Stable isotopes as indicators of nitrate attenuation across landscapes

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.

Towards performance-based design of integrated foundation-superstructure s…

Research papers, University of Canterbury Library

The nonlinear dynamic soil-foundation-structure interaction (SFSI) can signifi cantly affect the seismic response of buildings, causing additional deformation modes, damage and repair costs. Because of nonlinear foundation behaviour and interactions, the seismic demand on the superstructure may considerably change, and also permanent deformations at the foundation level may occur. Although SFSI effects may be benefi cial to the superstructure performance, any advantage would be of little structural value unless the phenomenon can be reliably controlled and exploited. Detrimental SFSI effects may also occur, including acceleration and displacement response ampli cation and differential settlements, which would be unconservative to neglect. The lack of proper understanding of the phenomenon and the limited available simpli ed tools accounting for SFSI have been major obstacles to the implementation of integrated design and assessment procedures into the everyday practice. In this study concepts, ideas and practical tools (inelastic spectra) for the seismic design and assessment of integrated foundation-superstructure systems are presented, with the aim to explicitly consider the impact of nonlinearities occurring at the soil-foundation interface on the building response within an integrated approach, where the foundation soil and superstructure are considered as part of an integrated system when evaluating the seismic response, working synergically for the achievement of a target global performance. A conceptual performance-based framework for the seismic design and assessment of integrated foundation-superstructure systems is developed. The framework is based on the use of peak and residual response parameters for both the superstructure and the foundation, which are then combined to produce the system performance matrix. Each performance matrix allows for worsening of the performance when different contributions are combined. An attempt is made to test the framework by using case histories from the 2011 Christchurch earthquake, which are previously shown to have been severely affected by nonlinear SFSI. The application highlights the framework sensitivity to the adopted performance limit states, which must be realistic for a reliable evaluation of the system performance. Constant ductility and constant strength inelastic spectra are generated for nonlinear SFSI systems (SDOF nonlinear superstructure and 3DOF foundation allowing for uplift and soil yielding), representing multistorey RC buildings with shallow rigid foundations supported by cohesive soils. Different ductilities/strengths, hysteretic rules (Bi-linear, Takeda and Flag-Shape), soil stiffness and strength and bearing capacity factors are considered. Footings and raft foundations are investigated, characterized respectively by constant (3 and 8) and typically large bearing capacity factors. It is confi rmed that when SFSI is considered, the superstructure yielding force needed to satisfy a target ductility for a new building changes, and that similarly, for an existing building, the ductility demand on a building of a given strength varies. The extent of change of seismic response with respect to xed-base (FB) conditions depends on the class of soils considered, and on the bearing capacity factor (SF). For SF equal to 3, the stiffer soils enhance the nonlinear rotational foundation behaviour and are associated with reduced settlement, while the softer ones are associated with increased settlement response but not signi ficant rotational behaviour. On average terms, for the simplifi ed models considered, SFSI is found to be bene cial to the superstructure performance in terms of acceleration and superstructure displacement demand, although exceptions are recorded due to ground motion variability. Conversely, in terms of total displacement, a signi cant response increase is observed. The larger the bearing capacity factor, the more the SFSI response approaches the FB system. For raft foundation buildings, characterized by large bearing capacity factors, the impact of foundation response is mostly elastic, and the system on average approaches FB conditions. Well de fined displacement participation factors to the peak total lateral displacement are observed for the different contributions (i.e. peak foundation rotation and translation and superstructure displacement). While the superstructure and foundation rotation show compensating trends, the foundation translation contribution varies as a function of the moment-to-shear ratio, becoming negligible in the medium-to-long periods. The longer the superstructure FB period, the less the foundation response is signifi cant. The larger the excitation level and the less ductile the superstructure, the larger the foundation contribution to the total lateral displacement, and the less the superstructure contribution. In terms of hysteretic behaviour, its impact is larger when the superstructure response is more signifi cant, i.e. for the softer/weaker soils and larger ductilities. Particularly, for the Flag Shape rule, larger superstructure displacement participation factors and smaller foundation contributions are recorded. In terms of residual displacements, the total residual-to-maximum ratios are similar in amplitudes and trends to the corresponding FB system responses, with the foundation and superstructure contributions showing complementary trends. The impact of nonlinear SFSI is especially important for the Flag Shape hysteresis rule, which would not otherwise suffer of any permanent deformations. By using the generated peak and residual inelastic spectra (i.e. inelastic acceleration/ displacement modifi cation factor spectra, and/or participation factor and residual spectra), conceptual simplifi ed procedures for the seismic design and assessment of integrated foundation-superstructure systems are presented. The residual displacements at both the superstructure and foundation levels are explicitly considered. Both the force- and displacement-based approaches are explored. The procedures are de fined to be complementary to the previously proposed integrated performance-based framework. The use of participation factor spectra allows the designer to easily visualize the response of the system components, and could assist the decision making process of both the design and assessment of SFSI systems. The presented numerical results have been obtained using simpli ed models, assuming rigid foundation behaviour and neglecting P-Delta effects. The consideration of more complex systems including asymmetry in stiffness, mass, axial load and ground conditions with a exible foundation layout would highlight detrimental SFSI effects as related to induced differential settlements, while accounting for PDelta effects would further amplify the displacement response. Also, the adopted acceleration records were selected and scaled to match conventional design spectra, thus not representing any response ampli cation in the medium-to-long period range which could as well cause detrimental SFSI effects. While these limitations should be the subject of further research, this study makes a step forward to the understanding of SFSI phenomenon and its incorporation into performance-based design/assessment considerations.