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.

Experimental study on the seismic performance of low damage systems for no…

Research papers, University of Canterbury Library

Field surveys and experimental studies have shown that light steel or timber framed plasterboard partition walls are particularly vulnerable to earthquake damage prompting the overarching objective of this research, which is to further the development of low damage seismic systems for non-structural partition walls in order to facilitate their adoption by industry to assist with reducing the losses associated with the maintenance and repair cost of buildings across their design life. In particular, this study focused on the behaviour of steel-framed partition walls systems with novel detailing that aim to be “low-damage” designed according to common practice for walls used in commercial and institutional buildings in New Zealand. This objective was investigated by (1) investigating the performance of a flexible track system proposed by researchers and industry by experimental testing of full-scale specimens; (2) investigating the performance of the seismic gap partition wall systems proposed in a number of studies, further developed in this study with input from industry, by experimental testing of full-scale specimens; and (3) investigating the potential implications of using these systems compared with traditionally detailed partition wall systems within multi-storey buildings using the Performance Based Earthquake Engineering loss assessment methodology. Three full-scale testing frames were designed in order to replicate, under controlled laboratory conditions, the effects of seismic shaking on partition walls within multi-storey buildings by the application of quasi-static uni-directional cyclic loading imposing an inter-storey drift. The typical configuration for test specimens was selected to be a unique “y-shape”, including one angled return wall, with typical dimensions of approximately 2400 mm along the main wall and 600 mm along (approximately) the returns walls with a height of 2405 mm from floor to ceiling. The specimens were aligned within test frames at an oblique angle to the direction of loading in order to investigate bi- directional effects. Three wall specimens with flexible track detailing, two identical plane specimens and the third including a doorway, were tested. The detailing involved removing top track anchors within the proximity of wall intersections, thus allowing the tracks to ‘bow’ out at these locations. Although the top track anchors were specified to be removed the proximity of wall intersections, a construction error was made whereby a single top track slab to concrete anchor was left in at the three-way wall junction. Despite this error, the experimental testing was deemed worthwhile since such errors will also occur in practice and because the behaviour of the wall can be examined with this fixing in mind. The specimens also included an acoustic/fire sealant at the top lining to floor boundary. In addition to providing drift capacities, the force-displacement behaviour is also reported, the dissipated energy was computed, and the parameters of the Wayne-Stewart hysteretic model were fitted to the results. The specimen with the door opening behaved significantly different to the plane specimens: damage to the doorway specimen began as cracking of the wallboard propagating from the corners of the doorway following which the L- and Y- shaped junctions behaved independently, whereas damage to the plane specimens began as cracking of the wallboard at the top of the L-junction and wall system deformed as a single unit. The results suggest that bi-directional behaviour is important even if its impact cannot be directly quantified by the experiments conducted. Damage to sealant implies that the bond between plasterboard and sealant is important for its seismic performance. Careful quality control is advised as defects in the bond may significantly impact its ability to withstand seismic movement. Two specimens with seismic gap detailing were tested: a steel stud specimen and a timber stud specimen. Observed drift capacities were significantly greater than traditional plasterboard partition systems. Equations were used to predict the drift at which damage state 1 (DS1) and damage state 2 (DS2) would initiate. The equation used to estimate the drift at the onset of DS1 accurately predicted the onset of plaster cracking but overestimated the drift at which the gap filling material was damaged. The equation used to predict the onset of DS2 provided a lower bound for both specimens and also when used to predict results of previous experimental tests on seismic gap systems. The gap-filling material reduced the drift at the onset of DS1, however, it had a beneficial effect on the re-centring behaviour of the linings. Out-of-plane displacements and return wall configuration did not appear to significantly impact the onset of plaster cracking in the specimens. A loss assessment according to the PBEE methodology was conducted on four steel MRF case study buildings: (1) a 4-storey building designed for the Christchurch region, (2) a 4-storey building designed for the Wellington region, (3) a 12-storey building designed for the Christchurch region, and (4) a 12- storey building designed for the Wellington region. The fragility parameters for a traditional partition system, the flexible track partition system, and the seismic gap steel stud and timber stud partition systems were included within the loss assessment. The order (lowest to highest) of each system in terms of the expected annual losses of each building when incorporating the system was, (1) the seismic gap timber stud system, (2) the seismic gap steel stud system, (3) the traditional/baseline system, and (4) the flexible track system. For the seismic gap timber stud system, which incurred the greatest reduction in expected annual losses for each case study building, the reduction in expected annual losses in comparison to the losses found when using the traditional system ranged from a 5% to a 30% reduction. This reinforces the fact that while there is a benefit to the using low damage partition systems in each building the extent of reduction in expected annual losses is significantly dependent on the particular building design and its location. The flexible track specimens had larger repair costs at small hazard levels compared to the traditional system but smaller repair costs at larger hazard levels. However, the resulting expected annual losses for the flexible track system was higher than the traditional system which reinforces findings from past studies which observed that the greatest contribution to expected annual losses arises from low to moderate intensity shaking seismic events (low hazard levels).