Disposing of waste on land has been a method practiced by many countries because it is relatively inexpensive. This has led to the fast increase of landfilling option which is also due to increase of waste generation, resulting in the increase in the urgency of investigating cheap measures of treating wastewater (leachate) that is generated from landfills prior to its discharge to the environment. After the application of the process of nitrification using Sequencing Batch Reactor (SBR) such as is applied at Mariannhill landfill site, Durban, the treated leachate still contains high level of nitrate ranging from 500 – 2000 mg/ℓ, which greatly exceeds the discharge limit of 12 mg/ℓ. Ex-situ bio-denitrification has been used widely around the world in various technological applications (SBRs, anaerobic trickling filters, etc.) that generally employ expensive chemicals. Hence the need to investigate the removal of nitrates using in-situ biodenitrification processes using readily available carbon sources such as fresh commercial garden refuse (CGRraw) and composted commercial garden refuse (CGR10). Both carbon sources were mixed with waste that had been treated for 8 weeks (Cell 1) and 16 weeks (Cell 2). The aim of this study is to determine the viability of pre-treated general waste at different degrees of stability (carbon contents) as carbon sources for in-situ bio-denitrification in landfills. The focus was mainly on determining the suitability, the kinetics and the performance of the different substrate. The suitability of the substrates to perform denitrification was assessed based on the carbon content and carbon to nitrogen ratio in the substrate. On establishing suitability, the kinetic rate of denitrification was assessed for each substrate. The kinetics analysis was based on the time taken for full denitrification to occur and the concentration of the byproducts of the denitrification process such as Ammonia. Characterization tests were performed to determine the suitability of the substrates to be used as carbon sources for denitrification. In situ denitrification processes were simulated at smaller scale in the laboratory using anaerobic batch reactors, with biologically treated leachate and seeded Treated leachate from the Sequencing Batch Reactor. Batch tests were conducted at a nitrate concentration level of 500 mg/ℓ. The combination of 8 weeks treated waste with Fresh Commercial Garden Refuse (Cell 1 + CGRraw) and with Commercial Garden Refuse (Cell 1 + CGR10), respectively, provided the most suitable substrates for denitrification as they contained the highest carbon content as well as relatively high carbon to nitrogen ratio (C:N) . Although the 16 weeks treated waste together mixed with Commercial Garden Refuse (Cell 2 + CGR10) had the lowest C:N ratio, this could be due to a lack of homogeneity within the sample. The results of the batch tests confirms that 8 weeks treated waste (Cell 1) and 16 weeks treated waste (Cell 2) substrates were both too stable and contained too little carbon to attain full denitrification. In addition to the inability to attain full denitrification, Cell 2 leached out nitrate of approximately 500 mg/ℓ NO3-N back into the batch. The batch test results showed that the cells substrates augmented with CGRraw and CGR10 achieved positive results as full denitrification was achieved within a maximum of 7 days for Cell 1 and 14 days for Cell 2. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2011.

This thesis is comprised of two phases; the first phase concerns the effect of arsenic on the denitrification process in the presence of naturally-produced volatile fatty acids (VFAs); while the second phase evaluates the arsenic removal efficiency of New Zealand Iron Sand (NZIS) by adsorption. To accomplish the first phase of the study, VFAs were first produced naturally in an acid-phase anaerobic digester by using commercially-available soy flour. Secondly, a denitrifying biomass was cultivated in a sequencing batch reactor (SBR) using domestic wastewater as a feed solution. Finally, a series of biological denitrification batch tests were conducted in the presence of different concentrations of arsenic and nitrate. As mentioned, the VFAs were generated from an anaerobic digester using 40 g/L soy solution as a synthetic feed. The digester was operated at a solids retention time (SRT) and hydraulic retention time (HRT) of 10 days. The pH of the digester was measured to be 4.7 to 4.9 while the mean temperature was 31 ± 4 °C; however, both these parameters were not controlled. In the effluent of the digester, a mean VFA concentration of 5,997 ± 538 mg/L as acetic acid was achieved with acid speciation results of acetic (33 %), propionic (29 %), butyric (21 %), iso-valeric (5%) and n-valeric acid (12 %). The specific VFA production rate was estimated to be 0.028 mg VFA as acetic acid/mg VSS per day. The effluent sCOD was measured to be 14,800 mg/L (27.9 % of the total COD), as compared to 9,450 mg/L (16.8 % of total COD) in the influent of the digester. Thus, the COD solubilization increased by 11.1 % during digestion yielding a specific COD solubilization rate of 0.025 mg sCOD/mg VSS per day. The extent of the digestion process converting the substrate from particulate to soluble form was also evaluated via the specific TOC solubilization rate (0.008 mg TOC/mg VSS per day), and VSS reduction percentage (17.7 ± 1.8 %). A denitrifying biomass was developed successfully in an SBR fed with domestic sewage (100 % denitrification was achieved for the influent concentration of sCOD = 285 ± 45 mg/L and NH₄⁺-N = 32.5 ± 3.5 mg/L). A mean mixed liquor suspended solids (MLSS) of 3,007 ± 724 mg/L and a mean SRT of 20.7 ± 4.4 days were measured during the period of the research. The settleability of the SBR sludge was excellent evidenced by a low sludge volume index (SVI) measured to be between 50-120 mL/g (with a mean value of 87 ± 33 mL/g) resulting in a very low effluent solids concentration (in many cases less than 20 mg/L). Several preliminary tests were conducted to estimate the right dosage of VFAs (digester effluent), nitrates and arsenic to be added and to confirm the occurrence of denitrification in an appropriate time frame of 4-6 h. From these tests, an optimum C/N ratio was observed to be somewhere between 2 to 4, somewhat higher than all the theoretical C/N ratios required for a complete denitrification using the four major VFAs identified in the digester effluent. During the denitrification batch tests, it was also observed that some NO₃⁻- N was removed instantaneously by reacting with As (III) (As₂O₃); while an increase in alkalinity of around 5.60 mg as CaCO₃ produced per mg NO₃⁻- N reduction was also observed. This latter number was very close to the theoretical value of alkalinity production (i.e. 5.41 mg as CaCO₃ per mg NO₃⁻- N). The effect of arsenic on the denitrification process was evaluated by observing the specific denitrification rate in series of denitrification batch tests (with different concentrations of arsenic). Results from the denitrification batch tests showed that there was a clear effect for both As (III) and As (V) on denitrification. In particular, the specific denitrification rate fell from 0.37 to 0.01 g NO₃⁻- N /g VSS per day as the concentration of As (III) increased from 0 to 50 mg/L. In contrast, there was comparatively less effect for As (V); i.e. only a 37 % decrease in the specific denitrification rate (from 0.34 g NO₃⁻- N /g VSS per day to 0.23 g NO₃⁻- N /g VSS per day) when the initial arsenic concentration increased from 0 to a very high level of 2,000 mg/L. The effects of both the As (III) and As (V) forms of inorganic arsenic on the denitrification rate were further quantified by constructing exponential equation models. It was suspected that the effect of As (III) on denitrification was more substantial than the effect of As (V) because of the former’s toxicity to microbes. Finally, the fate of arsenic was tracked by examining bacterial uptake. During the normal denitrification batch tests (i.e. designed for evaluation of the effect of arsenic on denitrification), no significant arsenic removal was observed. However, additional batch tests with a comparatively low concentration of biomass revealed that the denitrifying biomass removed 1.35 µg As (III) /g dry biomass and 2.10 µg As (V) /g dry biomass. In the second phase of this research, a series of arsenic adsorption batch tests as well as a column test were performed to examine the arsenic (As (III) and As (V)) removal efficiency of NZIS from an arsenic-contaminated water. The kinetics and isotherms for adsorption were analysed in addition to studying the effect of pH during the batch tests. Breakthrough characteristics for both As (III) and As (V) were studied to appraise the effectiveness of NZIS treating an arsenic contaminated water. Batch tests were performed with different concentrations of arsenic as well as at different pH conditions. A maximum adsorption of As (III) of approximately 90 % occurred at a pH of 7.5, while the As (V) adsorption reached its maximum value of 97.6 % at a very low pH value of 3. Both Langmuir and Freundlich Models were tested and found to fit with R² values of more than 0.92 in all cases. From the Langmuir adsorption model, the maximum adsorption capacity of NZIS for As (III) was estimated to be 1,250 µg/g, significantly higher (about three times) than for As (V) of 500 µg/g. In column tests, arsenic-contaminated water with total As concentration of 400 µg/L (in either form of As) were treated and a pore volume (PV) of 700 and 300 yielded a total arsenic level less than the WHO guideline value of 10 µg/L for As (III) and As (V) respectively; while, the breakthrough occurred after a throughput of approximately 3,000 PV of As (III) and 2,700 PV of As (V) with an average flow rate of approximately 1.0 mL/min.

<p> Eine Hauptquelle des vom Menschen verursachten klimaschädlichen Distick-stoffoxids (N₂O), das auch Lachgas genannt wird, sind landwirtschaftliche Böden. Im Hinblick auf die ansteigende Weltbevölkerung ist mit einer Erhöhung der landwirtschaftlichen Produktion zu rechnen - mit weitreichenden Auswirkungen auf den Stickstoffkreislauf. Allerdings sind noch immer nicht alle Stickstoffflüsse und Umbauprozesse in Böden bis ins Detail verstanden, im Speziellen die Denitrifikation als einer der Schlüsselprozesse. Bei der Denitrifikation wird Nitrat (NO₃^-) über Nitrit (NO2-) und Stickstoffmonoxid (NO) zu N₂O und schließlich zu Di-Stickstoff (N₂) umgesetzt, wobei N₂O parallel entstehen und verbraucht werden kann. Die Politik befasst sich angesichts des Klimawandels und dessen Folgen mit Maßnahmen zur Reduzierung der Treibhausgase gerade im Agrarbereich. Um die Emissionen von Klimagasen vorhersagen zu können, werden prozessbasierte Modelle verwendet, die mit Hilfe von Feldstudien eingeschätzt und verbessert werden sollen. Weiterhin können beispielsweise Isotopomermessungen dazu beitragen, die N₂O- Prozesse im Boden besser zu verstehen. </p> <p> Diese Arbeit beinhaltet verschiedene Untersuchungsergebnisse zum Thema „N₂O- Emissionen landwirtschaftlicher Böden“ und liefert hilfreiche Informationen, die dazu beitragen, die Wissenslücke bezüglich der N₂O- Prozesse und deren Einflussfaktoren zu füllen. </p> <p> In einer ersten Teilstudie wird der Langzeiteffekt unterschiedlicher Bodenbearbeitung (pflugbasiert vs. pfluglos) einerseits auf die Vorräte und die Verteilung organischen Kohlenstoffs und des Gesamtstickstoffs und andererseits auf die Jahresemission von N₂O und die jährliche Methanaufnahme beschrieben und diskutiert. Dabei sollte insbesondere untersucht werden, wie sich die Bearbeitung auch auf die Variation der Gasflüsse und auf die Faktoren, die die zeitliche und räumliche Variabilität bedingen, auswirkt. </p> <p> Zusätzlich wurden mit dem „Denitrification- Decomposition“-Modell (DNDC) die bei den Feldversuchen erfassten N₂O-Emissionen und Ernteerträge der zwei Bearbeitungsvarianten modelliert. Damit sollte die Eignung des Modells im Hinblick auf die Beschreibung und Vorhersagbarkeit der Emissionen und Erträge der unterschiedlich bewirtschafteten Böden getestet werden. </p> <p> Des Weiteren werden zwei Laborexperimente zur Identifizierung von Produktions- und Reduktionsprozessen des N₂O während der Denitrifikation in Ackerböden mit Hilfe stabiler Isotope präsentiert. Der erste Versuch zielte durch die zeitgleiche Erfassung der N₂O- Produktion und -Reduktion darauf ab herauszufinden, ob die Isotopensignaturen des emittierten N₂O unter der nicht-homogenen NO₃^-- und Denitrifikationsverteilung im Boden geeignet sind, die involvierten Prozesse besser zu beschreiben. </p> <p> Der zweite Versuch sollte neben dem Einfluss der initialen Bodenfeuchte auf die N₂- und N₂O- Flüsse auch dazu dienen festzustellen, inwieweit die Isotopensignaturen des emittierten N₂O und des NO₃^- im Boden die N₂-Flüsse und das Verhältnis von N₂O/N₂ widerspiegeln und ob die Isotopensignaturen des N₂O als Werkzeug zur Untersuchung der Denitrifikation im Boden geeignet sind. </p> <p> Für die Untersuchung des Einflusses der Bodenbearbeitung wurden die Versuchsstandorte Garte Süd und Hohes Feld bei Göttingen ausgewählt. Die lössbasierten Parabraunerden unterliegen seit über 40 Jahren der konventionellen (pflugbasierten) und der reduzierten (pfluglosen) Bodenbearbeitung, mit den jeweiligen Bearbeitungstiefen von 25 bis 28 und 5 bis 8 Zentimetern. Über einen Zeitraum von zwei Jahren wurden die N₂O- und Methan- Flussraten mittels Haubenmethode sowie einige Bodenparameter (Wassergehalt und mineralischer Stickstoffgehalt) wöchentlich gemessen und Wetterdaten (Temperatur und Niederschlag) täglich erfasst. Zusätzlich wurde zu Beginn der Untersuchung eine Bodeninventur durchgeführt. Ernteerträge wurden getrennt für die Flächen, Jahre und Bodenbearbeitungsvarianten bestimmt. </p> <p> Für die Modellierung wurde ein Testmodel, basierend auf der Parametrisierung einer Variante der ersten Teilstudie (Garte Süd, pflugbasiert) generiert, welches die erfassten Daten (N₂O-Emissionen, Erträge, Bodenwasserdynamik) am besten beschrieben hat. Diese Parametrisierung wurde dann an den anderen Varianten als zurückblickende Simulation angewendet. </p> <p> Die beiden Laborversuche fanden in England am Institute of Grassland and Environmental Research, North Wyke, statt. Mit Hilfe eines speziellen Denitrifikations-Inkubationssystems unter Ausschluss des N₂ wurden zwölf mit Ackerboden gefüllte Zylinder eingebaut und nach Über- und Durchströmen mit einem Helium/Sauerstoff Gemisch wurde Glukose (400 kg C ha-1) und Kaliumnitrat (75 kg N ha-1) bei einem wassergefüllten Porenvolumen von 85% über ein mittig angebrachtes zweites Gefäß von oben zugegeben. Nach 7,5 Tagen wurde statt des Helium/Sauerstoff Gemisches reines Helium verwendet, um eine vollständige Denitrifikation zu gewährleisten. Die Gasflüsse (N₂O, N₂ und Kohlenstoffdioxid) und Isotopensignaturen (&delta;¹⁸O-N₂O, &delta;¹⁵N^bulk-N₂O, &delta;¹⁵N^&alpha;, &delta;¹⁵N^&beta; und die ¹⁵N Positionspräferenz) des emittierten N₂O wurden über einen Zeitraum von 13 Tagen erfasst. </p> <p> Bei dem zweiten Laborversuch wurde ein Teil der Bodenproben bei trockenen (20% wassergefülltes Porenvolumen), der andere Teil bei deutlich feuchteren Bedingungen (75% wassergefüllter Porenvolumen) über einen Zeitraum von vier Wochen vorinkubiert. Anschließend wurden alle Proben auf denselben hohen Wassergehalt (85% wassergefülltes Porenvolumen) eingestellt, in die Versuchsanlage eingebaut, unter Helium/Sauerstoff Atmosphäre gesetzt. Nach Zugabe von Glukose (400 kg C ha-1) und Kaliumnitrat (75 kg N ha-1) (90% wassergefülltes Porenvolumen) wurden die Gasflüsse und Isotopensignaturen analog zum ersten Versuch zehn Tage lang untersucht. In diesem Versuch wurde nach sechs Tagen die Sauerstoffzufuhr gestoppt. </p> <p> Die Ergebnisse der ersten Studie ergeben, dass die jährlichen N₂O-Flüsse und Methan-Aufnahmen der untersuchten Ackerböden mehr von den Bodeneigen-schaften, dem Klima und der Bewirtschaftung abhingen als vom Bearbeitungs- system. Winteremissionen machten bis zu 50 Prozent der jährlichen N₂O-Emissionen aus und die Jahresemissionen spiegeln die Unterschiede der Jahresniederschläge wieder. Außerdem hat sich das jahrzehntelange Pflügen auf die Verteilung des organischen Kohlenstoffs im Bodenprofil ausgewirkt, jedoch nicht auf den Gesamtkohlenstoffvorrat der gepflügten und minimal bearbeiteten Flächen. Unterschiede der Gesamtkohlenstoffvorräte zwischen den Flächen lassen sich auf den unterschiedlichen Tongehalt zurückführen. </p> <p> Die standortspezifische Kalibration hat sich als essenzielle Voraussetzung für die Modellierung der N₂O-Flüsse und Ernteerträge herausgestellt. Insgesamt zeigen die Ergebnisse, dass die Kalibration mit experimentellen Daten und verfügbaren Literaturangaben zu annähernder Übereinstimmung zwischen modellierten und gemessenen Erträgen und den jährlichen N₂O- Emissionen geführt hat. Es wurden jedoch große Abweichungen bezüglich der modellierten und gemessenen N₂O-Emissionen im Jahresverlauf festgestellt. Die Pedotransferfunktionen das Denitrifikationsteilmodell des verwendeten DNDC Modells bedürfen daher weiterer Verbesserungen. </p> <p> Die dritte Studie legt dar, dass die N₂O- Isotopologen den zeitlichen Verlauf der beobachteten N₂O- und N₂-Flüsse widerspiegelten und hilfreiche Prozess-informationen lieferten. Die eindeutige Identifizierung der Quellprozesse wurde durch das Auftreten mehrerer Faktoren behindert und konnte abschließend nicht aufgeklärt werden. Dennoch wies der zeitgleiche Anstieg der 15N-Positions-präferenz und der &delta;¹⁸O-N₂O-Signaturen auf die N₂O-Reduktion zum N₂ hin. </p> <p> Der bedeutende Einfluss der Wiederbefeuchtung eines Bodens auf die N₂O-Emissionen belegt die vierte Studie. Der Versuchsansatz zeigt, dass das zeitgleiche Erfassen von N₂- und N₂O-Flüssen und der Isotopensignaturen von NO₃^- und N₂O zusammen mit der Modellierung der Isotopenfraktionierung Einblicke in die räumliche Verteilung von N Spezies und der mikrobiellen Aktivität im Boden erlaubt. </p> <p> Insgesamt bleibt festzuhalten, dass sich kein genereller Einfluss der betrachteten Bodenbearbeitungssysteme auf den Nettoaustausch des N₂O gezeigt hat und dass die Modellierung der N₂O-Gesamtemissionen der zwei Bodenbearbeitungs-systeme mit den gemessenen Werten übereinstimmte. Die Nutzung stabiler Isotope hat das Verständnis der N₂O-Produktions- und -Verbrauchsprozesse verbessert und die initialen Feuchtebedingungen haben die Emissionen und die Isotopensignaturen während der Denitrifikation in einem Ackerboden beeinflusst. </p>

Nitrate (NO3-) is a ubiquitous groundwater contaminant in agricultural and wastewater discharge areas. The prediction of microbial mediated NO3- removal in subsurface environments requires an understanding of the rates at which electron donors are utilized by denitrifying microbes. This study focuses specifically on the following organic carbon compounds as electron donors: glucose, acetate, adenine, cysteine and fulvic acid. Six triplicate series of flow through reactors (FTRs) containing 35 cm3 of natural, organic-poor sediment were supplied for 10 weeks with solutions containing nitrate and the individual carbon compounds, along with a no-carbon added control. The organic carbon compounds were selected to yield a range of different types of organic carbon (sugars, amino acids etc.) as well as a range of Gibbs Free Energy (???G) values when their oxidation is coupled to denitrification. The initial flow rate of the FTRs was 1 ml h-1. Once steady NO3- concentrations were reached in the outflow, the flow rate was increased to 2 ml h-1 and, subsequently, 4 ml h-1. Potential denitrification rates (RD) measured for the different carbon substrates spanned a range of 0 to 114 nmol cm-3 h-1. Fulvic acid did not induce denitrification, while acetate yielded the highest rate. The outflow solutions for FTRs supplied with adenine and cysteine contained ammonia and sulfate, respectively. These results are consistent with the molecular structure of adenine, which contains an amine group, and of cysteine, containing an amine and thiol group. The results show that the addition of C-substrates to the sediment promotes denitrification, and the rate at which it occurs are dependant on which C-substrate is provided. RD results were used to determine if the denitrification rates imposed by the different carbon substrates could be predicted using theoretical approaches such as ???GR or the nominal oxidation state of carbon (NOSC). However, predictions determined by thermodynamics alone were not significantly correlated with the observed trends in denitrification rates.

Dinitrous oxide (N2O) is a potent greenhouse gas some 354 times stronger than carbon dioxide (CO2) in the atmosphere. Recent studies show that lake denitrification contributes to a considerable part of the global N2O emissions. Despite this, lake-N2O emissions are not being accounted for in global greenhouse gas modeling because it has not yet been accurately understood and quantified. The aim of this study was to assess how denitrification varies between and within boreal lakes and how it is controlled by nitrate- (NO3) and carbon (C) availability and temperature. Studies on denitrification were performed using the acetylene inhibition technique on sediments from three lakes in northern Sweden (February to August, 2014). Results showed that denitrification was correlated (linear regression, r2=0.71) with NO3 concentrations in the hypolimnion water at ambient conditions and that additions of NO3 up to a concentration of 50 µg NO3-N L-1 increased denitrification. Temperature increased denitrification in all lakes, at all sites except in one lake in July, when nutrient concentrations were at its lowest. The spatial and temporal variation in denitrification was small at ambient conditions (1-3 µmol N2O m-2 h-1)but the variation in the response to nutrient additions and temperature increase was very high. This was in part attributed to differences in dissolved organic C (DOC). These findings have important implications for future denitrification research and how lake-N2O production is included in greenhouse gas modeling and contributes to our knowledge on how northern boreal lakes may respond to enhanced nutrient loadings and global warming.

Decades of agricultural use of fertilizer and manure has resulted in nitrogen being the most common groundwater contaminant. Of the known processes for nitrogen attenuation, both denitrification and anammox produce a complete transformation of nitrogen species to dinitrogen gas (N2); however, denitrification is typically also associated with the release of N2O and CO2, both greenhouse gases. Anaerobic ammonium oxidation (Anammox), which has been recently discovered to be more prevalent in groundwater environments than previously thought, simultaneously removes NH4+ and nitrate (NO3-), does not require dissolved organic carbon (DOC), and does not produce greenhouse gas by-products. This study evaluates the natural occurrence of anammox in a manure lagoon plume, as well as the feasibility of enhancing anammox activity by mixing NH4+ rich groundwaters and NO3- rich groundwaters together. Fifteen experiments were undertaken with NH4+-N concentrations ranging between 5-100 mg/L, and a NO3--N ranging from 5-88 mg/L. These experiments suggest a nitrogen removal rate (based on NH4 + removal in anaerobic conditions) from anammox generally in the range of 0.1-0.2 mg/L/day. Based on an absence of dissolved oxygen (DO), and concomitant loss of NO3--N with associated 15N-NO3- enrichment (2.1-8.7‰ ) in 11 experiments, it is considered unlikely that nitrification was the cause of the NH4+ loss observed in these experiments. Concurrent 15NNH4+ enrichment of 4.1-11.5‰ was observed in these 11 experiments. Real-time quantitative polymerase chain reaction (qPCR) DNA analyses were used to show the presence of anammox bacteria and to demonstrate temporal population increases during the experiments (up to 16.3% anammox in total bacteria population) in the three experiments analyzed. Although anammoxrelated N removal rates were modest in these trials, such rates could be significant with respect to the multi-year residence times associated with most groundwater flow systems.

Located in the south-west region of Spencer Gulf, South Australia, a multi-million dollar aquaculture industry based on the ranching of southern bluefin tuna (Thunnus maccoyii) contributes significantly to the regional economy. The interaction between aquaculture activities and the environment is of significant interest to industry stakeholders, management authorities and the broader science community. No studies, to the best of my knowledge, have investigated the relationships between the hydrodynamics and biogeochemistry of the system and the ability of the benthic ecosystem to deal with the increased loads of organic material from aquaculture activities. This thesis uses a multi-disciplinary approach combined with modern statistical techniques to explore the linkages between hydrodynamics, sediment geochemistry, sedimentary nutrient cycling and the aquaculture industry. Modelling results have identified that swell entering the mouth of Spencer Gulf from directly south causes the greatest swell heights in the central tuna farming zone. Winds from the north-east through to south-east generate the greatest wind-wave heights in the central tuna farming zone. This is directly related to the available fetch. The energy contained in the locally generated wind waves was the same order of magnitude as that of the dissipated oceanic swells. Yet the incoming swell poses the greatest risk to aquaculture activities as the increased wave length causes swell energy to penetrate to the seafloor. The results of this work suggest that the sediment geochemistry is tightly coupled to both the hydrodynamic regime and the buildup of silt originating from aquaculture activities. In the more exposed regions of the tuna farming zone, periodic resuspension events caused by swell propagating into the area from the Southern Ocean, resuspend fine unconsolidated sediments into the lower 10 m of the water column. This material is then advected through the region by the residual (low-frequency) currents until it settles out in areas of lower energy. This process has created two distinct provinces within the region that can either be classified as depositional or erosional. The combined effect of wave action and tidal currents have generated a heterogeneous distribution of biogeochemical properties within the sediments. Denitrification rates were measured in these heterogeneous sediments using a novel technique based on Bayesian statistics to explicitly account for the spatial variability of the sediment biogeochemistry. The denitrification rates were found to be generally low, largely due to the lack of organic matter entering the sediments. However, adjacent to aquaculture activities, the high organic loads stimulate sedimentary denitrification, with rates reaching values of up to three orders of magnitude greater than the control sites. Denitrification efficiencies were high adjacent to the aquaculture activities, with up to 95% of the dissolved inorganic nitrogen produced from the breakdown of organic matter in the sediments being removed. Variability in the denitrification efficiencies was related to the textural characteristics of the sediments, with high efficiencies in finer sediments. It is proposed that this is due to the lower permeability of these sediments restricting the advective exchange of porewater nutrients.

Thesis (Ph. D.)--University of Canterbury, 2006. / Typescript (photocopy). "December 2006." Includes bibliographical references (leaves 111-127). Also available via the World Wide Web.

Thesis (Ph.D.)--University of Wollongong, 2004. / Typescript. Includes bibliographical references: leaf 178-199.

Thesis (Ph. D.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references (leaves 140-175). Also available via the World Wide Web.