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.
Fine grained sediment deposition in urban environments during natural hazard events can impact critical infrastructure and properties (urban terrain) leading to reduced social and economic function and potentially adverse public health effects. Therefore, clean-up of the sediments is required to minimise impacts and restore social and economic functionality as soon as possible. The strategies employed to manage and coordinate the clean-up significantly influence the speed, cost and quality of the clean-up operation. Additionally, the physical properties of the fine grained sediment affects the clean-up, transport, storage and future usage of the sediment. The goals of the research are to assess the resources, time and cost required for fine grained sediment clean-up in an urban environment following a disaster and to determine how the geotechnical properties of sediment will affect urban clean-up strategies. The thesis focuses on the impact of fine grained sediment (<1 mm) deposition from three liquefaction events during the Canterbury earthquake sequence (2010-2011) on residential suburbs and transport networks in Christchurch. It also presents how geotechnical properties of the material may affect clean-up strategies and methods by presenting geotechnical analysis of tephra material from the North Island of New Zealand. Finally, lessons for disaster response planning and decision making for clean-up of sediment in urban environments are presented. A series of semi-structured interviews of key stakeholders supported by relevant academic literature and media reports were used to record the clean-up operation coordination and management and to make a preliminary qualification of the Christchurch liquefaction ejecta clean-up (costs breakdown, time, volume, resources, coordination, planning and priorities). Further analysis of the costs and resources involved for better accuracy was required and so the analysis of Christchurch City Council road management database (RAMM) was done. In order to make a transition from general fine sediment clean-up to specific types of fine disaster sediment clean-up, adequate information about the material properties is required as they will define how the material will be handled, transported and stored. Laboratory analysis of young volcanic tephra from the New Zealand’s North Island was performed to identify their geotechnical properties (density, granulometry, plasticity, composition and angle of repose). The major findings of this research were that emergency planning and the use of the coordinated incident management system (CIMS) system during the emergency were important to facilitate rapid clean-up tasking, management of resources and ultimately recovery from widespread and voluminous liquefaction ejecta deposition in eastern Christchurch. A total estimated cost of approximately $NZ 40 million was calculated for the Christchurch City clean-up following the 2010-2011 Canterbury earthquake sequence with a partial cost of $NZ 12 million for the Southern part of the city, where up to 33% (418 km) of the road network was impacted by liquefaction ejecta and required clearing of the material following the 22 February 2011 earthquake. Over 500,000 tonnes of ejecta has been stockpiled at Burwood landfill for all three liquefaction inducing earthquake events. The average cost per kilometre for the event clean-up was $NZ 5,500/km (4 September 2010), $NZ 11,650/km (22 February 2011) and $NZ 11,185/km (13 June 2011). The duration of clean-up time of residential properties and the road network was approximately two to three months for each of the three liquefaction ejecta events; despite events volumes and spatial distribution of ejecta. Interviews and quantitative analysis of RAMM data revealed that the experience and knowledge gained from the Darfield earthquake (4 September 2010) clean-up increased the efficiency of the following Christchurch earthquake induced liquefaction ejecta clean-up events. Density, particle size, particle shape, clay content and moisture content, are the important geotechnical properties that need to be considered when planning for a clean-up method that incorporates collection, transport and disposal or storage. The geotechnical properties for the tephra samples were analysed to increase preparedness and reaction response of potentially affected North Island cities from possible product from the active volcanoes in their region. The geotechnical results from this study show that volcanic tephra could be used in road or construction material but the properties would have to be further investigated for a New Zealand context. Using fresh volcanic material in road, building or flood control construction requires good understanding of the material properties and precaution during design and construction to extra care, but if well planned, it can be economically beneficial.
Environmental stress and disturbance can affect the structure and functioning of marine ecosystems by altering their physical, chemical and biological features. In estuaries, benthic invertebrate communities play important roles in structuring sediments, influencing primary production and biogeochemical flux, and occupying key food web positions. Stress and disturbance can reduce species diversity, richness and abundance, with ecological theory predicting that biodiversity will be at its lowest soon after a disturbance with assemblages dominated by opportunistic species. The Avon-Heathcote Estuary in Christchurch New Zealand has provided a novel opportunity to examine the effects of stress, in the form of eutrophication, and disturbance, in the form of cataclysmic earthquake events, on the structure and functioning of an estuarine ecosystem. For more than 50 years, large quantities (up to 500,000m3/day) of treated wastewater were released into this estuary but in March 2010 this was diverted to an ocean outfall, thereby reducing the nutrient loading by around 90% to the estuary. This study was therefore initially focussed on the reversal of eutrophication and consequent effects on food web structure in the estuary as it responded to lower nutrients. In 2011, however, Christchurch was struck with a series of large earthquakes that greatly changed the estuary. Massive amounts of liquefied sediments, covering up to 65% of the estuary floor, were forced up from deep below the estuary, the estuary was tilted by up to a 50cm rise on one side and a corresponding drop on the other, and large quantities of raw sewage from broken wastewater infrastructure entered the estuary for up to nine months. This study was therefore a test of the potentially synergistic effects of nutrient reduction and earthquake disturbance on invertebrate communities, associated habitats and food web dynamics. Because there was considerable site-to-site heterogeneity in the estuary, the sites in this study were selected to represent a eutrophication gradient from relatively “clean” (where the influence of tidal flows was high) to highly impacted (near the historical discharge site). The study was structured around these sites, with components before the wastewater diversion, after the diversion but before the earthquakes, and after the earthquakes. The eutrophication gradient was reflected in the composition and isotopic chemistry of primary producer and invertebrate communities and the characteristics of sediments across the sample sites. Sites closest to the former wastewater discharge pipe were the most eutrophic and had cohesive organic -rich, fine sediments and relatively depauperate communities dominated by the opportunistic taxa Capitellidae. The less-impacted sites had coarser, sandier sediments with fewer pollutants and far less organic matter than at the eutrophic sites, relatively high diversity and lower abundances of micro- and macro-algae. Sewage-derived nitrogen had became incorporated into the estuarine food web at the eutrophic sites, starting at the base of the food chain with benthic microalgae (BMA), which were found to use mostly sediment-derived nitrogen. Stable isotopic analysis showed that δ13C and δ15N values of most food sources and consumers varied spatially, temporally and in relation to the diversion of wastewater, whereas the earthquakes did not appear to affect the overall estuarine food web structure. This was seen particularly at the most eutrophic site, where isotopic signatures became more similar to the cleaner sites over two-and-a-half years after the diversion. New sediments (liquefaction) produced by the earthquakes were found to be coarser, have lower concentrations of heavy metals and less organic matter than old (existing) sediments. They also had fewer macroinvertebrate inhabitants initially after the earthquakes but most areas recovered to pre-earthquake abundance and diversity within two years. Field experiments showed that there were higher amounts of primary production and lower amounts of nutrient efflux from new sediments at the eutrophic sites after the earthquakes. Primary production was highest in new sediments due to the increased photosynthetic efficiency of BMA resulting from the increased permeability of new sediments allowing increased light penetration, enhanced vertical migration of BMA and the enhanced transport of oxygen and nutrients. The reduced efflux of NH4-N in new sediments indicated that the capping of a large portion of eutrophic old sediments with new sediments had reduced the release of legacy nutrients (originating from the historical discharge) from the sediments to the overlying water. Laboratory experiments using an array of species and old and new sediments showed that invertebrates altered levels of primary production and nutrient flux but effects varied among species. The mud snail Amphibola crenata and mud crab Austrohelice crassa were found to reduce primary production and BMA biomass through the consumption of BMA (both species) and its burial from bioturbation and the construction of burrows (Austrohelice). In contrast, the cockle Austrovenus stutchburyi did not significantly affect primary production and BMA biomass. These results show that changes in the structure of invertebrate communities resulting from disturbances can also have consequences for the functioning of the system. The major conclusions of this study were that the wastewater diversion had a major effect on food web dynamics and that the large quantities of clean and unpolluted new sediments introduced to the estuary during the earthquakes altered the recovery trajectory of the estuary, accelerating it at least throughout the duration of this study. This was largely through the ‘capping’ effect of the new liquefied, coarser-grained sediments as they dissipated across the estuary and covered much of the old organic-rich eutrophic sediments. For all aspects of this study, the largest changes occurred at the most eutrophic sites; however, the surrounding habitats were important as they provided the context for recovery of the estuary, particularly because of the very strong influence of sediments, their biogeochemistry, microalgal and macroalgal dynamics. There have been few studies documenting system level responses to eutrophication amelioration and to the best on my knowledge there are no other published studies examining the impacts of large earthquakes on benthic communities in an estuarine ecosystem. This research gives valuable insight and advancements in the scientific understanding of the effects that eutrophication recovery and large-scale disturbances can have on the ecology of a soft-sediment ecosystem.
