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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 purpose of this thesis is to conduct a detailed examination of the forward-directivity characteristics of near-fault ground motions produced in the 2010-11 Canterbury earthquakes, including evaluating the efficacy of several existing empirical models which form the basis of frameworks for considering directivity in seismic hazard assessment. A wavelet-based pulse classification algorithm developed by Baker (2007) is firstly used to identify and characterise ground motions which demonstrate evidence of forward-directivity effects from significant events in the Canterbury earthquake sequence. The algorithm fails to classify a large number of ground motions which clearly exhibit an early-arriving directivity pulse due to: (i) incorrect pulse extraction resulting from the presence of pulse-like features caused by other physical phenomena; and (ii) inadequacy of the pulse indicator score used to carry out binary pulse-like/non-pulse-like classification. An alternative ‘manual’ approach is proposed to ensure 'correct' pulse extraction and the classification process is also guided by examination of the horizontal velocity trajectory plots and source-to-site geometry. Based on the above analysis, 59 pulse-like ground motions are identified from the Canterbury earthquakes , which in the author's opinion, are caused by forward-directivity effects. The pulses are also characterised in terms of their period and amplitude. A revised version of the B07 algorithm developed by Shahi (2013) is also subsequently utilised but without observing any notable improvement in the pulse classification results. A series of three chapters are dedicated to assess the predictive capabilities of empirical models to predict the: (i) probability of pulse occurrence; (ii) response spectrum amplification caused by the directivity pulse; (iii) period and amplitude (peak ground velocity, PGV) of the directivity pulse using observations from four significant events in the Canterbury earthquakes. Based on the results of logistic regression analysis, it is found that the pulse probability model of Shahi (2013) provides the most improved predictions in comparison to its predecessors. Pulse probability contour maps are developed to scrutinise observations of pulses/non-pulses with predicted probabilities. A direct comparison of the observed and predicted directivity amplification of acceleration response spectra reveals the inadequacy of broadband directivity models, which form the basis of the near-fault factor in the New Zealand loadings standard, NZS1170.5:2004. In contrast, a recently developed narrowband model by Shahi & Baker (2011) provides significantly improved predictions by amplifying the response spectra within a small range of periods. The significant positive bias demonstrated by the residuals associated with all models at longer vibration periods (in the Mw7.1 Darfield and Mw6.2 Christchurch earthquakes) is likely due to the influence of basin-induced surface waves and non-linear soil response. Empirical models for the pulse period notably under-predict observations from the Darfield and Christchurch earthquakes, inferred as being a result of both the effect of nonlinear site response and influence of the Canterbury basin. In contrast, observed pulse periods from the smaller magnitude June (Mw6.0) and December (Mw5.9) 2011 earthquakes are in good agreement with predictions. Models for the pulse amplitude generally provide accurate estimates of the observations at source-to-site distances between 1 km and 10 km. At longer distances, observed PGVs are significantly under-predicted due to their slower apparent attenuation. Mixed-effects regression is employed to develop revised models for both parameters using the latest NGA-West2 pulse-like ground motion database. A pulse period relationship which accounts for the effect of faulting mechanism using rake angle as a continuous predictor variable is developed. The use of a larger database in model development, however does not result in improved predictions of pulse period for the Darfield and Christchurch earthquakes. In contrast, the revised model for PGV provides a more appropriate attenuation of the pulse amplitude with distance, and does not exhibit the bias associated with previous models. Finally, the effects of near-fault directivity are explicitly included in NZ-specific probabilistic seismic hazard analysis (PSHA) using the narrowband directivity model of Shahi & Baker (2011). Seismic hazard analyses are conducted with and without considering directivity for typical sites in Christchurch and Otira. The inadequacy of the near-fault factor in the NZS1170.5: 2004 is apparent based on a comparison with the directivity amplification obtained from PSHA.