Characterisation of denitrification in the subsurface environment of the Manawatū catchment, New Zealand : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Earth Science at Massey University, Palmerston North, New Zealand

Figures 2.1 & 2.2 have been removed for copyright reasons but may be accessed via their source listed in the References (Rivett et al., 2008, Fig. 2 & Saggar et al., 2013, Fig. 3).A sound understanding of the quantity of nitrate lost from agricultural soils, as well as their transport and transformation in soil-water systems is essential for targeted and effective management and/or mitigation of their impacts on the quality of receiving waters. However, there is currently little known about the occurrence, variability, or factors affecting, nitrate attenuation by subsurface (below the root zone) denitrification in New Zealand, particularly in the Manawatū River catchment. This thesis developed and applied a combination of regional- and local-scale hydrogeochemical surveys and experiments, to gain an insight into the occurrence, variability, and hydrogeological features of subsurface denitrification in the Manawatū River catchment, particularly in the Tararua Groundwater Management Zone (GWMZ). A regional survey and analysis of samples from 56 groundwater wells conducted in the Tararua GWMZ revealed mainly oxic groundwater with low denitrification potential in the southern part of the catchment (Mangatainoka sub-catchment), whereas mainly anoxic/reduced groundwaters with high potential to denitrify in the middle and northern parts (Upper Manawatū sub-catchments). Oxic groundwaters with enriched nitrate concentrations were generally correlated with coarse textured soil types and aquifer materials (e.g., well-drained soil, gravel rock type), allowing faster movement of percolating water and oxygen diffusion from surface to subsurface environments. Local-scale laboratory incubations and in-field, push-pull test techniques were evaluated and optimised to measure and quantify denitrification in unsaturated (vadose) and saturated (shallow groundwater) parts of the subsurface environment. A novel incubation technique using vacuum pouches was found to be more reliable than traditional Erlenmeyer flasks in determining denitrifying enzyme activity (DEA) in subsurface soils (>0.3 m depth) with low denitrification activity. A combination of 75 μg N g-1 dry soil and 400 μg C g-1 dry soil was also found to provide the optimum DEA in subsurface soils. In the evaluation of the push-pull test, denitrification rates estimated using the measurements of denitrification reactant (nitrate) were found to be significantly higher (6 to 60 times) as compared to the rates estimated using the measurements of denitrification product (nitrous oxide). The estimates of denitrification rates also differed depending on whether a zero-order or first-order kinetic model was assumed. However, either a zero-order or a first-order model appears to be valid to estimate the denitrification rate from push-pull test data. The optimised laboratory incubation technique and in-field, push-pull test were applied at four sites with contrasting redox properties; Palmerston North, Pahiatua, Woodville, and Dannevirke. The incubation technique revealed that denitrification potential in terms of DEA is highest in the surface soil and generally decreased with soil depth. The push-pull test measured large denitrification rates of 0.04 to 1.07 mg N L-1 h-1 in the reduced groundwaters at depths of 4.5-7.5 m below ground level at two of the sites (Woodville and Palmerston North), whereas there were no clear indications of denitrification in the oxidised shallow groundwaters at the other two sites (Pahiatua and Dannevirke). This new knowledge, information and techniques advance our scientific capability to assess and map subsurface denitrification potential for targeted and effective land use planning and water quality measures in the Manawatū catchment and other catchments across New Zealand’s agricultural landscapes and worldwide