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The aim of this research project was to use 15N nuclear magnetic resonance (NMR) spectroscopy to better understand nitrogen (N) cycling processes in forest plantations. In particular, the studies were designed to link to the effects of forest management practices and environmental conditions. 15N NMR cross polarization/magic angle spinning (CPMAS) and dipolar dephasing (DD)-CPMAS experiments of some simple N-containing compounds found widely in nature were first undertaken. This was done in order to understand how different sample conditions, such as the presence of moisture, sample mixing and dilution, affected the intensity and the observability of the NMR peaks corresponding to N containing functional groups. Our results exhibited changes in NMR signal intensities and various time constants calculated. In the case of variable contact time experiments, use of an equation that predicts both a bi-exponential rise and decay was found to fit the data obtained more accurately. The optimised parameters for 15N NMR CPMAS were then used along with other analytical techniques such as ion chromatography, total C and N and elemental analyses to study plant nutrient uptake, plant decomposition and the effect of forest ecosystem disturbances, in this case an insect infestation. These analytical data were also correlated with the changes in the 13C NMR spectra in order to gain a more comprehensive understanding of the chemical transformations in the forest ecosystem. / Doctor of Philosophy (PhD)

Winter wheat is commonly grown in rotation with leguminous and non-leguminous crops in the Willamette Valley. For agronomic, economic, and environmental reasons it is important to understand the influence of previous crops on availability of N and other nutrients. Objectives of this study were: (1) to evaluate the effects of long-term rotations on winter wheat response to N fertilizer, and (2) to evaluate the use of Plant Root Simulator���(PRS) probes for measuring soil N mineralization and N availability to winter wheat. Field experiments were conducted over three growing seasons in plots of `Stephens' soft white winter wheat at Hyslop farm. Plots receiving 0, 50, 100, 150 and 200 kg N ha����� at Feekes GS 4 were sampled to determine above ground N uptake, grain yield, and grain protein. In spring 1998, PRS probes were placed in 0 kg N ha����� plots and removed at one-week or two-week intervals. In autumn 1998, probes were placed in unfertilized plots and removed at 1-week, 4-week, and 8-week intervals. Probes measured the availability of NH������-N, NO������-N, K���, Ca�����, Mg�����, and P0��������-P. Grain yield and N uptake were greater for wheat following clover as compared to following oats. Three-year average fertilizer equivalent values calculated from N uptake and grain yield data were 44.5 kg N h����� and 49.0 kg N h�����, respectively. The similarity of these independent measurements suggest that differences in N availability were the primary reason for the rotation effect. PRS probes also detected rotational differences in N availability. Average N recovered by probes sampled at 1-week intervals indicated that there was 63% as much NO������-N available to wheat following oat as compared to clover. Wheat recovered 64% as much N following oats as compared to clover. This suggests that PRS probes are an effective method for predicting relative amounts of plant available N. PRS probes also detected rotational differences in plant available potassium. Agronomic responses are useful for assessing the availability of nutrients that are limiting plant growth. PRS probes, on the other hand, are effective for assessing the availability of both limiting and non-limiting nutrients. / Graduation date: 2000

In Scotland, environmental regulation restricts commercial cod culture to the equivalent of 66 % of that granted for commercial Atlantic salmon (Salmo salar L.) farms. This calculation is based on estimations of nitrogen discharge from the difference in protein content between salmon and cod diets, with the higher levels of protein in cod diets suggesting a higher nitrogen discharge compared to that observed for salmon diets. In turn, this could potentially result in increased nitrogen enrichment of a marine ecosystem. The aims of this study (quantifying and modeling of nitrogenous wastes associated with the commercial culture of Atlantic cod (Gadus morhua L.) were achieved through a series of tank and cage investigations, each of which studied juvenile and adult Atlantic cod. The study provided data with respect to nitrogen excretion from juvenile and adult fish in both systems. This would allow the development of dispersion models and the calculation of nitrogen budgets for commercial cod culture, thus providing environmental regulators data independent of salmon models to create regulations that would be specifically applied to cod farming. The tank - based studies investigated three diet formulations produced by EWOS® Innovation in Norway, as a 4 mm pellet (juvenile study) and as a 7 mm pellet (adult study). The three iso -energetic diets varied primarily in protein content (40%, 50% and 60%). Two tank studies, one on juvenile and one on adult cod, investigated growth, condition and tissue composition, and the production of dissolved nitrogenous wastes over a 5 and 7 month period respectively. At the beginning of the acclimation period prior to the adult tank study commencing, the fish had a mean weight of approximately 1275 g. The difference in the final weight promoted by each diet was not significant (with an approximate final weight of 2400g), suggesting that a low protein diet (40 % protein) promoted similar growth to a high protein diet (60 % protein). Other growth and condition parameters were also similar for all diets with the condition improving over the course of the study. As the fish completed spawning immediately prior to the commencement of the study, an increase in condition was not observed until approximately day 90 of the 210-day investigation. Over the course of the 5-month juvenile study, growth was approximately 224g for the 40% protein diet and approximately 275g for the 50% protein and 60% protein diets. This suggests that a higher protein diet is required for optimal growth of juvenile cod and that 50 % and 60% protein diets promote similar growth and condition, potentially reducing the protein requirement of juvenile diets. In the juvenile investigation, condition increased over the full range of the study. In both tank studies, nitrogen digestion was directly related to protein (and associated nitrogen) content of the diets in the juvenile study expressed as a percentage of the nitrogen content of the diet as 59.19% (40% protein), 56.90% (50% protein) and 52.23% (60 % protein) suggesting that nitrogen digestion is more efficient at lower protein content in the diet. When expressed as a percentage of the nitrogen content of the diet, nitrogen digestion observed in the adult study was 60.55%, (40% protein) 60.92% (50% protein) and 60.60% (60% protein) respectively, suggesting protein digestion is similar regardless of protein content in adult cod. In the adult tank study, under a manual feeding regime, a post-prandial-peak is observed at 105 min. following the cessation of feeding. Thereafter, ammonia levels drop over the course of the sampling period. Following the afternoon meal commencing at 420 min., ammonia levels rise at least until the final samples are collected at 450 min. Under an automated regime, a lesser post-prandial-peak is observed but the ammonia concentration is lower over the sampling period compared to the respective profile under a manual regime. The ammonia profile produced throughout the juvenile tank study follows a very similar trend to that observed in the adult study under the manual feeding regime. Two cage - based investigations took place at the No Catch® Ltd. commercial organic cod farm in Vidlin Voe on the east coast of Shetland. Both studies investigated growth, condition and tissue composition, as well as the production of dissolved nitrogenous and particulate wastes associated with the culture of juvenile and adult Atlantic cod in cage systems. Sampling for the adult study occurred over three days during three sampling trips (September 2005, November 2005 and February 2006). Sampling for the juvenile study took place over three days on a single trip to Vidlin in late April 2006. The diets used at No Catch® Ltd. were produced by Biomar® in Grangemouth. A relationship between feeding and ammonia concentration is less evident in the cage studies than in the tank studies, and similarly, the relationship between feeding and ammonia concentration is less evident in juvenile fish than in adult fish. As ammonia values were converted to (µg/L/tonne biomass), the ammonia concentration recorded is largely dependent upon the biomass of the sampled cages at both the nursery site and production site. Deposition rates of organic carbon and nitrogen around the production and nursery cage sites in Vidlin Voe are related to the position of the sediment trap relative to its location and proximity of the trap to the specific cage site. Weather condition also had an impact on deposition rates with calmer weather producing lesser deposition rates. Around the production site, deposition rates of organic carbon and nitrogen are greatest in the direction of the prevailing current. Deposition rates decrease with an increasing distance from the cages. Although sediment trap results were inconsistent, a similar trend is observed for each of the three sampling trips, although actual deposition values were different. Differences between the deposition rates at the highly dynamic production site and the low energy nursery site indicated that sedimentation of waste from cod culture is highly dependent on water currents. Models of particulate waste deposition associated with the production cage site in Vidlin Voe were produced using the spreadsheet - based Cage Aquaculture Particulate Output and Transport (CAPOT) model, developed at the Institute of Aquaculture. The models were parameterised using the data collected and tested against an established regulatory model, DEPOMOD. The similarity in results illustrated the robustness of the highly flexible spreadsheet waste model for cod culture.

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Environmental regulation of nitrogen cycling processes, denitrification and nitrification, was studied in sediment of Hamilton Harbour, with particular emphasis on the role of CH$ sb4$ metabolism (production and consumption). Through extensive sediment sampling and numerical analysis, it was found that particulate carbon was the best predictor of potential for anaerobic production of CH$ sb4$ and CO$ sb2$. The only predictor of denitrification capacity was anaerobic CO$ sb2$ production, indicating that beside NO$ sb3 sp-$ and O$ sb2$, a biotic factor involved in carbon metabolism may be important in the control of this activity. / Suppression of aerobic N$ sb2$O production in sediment slurries by C$ rm sb2H sb2$ and correlation with NO$ sb3$-production indicated that it was dependent on chemolithotrophic nitrification. Although CH$ sb4$ (1 to 24 $ mu$M) stimulated production of NO$ sb3 sp-$ and N$ sb2$O, we found that CH$ sb4$ at 84 $ mu$M or greater suppressed nitrification. Following extensive studies of pore water chemistry, potential microbial activities, and counts of nitrifiers and methanotrophs, we found that CH$ sb4$ oxidation (i) is more likely to suppress nitrification by competition for O$ sb2$ and NH$ sb4 sp+$ between methanotrophs and nitrifiers, and (ii) may be more important than nitrification as a sink of hypolimnetic O$ sb2$ in Hamilton Harbour. / Amongst a number of inhibitors, allylsulfide was found to be a differential inhibitor with much less effect on CH$ sb4$ oxidation in sediment slurries or in axenic cultures of Methylosinus trichosporium OB3b than on nitrification in sediment slurries.

A mass balance approach was used in an attempt to quantify nutrient flux to the nearshore at the West Coast, Barbados, W.I. Total nitrogen and total phosphorus levels of the groundwater at inland pumping stations and above beach margins, as well as in the water of the nearshore zone and approximately 2 km offshore, were obtained. Nearshore groundwater seepage rates and salinity data were also taken. This study attempted to use this raw data to estimate flushing rates, nutrient loading rates, and nutrient loss rates, to ultimately create a picture of the fate of nutrients as they travel in groundwater into the nearshore zone. Annual loading for the entire West Coast was calculated at 1.46 x 105 kg NO3---N for nitrogen and 1.19 x 103 kg PO4 3---P for phosphorus. Mean nutrient levels in groundwater above the beach margin were estimated at 969.83 muM for nitrogen and 3.63 muM for phosphorus. For nitrogen and phosphorus respectively, these levels were twice and three times higher than at the pumping stations farther inland; and there was also a fourfold and fivefold drop in nitrogen and phosphorus, respectively, in the nearshore zone relative to this groundwater above the beach margin. This indicated that the dense coastal population at the West Coast was adding significant amounts of nutrient to groundwater after it had left the inland pumping stations. There were no patterns of gradation in nutrient concentrations detected within the immediate nearshore, making completion of an accurate mass balance impossible, though indicating that there was significant advection of submarine groundwater offshore, beyond the study zone. This may contribute to the poor health of West Coast reefs, where sewage and fertiliser leaching and runoff are suspected as the primary sources for nutrient input to submarine groundwater to the south and northern parts of the West Coast, respectively.

Marine nitrogen (N) is an essential nutrient for all oceanic organisms. The cycling of N between biologically available and unavailable forms occurs through numerous reactions. Because of the vast number of reactions and chemical species involved, the N cycle is still not well understood. This dissertation focuses on understanding some of the reactions involved in the cycling of marine N, as well as improving techniques used to measure dissolved N2 gas. The largest loss term for global marine N is a reaction called denitrification. In this work, denitrification was measured in the sandy sediments of the Georgia continental shelf, an area where this reaction was thought to be unlikely because of the physical properties of the sediments. Nitrogen fixation, which is a reaction that produces biologically available N, was detected in Georgia estuarine sediments. N fixation was measured concurrently with denitrification in these sediments, resulting in a much smaller net loss of marine N than previously thought. Lastly, membrane inlet mass spectrometry (MIMS) is a technique that measures dissolved N2, the end product of denitrification and a reactant in N fixation reactions. This study suggests that N2 measurements by MIMS are influenced by O2 concentrations due to pressure differences inside of the ion source of the mass spectrometer. These findings seek to improve denitrification measurements using MIMS on samples with varying O2 concentrations. In conclusion, this dissertation suggests that the marine N cycle is more dynamic than has been suggested, due to the recognition of input and loss reactions in a wider range of marine and estuarine environments. However, improvements in the understanding of MIMS will help with direct measurements with reactions involved in the global marine N cycle.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 5 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 4 uppsatser.