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.
The assessment of damage and remaining capacity after an earthquake is an immediate measure to determine whether a reinforced concrete (RC) building is usable and safe for occupants. The recent Christchurch earthquake (22 February 2011) caused a uniquely severe level of structural damage to modern buildings, resulting in extensive damage to the building stock. About 60% of damaged multistorey concrete buildings (3 storeys and up) were demolished after the earthquake, and the cost of reconstruction amounted to 40 billion NZD. The aftermath disclosed issues of great complexities regarding the future of the RC buildings damaged by the earthquakes. This highlighted the importance of post-event decision-making, as the outcome will allow the appropriate course of action—demolition, repair or acceptance of the existing building—to be considered. To adopt the proper strategy, accurate assessment of the residual capacity and the level of damage is required. This doctoral dissertation aims to assess the damage and remaining capacity at constituent material and member level (i.e., concrete material and beams) through a systematic approach in an attempt to address part of an existing gap in the available literature. Since the residual capacity of RC members is not unique and depends on previously applied loading history, post-event residual capacity in this study was assessed in terms of fraction of fatigue life (i.e., the number of cycles required to failure). This research comprises three main parts: (1) residual capacity and damage assessment at material level (i.e., concrete), (2) post-yield bond deterioration and damage assessment at the interface of steel and concrete, and, finally, (3) residual capacity and damage assessment at member level (i.e., RC beam). The first part of this research focused on damage assessment and the remaining capacity of concrete from a material point of view. It aimed to employ appropriate and reliable durability-based testing and image-detection techniques to quantify deterioration in the mechanical properties of concrete on the basis that stress-induced damage occurred in the microstructural system of the concrete material. To this end, in the first phase, a feasibility study was conducted in which a combination of oxygen permeability, electrical resistivity and porosity tests were assessed to determine if they were robust and reliable enough to reveal damage which occurred in the microstructural system of concrete. The results, in terms of change in permeability, electrical resistivity and porosity features of disk samples taken from the middle third of damaged concrete cylinders (200 mm × 100 mm) monotonically pre-loaded to 50%, 70%, 90% and 95% of the ultimate strength (f′c), showed the permeability test is a reliable tool to identify the degree of damage, due to its high sensitivity to the load-induced microcracking. In parallel, to determine the residual capacity, the companion damaged concrete cylinders already loaded to the same level of compressive strength were reloaded up to failure. Comparing the stress–strain relationship of damaged concrete with intact material, it was also found that the strain capacity of the reloaded pre-damaged concrete cylinders decreases while strength remained virtually unchanged. In the second phase of the first part, a fluorescent microscopy technique was used to assess the damage and develop a correlation between material degradation, by virtue of the geometrical features, and damage to the concrete. To account for the effect of confinement and cyclic loading, in the third phase, the residual capacity and damage assessment of unconfined and GFRP confined concrete cylinders subjected to low-cycle fatigue loading, was investigated. Similar to the first phase, permeability testing technique was used to provide an indirect evaluation of fatigue damage. Finally, in the fourth phase of the first part, the suitability of permeability testing technique to assess damage was evaluated for cored concrete taken from three types of RC members: columns, beams and a beam-column joint. In view of the fact that the composite action of an RC member is highly dependent on the bond between reinforcement and surrounding concrete, understanding the deterioration of the bond in the post-yield range of strain in steel was crucial to assess damage at member level. Therefore, in the second phase of this research, a state-of-the- art distributed fibre optic strain sensor system (DFOSSS) system was used to evaluate bond deterioration in a cantilever RC beam subjected to monotonic lateral loading. The technology allowed the continuous capture of strain, every 2.6 mm along the length, in both reinforcing bars and cover concrete. The strain profile provided a basis by which the slip, axial stress and bond stress distributions were then established. In the third part, the study focused on the damage assessment and residual capacity of seven half-scale RC beams subjected to a constant-amplitude cyclic loading protocol. In the first stage, the structural performances of three specimens under constant-amplitude fatigue at 1%, 2% and 4% chord rotation (drift) were examined. In parallel, the number of cycles to failure, degradation in strength, stiffness and energy dissipation were characterized. In the second stage, four RC beams were subjected to loading up to 70% and 90% of their fatigue life, at 2% and 4% drift, and then monotonically pulled up to failure. To determine the residual flexural capacity, the lateral force–displacement results of pre-damaged specimens were compared with an undamaged specimen subjected to only monotonic loading. The study showed significant losses in strength, deformability, stiffness and energy dissipation capacity. A nonlinear finite element analysis (FEA) using concrete damage plasticity (CDP) model was also conducted in ABAQUS to numerically investigate the behaviour of the tested specimen. The results of the FE simulations indicated a reasonable response compared with the behaviour of the test specimen in terms of force–displacement and cracking pattern. During the Christchurch earthquake it was observed that the loading history has a significant influence on structural responses. While in conventional pseudo-static loading protocol, internal forces can be redistributed along the plastic length: there is little chance for structures undergoing high initial loading amplitude to redistribute pertinent stresses. As a result, in the third phase of this part, the effect of high rate of loading on the behaviour of seismically designed RC beams was investigated. Two half-scale cantilever RC beams were subjected to similar constant-amplitude cyclic loading at 2% and 4% drifts, but at a rate of 500 mm/s. Due to the incapability of conventional measuring techniques, a motion-tracking system was employed for data acquisition with the high-speed tests. The effect of rate of loading on the fatigue life of specimens (i.e., the number of cycles required to failure), secant stiffness, failure mode, cracking pattern, beam elongations and bar fracture surface were analysed. Integrating the results of all parts of this research has resulted in a better understanding of residual capacity and the development of damage at both the material and member level by using a low-cycle fatigue approach.
