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Research Papers, Lincoln University

Mitigating the cascade of environmental damage caused by the movement of excess reactive nitrogen (N) from land to sea is currently limited by difficulties in precisely and accurately measuring N fluxes due to variable rates of attenuation (denitrification) during transport. This thesis develops the use of the natural abundance isotopic composition of nitrate (δ15N and δ18O of NO₃-) to integrate the spatialtemporal variability inherent to denitrification, creating an empirical framework for evaluating attenuation during land to water NO₃- transfers. This technique is based on the knowledge that denitrifiers kinetically discriminate against 'heavy' forms of both N and oxygen (O), creating a parallel enrichment in isotopes of both species as the reaction progresses. This discrimination can be quantitatively related to NO₃- attenuation by isotopic enrichment factors (εdenit). However, while these principles are understood, use of NO₃- isotopes to quantify denitrification fluxes in non-marine environments has been limited by, 1) poor understanding of εdenit variability, and, 2) difficulty in distinguishing the extent of mixing of isotopically distinct sources from the imprint of denitrification. Through a combination of critical literature analysis, mathematical modelling, mesocosm to field scale experiments, and empirical studies on two river systems over distance and time, these short comings are parametrised and a template for future NO₃- isotope based attenuation measurements outlined. Published εdenit values (n = 169) are collated in the literature analysis presented in Chapter 2. By evaluating these values in the context of known controllers on the denitrification process, it is found that the magnitude of εdenit, for both δ15N and δ18O, is controlled by, 1) biology, 2) mode of transport through the denitrifying zone (diffusion v. advection), and, 3) nitrification (spatial-temporal distance between nitrification and denitrification). Based on the outcomes of this synthesis, the impact of the three factors identified as controlling εdenit are quantified in the context of freshwater systems by combining simple mathematical modelling and lab incubation studies (comparison of natural variation in biological versus physical expression). Biologically-defined εdenit, measured in sediments collected from four sites along a temperate stream and from three tropical submerged paddy fields, varied from -3‰ to -28‰ depending on the site’s antecedent carbon content. Following diffusive transport to aerobic surface water, εdenit was found to become more homogeneous, but also lower, with the strength of the effect controlled primarily by diffusive distance and the rate of denitrification in the sediments. I conclude that, given the variability in fractionation dynamics at all levels, applying a range of εdenit from -2‰ to -10‰ provides more accurate measurements of attenuation than attempting to establish a site-specific value. Applying this understanding of denitrification's fractionation dynamics, four field studies were conducted to measure denitrification/ NO₃- attenuation across diverse terrestrial → freshwater systems. The development of NO₃- isotopic signatures (i.e., the impact of nitrification, biological N fixation, and ammonia volatilisation on the isotopic 'imprint' of denitrification) were evaluated within two key agricultural regions: New Zealand grazed pastures (Chapter 4) and Philippine lowland submerged rice production (Chapter 5). By measuring the isotopic composition of soil ammonium, NO₃- and volatilised ammonia following the bovine urine deposition, it was determined that the isotopic composition of NO₃ - leached from grazed pastures is defined by the balance between nitrification and denitrification, not ammonia volatilisation. Consequently, NO₃- created within pasture systems was predicted to range from +10‰ (δ15N)and -0.9‰ (δ18O) for non-fertilised fields (N limited) to -3‰ (δ15N) and +2‰ (δ18O) for grazed fertilised fields (N saturated). Denitrification was also the dominant determinant of NO₃- signatures in the Philippine rice paddy. Using a site-specific εdenit for the paddy, N inputs versus attenuation were able to be calculated, revealing that >50% of available N in the top 10 cm of soil was denitrified during land preparation, and >80% of available N by two weeks post-transplanting. Intriguingly, this denitrification was driven by rapid NO₃- production via nitrification of newly mineralised N during land preparation activities. Building on the relevant range of εdenit established in Chapters 2 and 3, as well as the soil-zone confirmation that denitrification was the primary determinant of NO₃- isotopic composition, two long-term longitudinal river studies were conducted to assess attenuation during transport. In Chapter 6, impact and recovery dynamics in an urban stream were assessed over six months along a longitudinal impact gradient using measurements of NO₃- dual isotopes, biological populations, and stream chemistry. Within 10 days of the catastrophic Christchurch earthquake, dissolved oxygen in the lowest reaches was <1 mg l⁻¹, in-stream denitrification accelerated (attenuating 40-80% of sewage N), microbial biofilm communities changed, and several benthic invertebrate taxa disappeared. To test the strength of this method for tackling the diffuse, chronic N loading of streams in agricultural regions, two years of longitudinal measurements of NO₃- isotopes were collected. Attenuation was negatively correlated with NO₃- concentration, and was highly dependent on rainfall: 93% of calculated attenuation (20 kg NO₃--N ha⁻¹ y⁻¹) occurred within 48 h of rainfall. The results of these studies demonstrate the power of intense measurements of NO₃- stable isotope for distinguishing temporal and spatial trends in NO₃ - loss pathways, and potentially allow for improved catchment-scale management of agricultural intensification. Overall this work now provides a more cohesive understanding for expanding the use of NO₃- isotopes measurements to generate accurate understandings of the controls on N losses. This information is becoming increasingly important to predict ecosystem response to future changes, such the increasing agricultural intensity needed to meet global food demand, which is occurring synergistically with unpredictable global climate change.

Research papers, University of Canterbury Library

The 2010 Darfield and 2011 Christchurch Earthquakes triggered extensive liquefaction-induced lateral spreading proximate to streams and rivers in the Christchurch area, causing significant damage to structures and lifelines. A case study in central Christchurch is presented and compares field observations with predicted displacements from the widely adopted empirical model of Youd et al. (2002). Cone penetration testing (CPT), with measured soil gradation indices (fines content and median grain size) on typical fluvial deposits along the Avon River were used to determine the required geotechnical parameters for the model input. The method presented attempts to enable the adoption of the extensive post-quake CPT test records in place of the lower quality and less available Standard Penetration Test (SPT) data required by the original Youd model. The results indicate some agreement between the Youd model predictions and the field observations, while the majority of computed displacements error on the side of over-prediction by more than a factor of two. A sensitivity analysis was performed with respect to the uncertainties used as model input, illustrating the model’s high sensitivity to the input parameters, with median grain size and fines content among the most influential, and suggesting that the use of CPT data to quantify these parameters may lead to variable results.

Research papers, University of Canterbury Library

Liquefaction-induced lateral spreading in Christchurch and surrounding suburbs during the recent Canterbury Earthquake Sequence (2010-2011) caused significant damage to structures and lifelines located in close proximity to streams and rivers. Simplified methods used in current engineering practice for predicting lateral ground displacements exhibit a high degree of epistemic uncertainty, but provide ‘order of magnitude’ estimates to appraise the hazard. We wish to compare model predictions to field measurements in order to assess the model’s capabilities and limitations with respect to Christchurch conditions. The analysis presented focuses on the widely-used empirical model of Youd et al. (2002), developed based on multi-linear regression (MLR) of case history data from lateral spreading occurrence in Japan and the US. Two issues arising from the application of this model to Christchurch were considered: • Small data set of Standard Penetration Test (SPT) and soil gradation indices (fines content FC, and mean grain size, D50) required for input. We attempt to use widely available CPT data with site specific correlations to FC and D50. • Uncertainty associated with the model input parameters and their influence on predicted displacements. This has been investigated for a specific location through a sensitivity analysis.

Research papers, University of Canterbury Library

On February 22, 2011, a magnitude Mw 6.2 earthquake affected the Canterbury region, New Zealand, resulting in many fatalities. Liquefaction occurred across many areas, visible on the surface as ‘‘sand volcanoes’’, blisters and subsidence, causing significant damage to buildings, land and infrastructure. Liquefaction occurred at a number of sites across the Christchurch Boys High School sports grounds; one area in particular contained a piston ground failure and an adjacent silt volcano. Here, as part of a class project, we apply near-surface geophysics to image these two liquefaction features and determine whether they share a subsurface connection. Hand auger results enable correlation of the geophysical responses with the subsurface stratigraphy. The survey results suggest that there is a subsurface link, likely via a paleo-stream channel. The anomalous responses of the horizontal loop electromagnetic survey and electrical resistivity imaging highlight the disruption of the subsurface electrical properties beneath and between the two liquefaction features. The vertical magnetic gradient may also show a subtle anomalous response in this area, however the results are inconclusive. The ground penetrating radar survey shows disruption of the subsurface stratigraphy beneath the liquefaction features, in particular sediment mounding beneath the silt ejection (‘‘silt volcano’’) and stratigraphic disruption beneath the piston failure. The results indicate how near-surface geophysics allow the characteristics of liquefaction in the subsurface to be better understood, which could aid remediation work following liquefaction-induced land damage and guide interpretation of geophysical surveys of paleoliquefaction features.