. The mesocosm and field bioreactors shared some characteristics, such as the use of methanol as an external carbon source, but the mesocosm experiments were hydrologically controlled contrary to the field bioreactor's transient operating conditions. We found that methanol dosing in either carbon or nitrate limiting conditions had no significant effects (p-value >0.05) on internal hydraulic parameters (e.g., effective utilization of media) when compared to control bioreactors. The present study offers insight into the long-term hydraulic performance of bioreactors and may help develop small-footprint bioreactors that incorporate external carbon dosing.

High-frequency, in situ sampling of field woodchip bioreactors reveals sources of sampling error and hydraulic inefficiencies.

Woodchip bioreactors are a practical, low-cost technology for reducing nitrate (NO3) loads discharged from agriculture. Traditional methods of quantifying their performance in the field mostly rely on low-frequency, time-based (weekly to monthly sampling interval) or flow-weighted sample collection at the inlet and outlet, creating uncertainty in their performance and design by providing incomplete information on flow and water chemistry. To address this uncertainty, two field bioreactors were monitored in the US and New Zealand using high-frequency, multipoint sampling for in situ monitoring of NO3-N concentrations. High-frequency monitoring (sub hourly interval) at the inlet and outlet of both bioreactors revealed significant variability in volumetric removal rates and percent reduction, with percent reduction varying by up to 25 percentage points within a single flow event. Time series of inlet and outlet NO3 showed significant lag in peak concentrations of 1-3 days due to high hydraulic residence time, where calculations from instantaneous measurements produced erroneous estimates of performance and misleading relationships between residence time and removal. Internal porewater sampling wells showed differences in NO3 concentration between shallow and deep zones, and "hot spot" zones where peak NO3 removal co-occurred with dissolved oxygen depletion and dissolved organic carbon production. Tracking NO3 movement through the profile showed preferential flow occurring with slower flow in deeper woodchips, and slower flow further from the most direct flowpath from inlet to outlet. High-frequency, in situ data on inlet and outlet time series and internal porewater solute profiles of this initial work highlight several key areas for future research.

The effects of denitrification parameterization and potential benefits of spatially targeted regulation for the reduction of N-discharges from agriculture.

Diffuse nitrate leaching from agricultural areas is a major environmental problem in many parts of the world. Understanding where in a catchment nitrate is removed is key for designing effective land use management strategies that protect water quality, while minimizing the impact on economic development. In this study we assess the effects of spatially targeted nitrate leaching regulation in a basin with limited knowledge of the complexity of chemical heterogeneity. Three alternative nitrate reactivity spatial parameterizations were incorporated in a catchment-scale flow and transport model and used to evaluate the effectiveness of four possible spatially targeted regulation options. Our findings confirm that denitrification parameterization cannot be numerically determined based on model inversion alone. Detailed field based characterization using physical and geochemical methods should be considered and incorporated in the numerical inversion scheme. We also demonstrate that there are potential benefits of implementing spatially targeted regulation compared to spatially uniform regulation. Focusing regulation in areas where nitrate residence time is short, such as riparian zones or areas with low natural N-reduction, results in greater reduction of N-discharges through groundwater. Significantly improved efficiencies can be expected when delineation of management zones considers the chemical heterogeneity and groundwater flow paths. These improved efficiencies are achieved by adopting management rules that regulate land use in discharge sensitive areas, where leaching changes contribute the most to the catchment nitrate discharges. In our case study, regulation in discharge sensitive zones was twice as efficient compared to other management options.

Elucidating phosphorus removal dynamics in a denitrifying woodchip bioreactor.

Denitrifying woodchip bioreactors (DBRs) are an established nitrate mitigation technology, but uncertainty remains on their viability for phosphorus (P) removal due to inconsistent source-sink behaviour in field trials. We investigated whether iron (Fe) redox cycling could be the missing link needed to explain P dynamics in these systems. A pilot-scale DBR (Aotearoa New Zealand) was monitored for the first two drainage seasons (2017-2018), with supplemental in-field measurements of reduced solutes (Fe2+, HS-/H2S) and their conjugate oxidised species (Fe3+/SO42-) made in 2021 to constrain within-reactor redox gradients. Consistent with thermodynamics, the dissolution of Fe3+(s) to Fe2+(aq) within the DBR sequentially followed O2, NO3- and MnO2(s) reduction, but occurred before SO42- reduction. Monitoring of inlet and outlet chemistry revealed tight coupling between Fe and P (inlet R2 0.94, outlet R2 0.85), but distinct dynamics between drainage seasons. In season one, outlet P exceeded inlet P (net P source), and coincided with elevated outlet Fe2+, but at ⁓50 % lower P concentrations relative to inlet Fe:P ratios. In season 2 the reactor became a net P sink, coinciding with declining outlet Fe2+ concentrations (indicating exhaustion of Fe3+(s) hydroxides and associated P). In order to characterize P removal under varying source dynamics (i.e. inflows vs in-situ P releases), we used the inlet Fe vs P relationship to estimate P binding to colloidal Fe (hydr)oxide surfaces under oxic conditions, and the outlet Fe2+ concentration to estimate in-situ P releases associated with Fe (hydr)oxide reduction. Inferred P-removal rates were highest early in season 1 (k = 0.60 g P m3 d-1; 75-100 % removal), declining significantly thereafter (k = 0.01 ± 0.02 g P m3 d-1; ca. 3-67 % removal). These calculations suggest that microbiological P removal in DBRs can occur at comparable magnitudes to nitrate removal by denitrification, depending mainly on P availability and hydraulic retention efficiency.

Assessing changes in nitrogen contamination in groundwater using water aging: Waikato River, New Zealand.

Groundwater and surface water contamination by nitrogen can produce serious health issues particularly regarding the contraction of methemoglobinemia in infants; prevention of this disorder is a main reason for regulating drinking water quality in New Zealand. To assist the management of water quality in the Upper Waikato Catchment in the light of growing intensification of nitrogen producing land uses, a regional groundwater flow and contamination transport model was developed to assess probable future nitrogen concentrations. Calibration of the steady state model was achieved with a root mean square error of 4.7% for groundwater levels and 7.9% for gains and losses in river flow within the catchment. Model performance was assisted by relationships determined between SiO2 concentrations in groundwater and water age. Modelling coupled with water aging indicates that the mean residence time of contributing water in the Upper Waikato Catchment ranges from 5 to 101 years with an average of 50 years. Some 77% of surface water is sourced from groundwater which is likely to convey the predominant contribution to the total nitrogen load. Nitrogen concentrations are increasing but the long-term total load is difficult to estimate owing largely to lack of information about historical land use and the degree of attenuation of nitrogen. The model and results obtained may be employed to provide information on water travel time distributions, appropriate source location and surface water receiving reaches in rivers and streams all of which is important and necessary for effective water quality management in the Catchment.