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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

Deconstruction, at the end of the useful life of a building, produces a considerable amount of materials which must be disposed of, or be recycled / reused. At present, in New Zealand, most timber construction and demolition (C&D) material, particularly treated timber, is simply waste and is placed in landfills. For both technical and economic reasons (and despite the increasing cost of landfills), this position is unlikely to change in the next 10 – 15 years unless legislation dictates otherwise. Careful deconstruction, as opposed to demolition, can provide some timber materials which can be immediately re-used (eg. doors and windows), or further processed into other components (eg. beams or walls) or recycled (‘cascaded’) into other timber or composite products (e.g. fibre-board). This reusing / recycling of materials is being driven slowly in NZ by legislation, the ‘greening’ of the construction industry and public pressure. However, the recovery of useful material can be expensive and uneconomic (as opposed to land-filling). In NZ, there are few facilities which are able to sort and separate timber materials from other waste, although the soon-to-be commissioned Burwood Resource Recovery Park in Christchurch will attempt to deal with significant quantities of demolition waste from the recent earthquakes. The success (or otherwise) of this operation should provide good information as to how future C&D waste will be managed in NZ. In NZ, there are only a few, small scale facilities which are able to burn waste wood for energy recovery (e.g. timber mills), and none are known to be able to handle large quantities of treated timber. Such facilities, with constantly improving technology, are being commissioned in Europe (often with Government subsidies) and this indicates that similar bio-energy (co)generation will be established in NZ in the future. However, at present, the NZ Government provides little assistance to the bio-energy industry and the emergence worldwide of shale-gas reserves is likely to push the economic viability of bio-energy further into the future. The behaviour of timber materials placed in landfills is complex and poorly understood. Degrading timber in landfills has the potential to generate methane, a potent greenhouse gas, which can escape to the atmosphere and cancel out the significant benefits of carbon sequestration during tree growth. Improving security of landfills and more effective and efficient collection and utilisation of methane from landfills in NZ will significantly reduce the potential for leakage of methane to the atmosphere, acting as an offset to the continuing use of underground fossil fuels. Life cycle assessment (LCA), an increasingly important methodology for quantifying the environmental impacts of building materials (particularly energy, and global warming potential (GWP)), will soon be incorporated into the NZ Green Building Council Greenstar rating tools. Such LCA studies must provide a level playing field for all building materials and consider the whole life cycle. Whilst the end-of-life treatment of timber by LCA may establish a present-day base scenario, any analysis must also present a realistic end-of-life scenario for the future deconstruction of any 6 new building, as any building built today will be deconstructed many years in the future, when very different technologies will be available to deal with construction waste. At present, LCA practitioners in NZ and Australia place much value on a single research document on the degradation of timber in landfills (Ximenes et al., 2008). This leads to an end-of-life base scenario for timber which many in the industry consider to be an overestimation of the potential negative effects of methane generation. In Europe, the base scenario for wood disposal is cascading timber products and then burning for energy recovery, which normally significantly reduces any negative effects of the end-of-life for timber. LCA studies in NZ should always provide a sensitivity analysis for the end-of-life of timber and strongly and confidently argue that alternative future scenarios are realistic disposal options for buildings deconstructed in the future. Data-sets for environmental impacts (such as GWP) of building materials in NZ are limited and based on few research studies. The compilation of comprehensive data-sets with country-specific information for all building materials is considered a priority, preferably accounting for end-of-life options. The NZ timber industry should continue to ‘champion’ the environmental credentials of timber, over and above those of the other major building materials (concrete and steel). End-of-life should not be considered the ‘Achilles heel’ of the timber story.