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Item Modelling and mapping of subsurface nitrate-attenuation index in agricultural landscapes(Elsevier Ltd, 2025-06) Collins SB; Singh R; Mead SR; Horne DJ; Zhang LEnvironmental management of nutrient losses from agricultural lands is required to reduce their potential impacts on the quality of groundwater and eutrophication of surface waters in agricultural landscapes. However, accurate accounting and management of nitrogen losses relies on a robust modelling of nitrogen leaching and its potential attenuation – specifically, the reduction of nitrate to gaseous forms of nitrogen – in subsurface flow pathways. Subsurface denitrification is a key process in potential nitrate attenuation, but the spatial and temporal dynamics of where and when it occurs remain poorly understood, especially at catchment-scale. In this paper, a novel Landscape Subsurface Nitrate-Attenuation Index (LSNAI) is developed to map spatially variable subsurface nitrate attenuation potential of diverse landscape units across the Manawatū-Whanganui region of New Zealand. A large data set of groundwater quality across New Zealand was collated and analysed to assess spatial and temporal variability of groundwater redox status (based on dissolved oxygen, nitrate and dissolved manganese) across different hydrogeological settings. The Extreme Gradient Boosting algorithm was used to predict landscape unit subsurface redox status by integrating the nationwide groundwater redox status data set with various landscape characteristics. Applying the hierarchical clustering analysis and unsupervised classification techniques, the LSNAI was then developed to identify and map five landscape subsurface nitrate attenuation classes, varying from very low to very high potential, based on the predicted groundwater redox status probabilities and identified soil drainage and rock type as key influencing landscape characteristics. Accuracy of the LSNAI mapping was further investigated and validated using a set of independent observations of groundwater quality and redox assessments in shallow groundwaters in the study area. This highlights the potential for further research in up-scaling mapping and modelling of landscape subsurface nitrate attenuation index to accurately account for spatial variability in subsurface nitrate attenuation potential in modelling and assessment of water quality management measures at catchment-scale in agricultural landscapes.Item Quantification of denitrification rate in shallow groundwater using the single-well, push-pull test technique(Elsevier BV, Amsterdam, 2025-02) Rivas A; Singh R; Horne D; Roygard J; Matthews A; Hedley MDenitrification has been identified as a significant nitrate attenuation process in groundwater systems. Hence, accurate quantification of denitrification rates is consequently important for the better understanding and assessment of nitrate contamination of groundwater systems. There are, however, few studies that have investigated quantification of shallow groundwater denitrification rates using different analytical approaches or assuming different kinetic reaction models. In this study, we assessed different analytical approaches (reactant versus product) and kinetic reaction (zero-order and first-order) models analysing observations from a single-well, push-pull tests to quantify denitrification rates in shallow groundwater at two sites in the Manawatū River catchment, Lower North Island of New Zealand. Shallow groundwater denitrification rates analysed using the measurements of denitrification reactant (nitrate reduction) and zero-order kinetic models were quantified at 0.42-1.07 mg N L-1 h-1 and 0.05-0.12 mg N L-1 h-1 at the Palmerston North (PNR) and Woodville (WDV) sites, respectively. However, using first-order kinetic models, the denitrification rates were quantified at 0.03-0.09 h-1 and 0.002-0.012 h-1 at the PNR and WDV sites, respectively. These denitrification rates based on the measurements of denitrification reactant (nitrate reduction) were quantified significantly higher (6 to 60 times) than the rates estimated using the measurements of denitrification product (nitrous oxide production). However, the denitrification rate quantified based on the nitrate reduction may provide representative value of denitrification characteristics of shallow groundwater systems. This is more so when lacking practical methods to quantify all nitrogen species (i.e., total N, organic N, nitrite, nitrate, ammoniacal N, nitrous oxide, nitric oxide, and nitrogen gas) in a push-pull test. While estimates of denitrification rates also differed depending on the kinetic model used, both a zero-order and a first-order model appear to be valid to analyse and estimate denitrification rate from push-pull tests. However, a discrepancy in estimates of denitrification rates using either reactant or product and using zero- or first-order kinetics models may have implications in assessment of nitrate transport and transformation in groundwater systems. This necessitates further research and analysis for appropriate measurements and representation of spatial and temporal variability in denitrification characteristics of the shallow groundwater system.