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Item Assessment of biogeochemical transformation of nitrate in shallow groundwater in the agricultural landscape : a thesis presented in partial fulfilment of the requirements for the degree of Master of Science in Soil Science at Massey University, Manawatu, New Zealand(Massey University, 2019) Gonzalez Moreno, Marcela AngelicaIn groundwaters, denitrification or subsurface denitrification (SD) has been identified as a key attenuation process. Where leached nitrate (NO₃⁻) can be reduced to dinitrogen (N₂ — a harmless gas), offering an ecosystem service in terms of reducing water pollution. However, partial denitrification (PD) can release nitrous oxide (N₂ — a greenhouse gas), resulting in a pollution swap from liquid to gaseous pollution and adding to greenhouse gas emission. There is very limited information available about occurrence, characteristics and dynamics of subsurface denitrification in shallow groundwaters across New Zealand agricultural catchments. We studied 6 pastoral farms (DF 1, 2, 3; SC 1, 2, 3; ARM 1, 2, 3; CAM 1, 3; SR 1, 2, 3; BUR 1, 2 and 3) located in various hydrogeological settings in the Manawatu and Rangitikei Rivers catchments, in the lower North Island of New Zealand. We collected 7 sets of monthly groundwater observations at 17 piezometers from March to September 2018 to characterize the groundwater monthly chemical variations. The collected groundwater samples were analyzed for groundwater redox status, including dissolved oxygen (DO), oxidation-reduction potential, pH, NO₃⁻-N, iron (Fe²⁺), manganese (Mn²⁺) and sulphate (SO₄²⁻). We also conducted a set of push-and-pull tests to gain insights into dynamics of subsurface denitrification occurring in the groundwater samples at the study sites. We quantified changes in concentration of NO₃⁻-N, Br⁻ (tracer), dissolved N₂O-N and excess N₂ during the push-and-pull tests. Our results suggested a spatially variable groundwater redox conditions and SD occurring across the study sites. The piezometers DF 2, 3; SC 1, 2; CAM 3; ARM 1, 2 and 3 showed anoxic redox status. Only the piezometers SC 3 and CAM 1 presented mixed redox condition. While the piezometers DF 1; SR 1, 2, 3; BUR 1, 2 and 3 indicated oxic conditions with some variability over the study. Nitrate is being reduced in the anoxic piezometers DF 2, 3; SC 1, 3; ARM 1, 2, 3 and CAM 3, showing no NO₃⁻-N accumulation (< 0.5 mg L⁻¹). One of the piezometers with mixed redox condition (CAM 1) showed NO₃⁻-N accumulation (> 6 mg L⁻¹) while the piezometer SC 3 showed variability in NO₃⁻-N accumulation ranging from 0.02 mg L⁻¹ to 22.56 mg L⁻¹. The oxic piezometers SR 1, 2, 3; BUR 1, 2 and 3 showed NO₃⁻-N accumulation (> 3 mg L⁻¹) except for piezometer DF 1 that showed variability in NO₃⁻-N concentrations ranging from 0.01 mg L⁻¹ to 3.75 mg L⁻¹ over the study. The concentrations of the electron donors Fe²⁺ and Mn²⁺ were found to be suitable for SD on anoxic piezometers DF 2, 3; SC 1, 2; CAM 3 and ARM 1, 2, 3 (> 1 mg L⁻¹ and > 0.05 mg L⁻¹ respectively). The piezometers with mixed redox status SC 3 and CAM 1 ranged just over the redox threshold for identifying redox processes (0.1 – 1.0 mg L⁻¹ and > 0.05 mg L⁻¹ respectively). In general, the piezometer with oxic redox status (DF 1, SR 1, 2, 3 and BUR 1, 2, 3) showed [Fe²⁺] and [Mn²⁺] below the threshold for identifying redox processes (< 0.1 mg L⁻¹ and < 0.05 mg L⁻¹ respectively) and not suitable to support SD. The dominant terminal product of SD, whether was complete denitrification (N₂ — as end product) or partial SD (N₂O — as end product) spatially varied according to the redox status of the groundwater. Push-pull test results showed an increase in excess N₂ and N₂O-N concentrations at DF 3, ARM 3, CAM 3, BUR 3. The push-pull test conducted at SR 3 and SC 3 showed inconclusive results. Piezometers CAM 3 and ARM 3 showed the highest suitable conditions for SD followed by DF 3. Piezometer BUR 3 showed the highest partial SD rate. Therefore BUR 3 is considered in general, the less suitable piezometer for SD. Our observations highlight the influence of different hydrogeological settings on spatial variability of partial (pollution swamp) or complete (ecosystem service) SD in shallow groundwaters. A better understanding and quantification of spatial and temporal variability of SD process will support information, design and formulation of targeted and effective management measures for sustainable agricultural production while protecting soil, water and air quality.Item 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(Massey University, 2018) Rivas, Aldrin AlamedaA 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.Item Application and evaluation of sediment fingerprinting techniques in the Manawatu River catchment, New Zealand : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Geography at Massey University, Palmerston North, New Zealand(Massey University, 2016) Vale, SimonSuspended sediment is an important component of the fluvial environment, contributing not only to the physical form, but also the chemical and ecological character of river channels and adjacent floodplains. Fluvial sediment flux reflects erosion of the contributing catchment, which when enhanced can lead to a reduction in agricultural productivity, effect morphological changes in the riparian environment and alter aquatic ecosystems by elevating turbidity levels and degrading water quality. It is therefore important to identify catchment-scale erosion processes and understand rates of sediment delivery, transport and deposition into the fluvial system to be able to mitigate such adverse effects. Sediment fingerprinting is a well-used tool for evaluating sediment sources, capable of directly quantifying sediment supply through differentiating sediment sources based on their inherent geochemical signatures and statistical modelling. Confluence-based sediment fingerprinting has achieved broad scale geochemical discrimination within the 5870 km2 Manawatu catchment, which drains terrain comprising soft-rock Tertiary and Quaternary sandstones, mudstones, limestones and more indurated greywacke. Multiple sediment samples were taken upstream and downstream of major river confluences, sieved to < 63 μm and analysed through step-wise discrimination, principle component analysis and a range of geochemical indicators to investigate and identify the sub-catchment geochemical signatures. Discrimination between the main sub-catchments was attained despite each sub-catchment containing similar rock types, albeit with varying proportions of specific lithologies. This meant that source groups were categorized as a mixture of both lithological and geomorphological sources in order to best capture the unique sediment origins. Comprehensive sampling quantified 8 geomorphological sediment sources using two mixing models; the traditional mixing model after Collins et al. (1997) and the Hughes et al. (2009) mixing model which were each optimized using a ‘Generalized Reduced Gradient (GRG) Nonlinear’ and an ‘Evolutionary’ technique providing four mixing model scenarios. These models showed good agreement attributing mudstone derived sediment (≈ 38 – 46 %) as the dominant source of suspended sediment to the Manawatu River. Sediment contributions were also estimated from the Mountain Range, ≈ 15 – 18 %; Hill Surface, ≈ 12 – 16 %; Hill subsurface, ≈ 9 – 11 %; Loess, ≈ 9 – 15 %; Gravel Terrace, ≈ 0 – 4 %; Channel Bank, ≈ 0 – 5 %; and Limestone, ≈ 0 %. Intra-storm analysis of sediment sources was investigated through hourly suspended sediment samples taken in the lower Manawatu River during a 53 hour storm event to detect changes in sediment sources. The suspended sediment samples displayed high hourly variability which was attributed to model uncertainty and sediment pulses occurring between sampling. Mudstone proportions fluctuated ≈ 20 – 60 % throughout the storm duration from a range of erosion processes, while Mountain Range sediment fluctuated from ≈ 24 – 46 % and Hill Subsurface and Hill Surface both were near 0 %, but approached upper values of ≈ 23 % and ≈ 24 % respectively. Significant shifts in sediment source proportions were observed between 2:00 – 8:00 am 29th November 2013 in relation to flow dynamics of the Pohangina River and shifting flow dominance from the Pohangina River to the Upper Manawatu. The geochemical suite was reanalysed to determine the variability of source groups and individual geochemical elements, in order to evaluate the suitability and impact of changing the geochemical suite used in estimated relative sediment source proportions. Mountain Range sediment displayed the highest average S.D. % of 39.4, followed by Gravel Terrace (S.D. % = 34.6) and Loess (28.1), while the lowest was found in Limestone (S.D. % = 18.1) and Channel Bank (S.D. % = 18.3). The highest variability of individual elements was found in the transition elements such as Cu, Ni, Cr, and Mn, as well as Ca, and Tm. Revised mixing models were run based on two geochemical tracer suites which removed elements with S.D. percentage of > 40 and > 35 respectively. The revised mixing model estimated Mudstone terrain to contribute 59.3 % and 61.8 %, with significant contributions estimated from Mountain Range (12.0 % and 11.4 %) and Hill Surface (11.5 % and 11.3 %) respectively, indicating that Tm, Ni, Cu, Ca, P, Mn and Cr have an influence on these sediment source estimations.