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.
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.
The Avon and Heathcote Rivers, located in the city of Christchurch, New Zealand, are lowland spring-fed rivers linked with the Christchurch Groundwater System. At present, the flow paths and recharge sources to the Christchurch Groundwater System are not fully understood. Study of both the Avon and Heathcote Rivers can provide greater insight into this system. In addition, during the period 2010-2012, Christchurch has experienced large amounts of seismic activity, including a devastating Mw 6.2 aftershock on February 22nd, 2011, which caused widespread damage and loss of life. Associated with these earthquakes was the release of large amounts of water through liquefaction and temporary springs throughout the city. This provided a unique opportunity to study groundwater surface water interactions following a large scale seismic event. Presented herein is the first major geochemical study on the Avon and Heathcote Rivers and the hydrological impact of the February 22, 2011 Christchurch Earthquake. The Avon, Heathcote, and Waimakariri Rivers were sampled in quarterly periods starting in July 2011 and analyzed for stable Isotopes δ¹⁸O, δD, and δ¹³C and major anion composition. In addition, post -earthquake samples were collected over the days immediately following the February 22, 2011 earthquake and analyzed for stable isotopes δ¹⁸O and δD and major anion composition. A variety of analytical methods were used identify the source of the waters in the Avon-Heathcote System and evaluate the effectiveness of stable isotopes as geochemical tracers in the Christchurch Groundwater System. The results of this thesis found that the waters from the Avon and Heathcote Rivers are geochemically the same, originating from groundwater, and exhibit a strong tidal influence within 5km of the Avon-Heathcote Estuary. The surface waters released following the February 22nd, 2011 earthquake were indistinguishable from quarterly samples taken from the Avon and Heathcote Rivers when comparing stable isotopic composition. The anion data suggests the waters released following the February 22nd, 2011 Christchurch Earthquake were sourced primarily from shallow groundwater, and also suggests a presence of urban sewage at some sites. Attempts to estimate recharge sources for the Avon-Heathcote Rivers using published models for the Christchurch Groundwater System yielded results that were not consistent between models. In evaluating the use of geochemical constituents as tracers in the Christchurch Groundwater System, no one isotope could provide a clear resolution, but when used in conjunction, δ¹⁸O, δ¹³C, and DIC, seem to be the most effective tracers. Sample sizes for δ¹³C were too small for a robust evaluation. Variability on the Waimakariri River appears to be greater than previously estimated, which could have significant impacts on geochemical models for the Christchurch Groundwater System. This research demonstrates the value of using multiple geochemical constituents to enrich our understanding of the groundwater surfaces-water interactions and the Christchurch Groundwater System as a whole.
This thesis is concerned with springs that appeared in the Hillsborough, Christchurch during the 2010-2011 Canterbury Earthquake Sequence, and which have continued to discharge groundwater to the surface to the present time. Investigations have evolved, measurements of discharge at selected sites, limited chemical data on anions and isotope analysis. The springs are associated with earthquake generated fissures (extensional) and compression zones, mostly in loess-colluvium soils of the valley floor and lower slopes. Extensive peat swamps are present in the Hillsborough valley, with a groundwater table at ~1m below ground. The first appearance of the ‘new’ springs took place following the Mw 7.1 Darfield Earthquake on 4 September 2010, and discharges increased both in volume and extent of the Christchurch Mw 6.3 Earthquake of 22 February 2011. Five monitored sites show flow rates in the range of 4.2-14.4L/min, which have remained effectively constant for the duration of the study (2014-2015). Water chemistry analysis shows that the groundwater discharges are sourced primarily from volcanic bedrocks which underlies the valley at depths ≤50m below ground level. Isotope values confirm similarities with bedrock-sourced groundwater, and the short term (hours-days) influence of extreme rainfall events. Cyclone Lusi (2013-2014) affects were monitored and showed recovery of the bedrock derived water signature within 72 hours. Close to the mouth of the valley sediments interfinger with Waimakiriri River derived alluvium bearing a distinct and different isotope signature. Some mixing is evident at certain locations, but it is not clear if there is any influence from the Huntsbury reservoir which failed in the Port Hills Earthquake (22 February 2011) and stored groundwater from the Christchurch artesian aquifer system (Riccarton Gravel).
Saltwater Forest is a Dacrydium cupressinum-dominated lowland forest covering 9000 ha in south Westland, South Island, New Zealand. Four thousand hectares is managed for sustainable production of indigenous timber. The aim of this study was to provide an integrated analysis of soils, soil-landform relationships, and soil-vegetation relationships at broad and detailed scales. The broad scale understandings provide a framework in which existing or future studies can be placed and the detailed studies elucidate sources of soil and forest variability.
Glacial landforms dominate. They include late Pleistocene lateral, terminal and ablation moraines, and outwash aggradation and degradation terraces. Deposits and landforms from six glacial advances have been recognised ranging from latest Last (Otira) Glaciation to Penultimate (Waimea) Glaciation. The absolute ages of landforms were established by analysis of the thickness and soil stratigraphy of loess coverbeds, augmented with radiocarbon dating and phytolith and pollen analysis.
In the prevailing high rainfall of Westland soil formation is rapid. The rate of loess accretion in Saltwater
Forest (ca. 30 mm ka⁻¹) has been low enough that soil formation and loess accretion took place contemporaneously. Soils formed in this manner are known as upbuilding soils. The significant difference between upbuilding pedogenesis and pedogenesis in a topdown sense into an existing sediment body is that each subsoil increment of an upbuilding soil has experienced processes of all horizons above. In Saltwater Forest subsoils of upbuilding soils are strongly altered because they have experienced the extremely acid environment of the soil surface at some earlier time. Some soil chronosequence studies in Westland have included upbuilding soils formed in loess as the older members of the sequence. Rates and types of processes inferred from these soils should be reviewed because upbuilding is a different pedogenic pathway to topdown pedogenesis.
Landform age and morphology were used as a primary stratification for a study of the soil pattern and nature of soil variability in the 4000 ha production area of Saltwater Forest. The age of landforms (> 14 ka) and rapid soil formation mean that soils are uniformly strongly weathered and leached. Soils include Humic Organic Soils, Perch-gley Podzols, Acid Gley Soils, Allophanic Brown Soils, and Orthic or Pan Podzols. The major influence on the nature of soils is site hydrology which is determined by macroscale features of landforms (slope, relief, drainage density), mesoscale effects related to position on landforms, and microscale influences determined by microtopography and individual tree effects. Much of the soil variability arises at microscales so that it is not possible to map areas of uniform soils at practical map scales. The distribution of soil variability across spatial scales, in relation to the intensity of forest management, dictates that it is most appropriate to map soil complexes with boundaries coinciding with landforms.
Disturbance of canopy trees is an important agent in forest dynamics. The frequency of forest disturbance in the production area of Saltwater Forest varies in a systematic way among landforms in accord with changes in abundance of different soils. The frequency of forest turnover is highest on landforms with the greatest abundance of extremely poorly-drained Organic Soils. As the abundance of better-drained soils increases the frequency of forest turnover declines. Changes in turnover frequency are reflected in the mean size and density of canopy trees (Dacrydium cupressinum) among landforms. Terrace and ablation moraine landforms with the greatest abundance of extremely poorly-drained soils have on average the smallest trees growing most densely. The steep lateral moraines, characterised by well drained soils, have fewer, larger trees. The changes manifested at the landform scale are an integration of processes operating over much shorter range as a result of short-range soil variability. The systematic changes in forest structure and turnover frequency among landforms and soils have important implications for sustainable forest management.
The structure and geomorphology of active orogens evolves on time scales ranging from a single earthquake to millions of years of tectonic deformation. Analysis of crustal deformation using new and established remote sensing techniques, and integration of these data with field mapping, geochronology and the sedimentary record, create new opportunities to understand orogenic evolution over these timescales. Timor Leste (East Timor) lies on the northern collisional boundary between continental crust from the Australian Plate and the Banda volcanic arc. GPS studies have indicated that the island of Timor is actively shortening. Field mapping and fault kinematic analysis of an emergent Pliocene marine sequence identifies gentle folding, overprinted by a predominance of NW-SE oriented dextral-normal faults and NE-SW oriented sinistral-normal faults that collectively bound large (5-20km2) bedrock massifs throughout the island. These fault systems intersect at non-Andersonian conjugate angles of approximately 120° and accommodate an estimated 20 km of orogen-parallel extension. Folding of Pliocene rocks in Timor may represent an early episode of contraction but the overall pattern of deformation is one of lateral crustal extrusion sub-parallel to the Banda Arc. Stratigraphic relationships suggest that extrusion began prior to 5.5 Ma, during and after initial uplift of the orogen. Sedimentological, geochemical and Nd isotope data indicate that the island of Timor was emergent and shedding terrigenous sediment into carbonate basins prior to 4.5 Ma. Synorogenic tectonic and sedimentary phases initiated almost synchronously across much of Timor Leste and <2 Myr before similar events in West Timor. An increase in plate coupling along this obliquely converging boundary, due to subduction of an outlying continental plateau at the Banda Trench, is proposed as a mechanism for uplift that accounts for orogen-parallel extension and early uplift of Timor Leste. Rapid bathymetric changes around Timor are likely to have played an important role in evolution of the Indonesian Seaway. The 2010 Mw 7.1 Darfield (Canterbury) earthquake in New Zealand was complex, involving multiple faults with strike-slip, reverse and normal displacements. Multi-temporal cadastral surveying and airborne light detection and ranging (LiDAR) surveys allowed surface deformation at the junction of three faults to be analyzed in this study in unprecedented detail. A nested, localized restraining stepover with contractional bulging was identified in an area with the overall fault structure of a releasing bend, highlighting the surface complexities that may develop in fault interaction zones during a single earthquake sequence. The earthquake also caused river avulsion and flooding in this area. Geomorphic investigations of these rivers prior to the earthquake identify plausible precursory patterns, including channel migration and narrowing. Comparison of the pre and post-earthquake geomorphology of the fault rupture also suggests that a subtle scarp or groove was present along much of the trace prior to the Darfield earthquake. Hydrogeology and well logs support a hypothesis of extended slip history and suggests that that the Selwyn River fan may be infilling a graben that has accumulated late Quaternary vertical slip of <30 m. Investigating fault behavior, geomorphic and sedimentary responses over a multitude of time-scales and at different study sites provides insights into fault interactions and orogenesis during single earthquakes and over millions of years of plate boundary deformation.
The Avon-Heathcote Estuary, located in Christchurch, New Zealand, experienced coseismic deformation as a result of the February 22nd 2011 Christchurch Earthquake. The deformation is reflected as subsidence in the northern area and uplift in the southern area of the Estuary, in addition to sand volcanoes which forced up sediment throughout the floor of the Estuary altering estuary bed height and tidal flow. The first part of the research involved quantifying the change in the modern benthic foraminifera distribution as a result of the coseismic deformation caused by the February 22nd 2011 earthquake. By analysing the taxa present immediately post deformation and then the taxa present 2 years post deformation a comparison of the benthic foraminifera distribution can be made of the pre and post deformation. Both the northern and the southern areas of the Estuary were sampled to establish whether foraminifera faunas migrated landward or seaward as a result of subsidence and uplift experienced in different areas. There was no statistical change in overall species distribution in the two year time period since the coseismic deformation occurred, however, there were some noticeable changes in foraminifera distribution at BSNS-Z3 showing a landward migration of taxa. The changes that were predicted to occur as a result of the deformation of the Estuary are taking longer than expected to show up in the foraminiferal record and a longer time period is needed to establish these changes. The second stage involved establishing the modern distribution of foraminifera at Settlers Reserve in the southern area of the Avon-Heathcote Estuary by detailed sampling along a 160 m transect. Foraminifera are sensitive to environmental parameters, tidal height, grainsize, pH and salinity were recorded to evaluate the effect these parameters have on distribution. Bray-Curtis two-way cluster analysis was primarily used to assess the distribution pattern of foraminifera. The modern foraminifera distribution is comparable to that of the modern day New Zealand brackish-water benthic foraminifera distribution and includes species not yet found in other studies of the Avon-Heathcote Estuary. Differences in sampling techniques and the restricted intertidal marshland area where the transect samples were collected account for some of the differences seen between this model and past foraminifera studies. xiii The final stage involved sampling a 2.20 m core collected from Settlers Reserve and using the modern foraminiferal distribution to establish a foraminiferal history of Settlers Reserve. As foraminifera are sensitive to tidal height they may record past coseismic deformation events and the core was used to ascertain whether record of past coseismic deformation is preserved in Settlers Reserve sediments. Sampling the core for foraminifera, grainsize, trace metals and carbon material helped to build a story of estuary development. Using the modern foraminiferal distribution and the tidal height information collected, a down core model of past tidal heights was established to determine past rates of change. Foraminifera are not well preserved throughout the core, however, a sudden relative rise in sea level is recorded between 0.25 m and 0.85 m. Using trace metal and isotope analysis to develop an age profile, this sea level rise is interpreted to record coseismic subsidence associated with a palaeoseismic event in the early 1900’s. Overall, although the Avon-Heathcote Estuary experienced clear coseismic deformation as a result of the 22nd of February 2011 earthquake, modern changes in foraminiferal distribution cannot yet be tracked, however, past seismic deformation is identified in a core. The modern transect describes the foraminifera distribution which identifies species that have not been identified in the Avon-Heathcote Estuary before. This thesis enhances the current knowledge of the Avon-Heathcote Estuary and is a baseline for future studies.
