The major land use in New Zealand is pastoral farming of sheep and cattle. In intensively grazed dairy-pasture systems, animals graze on nitrogen (N)-rich legume-based pastures, but do not efficiently utilize the N they ingest. On average only 10.5% of the N in forage-based animal feed is converted into milk and the remainder is excreted in dung and urine. In the pastures, a cow urine patch can typically contain up to 1000 kg N ha-1. Nitrogen input, either in the form of cow urine or fertilizer, often exceeds immediate plant requirements and hence is susceptible to losses as ammonia (NH3) volatilisation and nitrous oxide (N2O) emissions and removal in drainage water through nitrate (NO3-) leaching. This loss of N from grazed pastures causes detrimental environmental impacts in the form of acidification and eutrophication of the soil and water bodies, global warming, destruction of stratospheric ozone, and NO3- toxicity. Various approaches have been attempted to mitigate the economic and environmental impacts of N losses. One such approach is the use of Urease (UIs) and Nitrification (NIs) inhibitors. There have been extensive studies on the value of UIs in arable farming and NIs in grazed pastures. However, only limited work on the impact of UI and NI alone and in combination in influencing the N dynamics, and thus mitigating N gaseous losses from pastures, has been conducted. This thesis examines the impact of UI (Agrotain; N-(n-butyl) thiophosphoric triamide) and NI (Dicyandiamide, commonly known as DCD), when applied alone or in combination to cow urine and urea fertiliser, on N losses through NH3 and N2O emissions and NO3- leaching, and on herbage production under glasshouse conditions and a field-plot study. The degradation rate of DCD, and its effect on nitrification and on N2O emissions from four soils varying in their physical and chemical properties was also examined under laboratory incubations. The results from the field-plot study were then used to predict the effect of DCD on N2O emissions reductions from urine by adapting the process-based NZ-DNDC model. Both NH3 and N2O emissions have common sources in agriculture. Therefore, chambers were adapted to measure their emissions simultaneously using active and passive gas sampling. Active sampling involved continuous air flow and the use of acid (0.05 M H2SO4 and 2% H3BO3) traps for NH3 measurements and passive sampling involved collecting three gas samples over a one-hour period from a static chamber used for N2O emissions. The first glasshouse experiment used UI with urine or urea to assess its effect on NH3 and N2O emissions, changes in soil mineral-N and N uptake by pasture plants. The UI treatments also involved two commercial products, Sustain Yellow (urea coated with Agrotain and elemental S) and Sustain Green (urea coated with Agrotain). The use of UI effectively decreased total NH3 emissions, as well as delaying the time of maximum NH3 emissions from both urea (600 kg N ha-1) and urine (476 kg N ha-1) by 27% and 22%, respectively. The UI-induced decrease in NH3 volatilization ranged from 42-48% when urea was applied @ 100 kg N ha-1. Urease inhibitor was also effective in decreasing N2O emissions significantly from urine and urea applied @ 100 kg N ha-1. The addition of UI increased dry matter yield by 13-19% as compared to the urea-alone treatment. In the second glasshouse study, NI (DCD) was added @ 25 kg ha-1 to urea (@ 25, 50 and 75 kg N ha-1) and urine (@ 144, 290 and 570 kg N ha-1) applied at different rates. Addition of DCD reduced N2O emissions from both urea and urine and NO3- leaching from urine. Dicyandiamide reduced N2O emissions by 34-93% from the added urea and 33-80% from the added urine. However, its use increased the amount of ammonium (NH4+) present in the soil by 3 to 13% both in the urea and urine treatments, and this NH4+ was susceptible to leaching and volatilisation losses. The addition of DCD, however, resulted in a 60-65% reduction in NO3- leaching from urine applied to pasture soil cores. It also caused a significant reduction in NO3- -induced cation leaching. Leaching of K+, Mg+2 and Ca+2 ions was reduced by 36-42%, 33-50% and 72%, respectively, with DCD applied to cattle urine (290 and 570 kg N ha-1). The combined use of UI and NI was more effective in controlling N gaseous losses than using them individually. The combination of UI and NI retarded NH3 emissions by 70% in the urea treatment and by 4% in the urine treatment (field-plot study). It also considerably reduced N2O emissions (50-51%) following the application of urea and urine (field-plot study) to pasture soil. With the combined inhibitors, there was a 14 and 38% increase in herbage yield from added urea and urine (field-plot study), respectively. A laboratory incubation experiment was undertaken to study the effect of soil types and the rate of DCD application on the degradation kinetics of DCD. The rate of degradation of DCD varied among the four soils studied. The degradation was slowest (half-life period of 6 to 11 days) in an allophanic soil with a high concentration of organic matter. The effectiveness of DCD in inhibiting nitrification also varied depending on the nature and amount of soil organic matter and clay content. The maximum inhibition was observed in a soil with low organic matter and high clay content. Finally, 'NZ-DNDC', a process-based model, was adapted and used to simulate the effect of DCD on emissions reduction using DCD inhibition values that vary according to different soil types. This model effectively simulated the effect of DCD on N2O emissions reductions in Tokomaru silt loam following urine application. However, more field data are required from a range of pasture soils with contrasting amount of soil organic matter and clay content under differing climatic conditions to further test this model modification to predict emission-reductions with DCD application in different soil types.

The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.

Sulphur is an important nutrient to plants, and reports of its deficiency have been increasing worldwide. Sulphur starvation causes losses in both yield and quality, and it reduces nitrogen use efficiency of plants. As the timing for fertilisation can be decisive for avoiding deleterious effects, improvements in the description of the sulphur balance in fields are a valuable contribution for assisting fertiliser management. Sulphate is the most important inorganic form of sulphur in soils. Being the mobile form, sulphate is readily available for plants, and also prone to be leached. Therefore the description of the movement of sulphate is the key component of the sulphur balance. Leaching of sulphate from the soil can be significantly delayed by its adsorption onto the soil particles. Soil type and pH are the main factors defining the sulphate adsorption capacity; although the presence of other ions in the soil solution can have a considerable effect. It has been reported that in some soils, typically volcanic and tropical soils with variable-charge characteristics, the co-presence of sulphate and calcium can substantially enhance their retention via ion-pair adsorption (IPA). To determine the influence of cations on the movement of sulphate, series of batch and miscible displacement experiments were conducted using two New Zealand soils, of contrasting ion adsorption capacities: the Taupo sandy and Egmont loam soils. These experiments demonstrated the occurrence of cooperative adsorption of sulphate and calcium in the Egmont soil, but not in the Taupo soil. Batch experiments were conducted to examine the IPA adsorption process in the Egmont soil in more detail. Based on the analyses of the results from these two series of experiments, plus the review of published data, three different mathematical approaches for evaluating the amount of solute adsorbed as ion-pairs are proposed. A computer program was built for solving an adsorption model using these three approaches, and was used to compare the model's predictions and the observed adsorption data. An extension of this program, coupling the adsorption model with a solute transport description, was used to simulate the movement of sulphate and calcium. Comparisons between the data from the miscible displacements and the results from this model are used to demonstrate the applicability of the proposed IPA description for modelling the transport of these ions in the soil. Finally, results from a pot trial with Egmont soil are used to examine the relevance of IPA for the movement of sulphate under non-equilibrium conditions, and with active plant growth. Although the results from this experiment regarding IPA were statistically non-significant, some insights could be obtained and are discussed. More studies involving IPA under non-equilibrium experiments are needed for a better understanding of the relevance of IPA in field conditions.

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

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 3 uppsatser.

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

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 4 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 5 uppsatser.

Made available in DSpace on 2015-04-17T14:49:40Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5158735 bytes, checksum: d64b50bf830c8bd62e17003f74b24b43 (MD5) Previous issue date: 2014-01-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study aimed to evaluate the profile and stability of amino acids in meals and feeds used in shrimp farming. The study was divided into three experiments. In the experiment I the percent composition and profile of amino acids in fish meal and soya meal feeds with protein levels of 35 and 40% used in shrimp farming were evaluated. Comparing the results of amino acid profile of the feeds used in this study with those determined by chemical score, it can be noted that feeds A and B were not satisfactory in the content of essential amino acids, except lysine, which showed chemical score (CS) higher than the standard. The fish meal and soya meal used in the formulation of commercial feed (RA) had amino acid profile superior to those found in meals used for obtaining commercial feed (RB). In experiment II the aim was to evaluate the stability of amino acids in commercial feeds with different protein contents subject to leaching. The feed samples were exposed to the leaching process during time period of 04, 08 and 12 hours. Analyses of degradation of amino acids were performed using an elution gradient in HPLC system. In all feeds evaluated it was found that lysine and histidine are essential amino acids which suffered less degradation processes. It is important to mention that arginine is considered an important amino acid for growth of shrimp, and that both diets with 35% protein (RB35 and RA35) had losses of 79 and 89% respectively. The results obtained in this study indicate that the leaching process significantly reduces the content of amino acids in the feeds. The physical structure of the feed does not prevent the degradation process of amino acids in the leaching process. Experiment III was to evaluate the stability of amino acids in meals and commercial feeds with different protein levels subjected to hightemperature storage. The samples were exposed to temperature of 50 􀀀 C and evaluated every 5 days for 30 days. Analyses of degradation of amino acids were performed using an elution gradient in HPLC system. In all evaluated meals it was observed that valine and arginine suffered greater losses of amino acids during the experiment and histidine and alanine suffered less degradation processes. It was observed difference in the content of all amino acids studied after the exposure of feeds to the temperature of 50 º C, with reduction of the amino acid content of the feeds. The results obtained in this study indicate that meals and feeds exposed to high temperatures had their amino acid content significantly reduced. / O presente trabalho objetivou avaliar o perfil e estabilidade de aminoácidos em farinhas e em rações utilizadas na carcinicultura. O trabalho foi subdividido em três experimentos. No experimento I foi avaliada a composição centesimal e o perfil de aminoácidos em farinha de peixe, em farinha de soja e em rações com teores proteicos de 35% e 40% utilizadas na carcinicultura. Comparando-se os resultados de perfil de aminoácidos das rações utilizadas na presente pesquisa com os determinados pelo escore químico (EQ), nota-se que as rações A e B não se mostraram satisfatórias quanto ao teor de aminoácidos essenciais, com exceção apenas da lisina que mostrou EQ superior ao padrão. As farinhas de peixe e soja utilizadas na formulação da ração comercial (RA) apresentaram perfil de aminoácidos de qualidade superior aos encontrados nas farinhas utilizadas para obtenção da ração comercial (RB). No experimento II, o objetivo foi avaliar a estabilidade de aminoácidos em rações comerciais com diferentes teores proteicos, submetidas à lixiviação. As amostras de ração foram expostas ao processo lixiviatório durante período de tempo de 04, 08 e 12 horas. As análises de degradação de aminoácidos foram realizadas utilizando-se um sistema de HPLC, em modo de gradiente de eluição. Destacadamente, em todas as rações avaliadas, observou-se que a lisina e a histidina, foram os aminoácidos essenciais que sofreram menor processo degradativo. É importante ressaltar que a arginina é considerada um aminoácido importante para o crescimento de camarões, e que, em ambas as rações com 35% de proteína (RA35 e RB35) tiveram perdas de 79% e 89%, respectivamente. Os resultados obtidos no presente estudo indicam que o processo de lixiviação diminui consideravelmete o conteúdo de aminoácidos das rações. No processo de lixiviação a estrutura física da ração não impede o processo de degradação dos aminoácidos. O experimento III teve como objetivo avaliar a estabilidade de aminoácidos em farinhas e em rações comerciais com diferentes teores proteicos, submetidas a temperaturas elevadas de armazenamento. As amostras foram expostas à temperatura de 50􀀀C, e avaliadas a cada cinco dias durante trinta dias. As análises de degradação de aminoácidos foram realizadas utilizando-se um sistema de HPLC, em modo de gradiente de eluição. Em todas as farinhas avaliadas observou-se que valina e arginina, foram os aminoácidos que sofreram maior perda durante o período do experimento, enquanto que histidina e alanina sofreram menor processo degradativo. Observou-se diferença significativa no conteúdo de todos os aminoácidos estudados depois da exposição das dietas à temperatura de 50ºC, com redução do conteúdo de aminoácidos das rações. Os resultados obtidos no presente estudo indicam que farinhas e rações expostas a temperaturas elevadas diminuem consideravelmente o conteúdo de aminoácidos.

68 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-05T17:50:29Z No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-06T14:53:28Z (GMT) No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) / Made available in DSpace on 2013-06-06T14:53:28Z (GMT). No. of bitstreams: 1 Dissertacao - Wdson Costa Santos.PDF: 1066509 bytes, checksum: 0409b0432c52d5bd01e90ebcf214766a (MD5) Previous issue date: 2012 / CAPES / No presente trabalho foram investigados os efeitos sobre a recuperação de elementos causados por modificações em processos prévios a amostragem laboratorial e lixiviação dos analitos das polpas de abóbora e batata. Inicialmente, foi avaliado o efeito da inversão na ordem de operações do procedimento de tratamento preliminar das amostras brutas das polpas sobre as recuperações dos elementos. As amostras das polpas foram secas para posterior trituração (PA) ou as amostras foram trituradas antes de serem submetidas à secagem (PB). Os resultados obtidos empregando ambos os procedimentos foram comparados para 95% de confiança e eles mostraram diferenças significativas para alguns elementos determinados na amostra de batata. As concentrações de K, P e Mn, na polpa de batata, determinadas aplicando o primeiro procedimento de pré-tratamento (PA) foram 13,6±0,4 mg K g-1, 1,95±0,04 mg P g-1 e 5,7±0,2 μg Mn g-1, enquanto 12,2±0,3 mg K g-1, 1,62±0,03 mg P g-1 e 2,6±0,2 μg Mn g-1 foram determinadas quando a mesma amostra bruta foi submetida ao pré-tratamento PB para a obtenção da amostra teste. Em contraposição, no caso da amostra bruta de polpa de abóbora, os resultados para os elementos (K, P, Mn, Mg) foram maiores quando a polpa foi previamente esmagada antes da secagem. Em um estudo independente, a eficiência da extração de metais de amostras de polpas trituradas de abóbora ou batata para soluções diluídas de HNO3 foi avaliada variando o modo (agitação mecânica ou irradiação ultrassônica) e o período (de 10 a 30 min) de agitação, bem como a concentração da solução de HNO3 na solução de lixiviação (de 0,7 a 2,1 mol L-1). Os resultados foram também comparados com aqueles obtidos nas digestões assistidas por micro-ondas das amostras teste v em meio nítrico-peróxido. Foi observado que para ambas as amostras teste (abóbora e batata) e independentemente do modo ou período de agitação que a eficiência de extração de Ca, K, Mg e Mn foi diminuída para solução para 2,1 mol L-1 HNO3. Uma melhora no nível de recuperação de P foi obtida quando a lixiviação foi realizada com soluções diluídas de HNO3 (0,7 e 1,4 mol L-1) e sob irradiação ultrassônica. Esse efeito foi relacionado à presença de átomos de fósforo em moléculas estruturais de células de abóbora e batata, bem como à cominuição (ou fragmentação) das partículas submetidas a um campo ultrassônico intenso. Contudo, efeitos indesejados foram também observados para alguns elementos quando submetidos às lixiviações assistidas com ultrassom, como exemplificado pelo teor de cálcio determinado após a lixiviação da amostra teste de batata ter atingido valor 2,3 vezes maior que o valor obtido após a mineralização da amostra em micro-ondas. Muitos desses efeitos foram relacionados à erosão da superfície interna frascos irradiados. / Salvador