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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, Victoria University of Wellington

<strong>Sea level rise is one consequence of Earth’s changing climate. Century-long tide gauge records show that global-mean sea-level rise reached 11-16 cm during the twentieth century at a mean rate of 1.2 mm/y. Today, the average rate of global-mean sea-level rise is higher at 3-4 mm/y and is expected to increase in the future. This represents a hazard to low elevation coastal zones worldwide. Yet, before global sea level projections can be used to characterise future coastal flood hazard at a local scale, the effects of tectonics (and other processes) that drive vertical land motion (VLM) must be considered. VLM is defined as the vertical velocity (uplift or subsidence) of the solid surface with respect to the centre of Earth. In this study, new VLM maps are generated over coastal strips in New Zealand, using Sentinel-1 InSAR and GNSS data.</strong>In New Zealand, measuring VLM using InSAR on naturally vegetated or agricultural land is difficult due to signal decorrelation. Along the rural Bay of Plenty coastal strip, I use a persistent-scatterer approach to generate a VLM map from both east-looking ascending and west-looking descending Sentinel-1 data between 2015-2021. Using time-series data over the same time period from a dense network of 20 GNSS sensors, I tie InSAR-derived line-of-sight velocity to the 2014 ITRF reference frame. I test two different methods for measuring VLM and compare the results against GNSS vertical velocity along the Bay of Plenty coast. Best results are achieved by first removing the interpolated horizontal GNSS velocity field from each of the InSAR datasets, before averaging the two VLM estimates. Measured VLM is between -3 and 3 mm/y, with negative values (subsidence) occurring within the low-lying Rangitāiki Plain and Ōpōtiki valley, and uplift across the elevated region west of Matatā.This thesis integrates geomorphological, geological, and historical levelling VLM records with modern satellite datasets to assess VLM across timescales ranging from 10 to 100,000 years at Matatā. Uplift rate has been variable through time, with average uplift over the last 300,000 years of 1 mm/y, 4.5 mm/y since 1720 years, 2 mm/y between 1950-1978, and 10 mm/y between 2004-2011. Previous modelling has shown that the best fit to the 2004-2011 rapid uplift rates is an inflating magmatic source at ~10 km depth beneath Matatā. To reconcile all data, I present a VLM model that consists of short-lived periods (7 years) of rapid uplift (10 mm/y), separated by longer periods (30 years) of lower background uplift (3 mm/y). The episodic nature of VLM at Matatā likely reflects short-lived periods of magmatic intrusion. Episodic VLM characterised by large rates of uplift (10 mm/y) has been seen at Taupō volcano, and other volcanic centers globally. It has been 12 years since the end of the last intrusion episode; this modelling suggest one may expect to observe increased uplift rates at Matatā in the coming decades. Densely populated urban coastal strips are most at risk from the effects of relative sea-level rise. At the same time, anthropogenic activities associated with urbanization, such as groundwater withdrawal, and land reclamation can lead to local land subsidence (LLS), further exacerbating the risk to urban infrastructure. LLS refers to subsidence relative to nearby land area assumed to be stable. In this thesis, I create the first high-resolution (10 m) maps of LLS at six urban coastal strips in New Zealand, with a combined length of 285 km, using Sentinel-1 InSAR data between 2018-2021. This analysis reveals 89% of urban coastal strips are subsiding at rates of -0.5 mm/y or greater, and 11% is subsiding at higher rates of -3.0 mm/y or greater. On average, subsidence is -0.6 to -2.9 mm/y higher at the coastal strip, compared to inland areas occupied by GNSS stations. This analysis also documents highly-localised hotspots of LLS, with subsidence rates of up to -15 mm/y. In Christchurch, rapid and localised subsidence (-8 mm/y) is observed within coastal suburbs New Brighton and Southshore. In most cities, the highest subsidence rates occur on land reclaimed in the early-late twentieth century, and in areas built on Holocene sediment. Time-series analysis of LLS at sites of reclaimed land shows both linear and non-linear rates of deformation over time periods of up to 6-8 years. This thesis highlights the variable exposure to relative sea-level rise of New Zealand coastal strips, and demonstrates that in many cases current rates of VLM should be expected to continue for the next few decades.