Agriculture has been the backbone of the economy in Nigeria providing employment and source of livelihood for the increasing population and accounting for over half of the GDP of the Nigeria economy at independence in 1960. However, the role it plays in the regional and economic development of the country has diminished over the years due to the dominant role of the crude oil sector in the economy. With the increasing food demand in Nigeria, the country has available input natural resources and potential for increasing the volume of crop production towards meeting the food and nutritional requirement of the rapidly increasing population and guarantee food security in the country. The study was undertaken to analyse the effect of different factors and policies on the changes in trend of crop production and investigate the possible effect of water resources development on increased volume of agricultural crop production in Nigeria. The study revealed that there are opportunities for water resources development in the country through irrigation to supplement the water requirements and needs of farmers for agricultural production activities in many areas in the semi-arid and arid regions. Available data shows that there are available land and water resources that could be developed to support the production of food and agricultural development with opportunity for increased productivity. However, while the water resources are unevenly distributed in the country, there is need for the efficient use and management of the available water resources and increasing the productive use especially in the northern region of the country where there is increasing incidence of drought and competing need for water among the different sectors of the economy. The study also made possible recommendations for policy formulation to address the current problems facing the agricultural sector in conjunction with the requirement for the development of the water resources.

Orientadores: Marcos Nogueira Eberlin, Eugenio Vaz dos Santos Neto / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T16:54:54Z (GMT). No. of bitstreams: 1 Pereira_RosanaCardosoLopes_D.pdf: 5832219 bytes, checksum: 88820b58f8b6360b78a6aa2f16ceb943 (MD5) Previous issue date: 2012 / Resumo: Este trabalho consistiu na aplicação de tecnologia que se encontra hoje na vanguarda do conhecimento: a Petroleômica via ESI FT-ICR MS, com o objetivo de caracterizar as mais diversas classes de compostos polares ácidos presentes em amostras representativas de óleos de bacias brasileiras. O propósito ambicioso foi o de focalizar aspectos relacionados à toda cadeia de valor da indústria do petróleo, desde a geração do óleo até o seu refino, visando contribuir para novos estudos de interesse às atividades de upstream e downstream da PETROBRAS e, principalmente, fomentar a integração dos conhecimentos das diferentes áreas, o que contribuirá para ganhos de produtividade da empresa. A técnica ESI FT-ICR-MS mostrou-se uma técnica rápida e adequada para acompanhar as alterações verificadas na composição de amostras de petróleo, fornecendo subsídios a partir de uma caracterização única, para estudos diversos, abrangendo toda a cadeia de valor da indústria do petróleo. As alterações composicionais de óleos e extratos obtidos em experimentos de maturação artificial por hidropirólise de matéria orgânica dos tipos I e III foram avaliadas, evidenciando o potencial da técnica para utilização em estudos cinéticos. O estudo de biodegradação utilizando trinta amostras de óleos da Bacia Potiguar evidenciou que a técnica é sensível as variações de composição dos compostos polares que ocorrem em função do processo de biodegradação, e as amostras puderam ser agrupadas de acordo com o grau de biodegradação através da utilização de ferramentas quimiométricas (PCA). A partir dos dados de caracterização obtidos por ESI FT-ICR MS, foi possível agregar informações úteis para o entendimento de comportamentos diferenciados frente à tendência de formação de emulsão/gel durante a produção e frente à corrosão durante o refino / Abstract: This work focuses on the application of a technology that is cutting edge: Petroleomics by ESI FT-ICR MS with the goal of characterizing the large variety of acidic polar compound classes present in representative petroleum samples from Brazilian basins. The ambitious proposal was to focus on aspects related to the whole petroleum industry chain, since crude oil generation up to its processing in refinery units, to contribute to state-of-the-art studies of interest to upstream and downstream activities in PETROBRAS and mostly to encourage the knowledge integration, i.e. to form or blend the information into a whole, to UNITE, accessing high levels of productivity. The ESI FT-ICR MS technique exhibits characteristics like fast response, resolution, selectivity and sensibility, which make it suitable to monitor the changes in composition of petroleum samples and because of its unique and comprehensive characterization attained, to help different studies in the whole petroleum industry chain. The compositional alteration observed in extracts and oils during artificial maturation experiments by hydrouspyrolysis of organic matter types I and III were evaluated showing the potential of the technique to kinetic studies. Biodegradation studies were performed on 30 petroleum samples from Potiguar Basin and the results showed that the technique is sensitive to the variations on the composition of the polar compounds that occur as a result of the biodegradation process, and additionally, that the samples can be grouped according to their biodegradation level by the use of chimiometric tools (PCA). Also from the characterization data from ESI FT-ICR MS analysis it was shown that very useful information can be provided to better understand the differences in the rheological and corrosion behaviors of petroleum samples / Doutorado / Quimica Analitica / Doutora em Ciências

The influence of crude oil-contaminated and remediated sites on agrifood production is not clearly understood. To address this knowledge gap, the research was divided into two stages involving: (1) assessment of the efficiency of two bioremediation strategies to support hydrocarbons degradation as well as agrifood production with the initial analysis of the experimental materials, and (2) evaluation of the effect of different crude oil remediation intervention values (CRIV) on selected vegetables (Brassica juncea, Brassica oleracea, Lactuca sativa and two different cultivars of Solanum lycopersicum). Results from the first stage showed that the crude oil used had a pristane/phytane ratio of 0.98 (within the 0.8 – 3.0 range of most crude oils), higher concentrations of C10 – C14, C15 – C20 and C21 – C27 alkanes than the C28 – C36 alkanes including higher concentrations of two of the US EPA priority pollutant polycyclic aromatic hydrocarbons (PAHs) - phenanthrene and anthracene. Four treatments were prepared in which weekly tillage enhanced the degradation of C15 – C20 and C21 - C27 alkanes in the Remediation by Enhanced Natural Attenuation (RENA) treatment. The two bioremediation strategies (RENA and bioaugmentation) enhanced PAHs degradation compared with the remediation-study control treatment while only RENA application among the two approaches supported the growth of B. juncea. Although there was no statistical significant difference (p > 0.05) between the major dietary mineral contents of samples from the various treatments compared with the control treatment samples, RENA application affected the Cr, Zn and Pb contents. Meanwhile, the Ca/P (> 1.0) and Na/K (< 0.60) ratios of all the harvested samples imply that they provide a good source of these minerals for bone formation and would not contribute to high blood pressure. The crude oil used also deterred the attack of juvenile caterpillars of cabbage white butterfly. Findings from the second stage revealed that the yield of the green leafy vegetables including one of the selected tomato cultivars (Micro-Tom), was in most cases impaired at CRIV ≥ 3,000 mg/kg total petroleum hydrocarbon (TPH). Compared with the control treatment samples’ composition, crude oil stress at 10,000 mg/kg TPH enhanced the concentration of K, Mn and crude protein of B. oleracea and L. sativa as well as the sucrose, total sugars, total phenolics and total flavonoids contents of the latter vegetable. Sucrose was also only detected in M82 tomato cultivar samples from the crude oil-containing treatments. The Cd content of B. oleracea, Pb contents of: L. sativa and M82 tomato harvested samples were all below the FAO/WHO Codex Alimentarius Commission 2015 recommended maximum levels. However, tartaric acid was only detected in B. oleracea and L. sativa samples from the 10,000 mg/kg TPH treatment as well as in M82 tomato cultivar samples from the treatment involving CRIV of 5,000 mg/kg TPH. Generally, the yield of these crops in response to crude oil contamination varied in which B. juncea had the least tolerance to crude oil stress among the green leafy vegetables tested. Most of the quality parameters in the two tomato cultivars were not affected by CRIV between 750 - 5,000 mg/kg TPH with p-xylene having the greatest toxic potential among the VOCs emitted from the 5,000 mg/kg TPH treatment. The research findings, under the experimental conditions, indicated the effectiveness of RENA for the degradation of low molecular weight PAHs and its agricultural benefits. They also suggest that crude oil-contaminated sites at ≤ 3,000 mg/kg TPH present a similar growing environment to a clean site for agrifood production and the possibility that crude oil stress at 10,000 mg/kg TPH could enhance crop quality. Nonetheless, the contribution of bio- accumulated PAHs in these crops to the food chain demands further investigation.

Le 7 août 2009, un pipeline transportant du pétrole brut s'est rompu, provoquant le déversement de 5100 m3 de brut sur 5 hectares de la Réserve Naturelle des Coussouls de Crau. Le pétrole a atteint l'aquifère et a formé un LNAPL qui alimente un panache de polluants dissous, dont le benzène, composé cible car toxique. Cette étude vise à montrer que la biodégradation du pétrole (biostimulation ou atténuation naturelle), en particulier des composés dissous, est une mesure efficace de gestion à long terme des risques pour la ressource en eau. Une première étude en microcosmes a montré la biodégradation, même dans les conditions les plus réductrices, des composés cibles dont le benzène. Cette étude a confirmé que la disponibilité en oxydant est un facteur limitant et que le phosphate est un levier puissant pour stimuler la croissance bactérienne. Une seconde étude sur site a prouvé la faisabilité de la biostimulation par injection de nitrate et de phosphate dans la nappe et son efficacité pour l'abattement des concentrations en polluants dissous. L'utilisation du radon comme traceur pour estimer la saturation en pétrole dans l'aquifère a été évaluée dans une troisième étude. La facilité de mise en oeuvre de la méthode ainsi que les résultats offrent des perspectives intéressantes pour l'optimisation des systèmes de pompage-écrémage sur des sites ayant un NAPL. Une dernière étude portant sur la mise en place des processus d'oxydoréduction et de dégradation sur site a montré une évolution rapide des conditions après l'accident, traduisant un environnement favorable à l'atténuation naturelle. La dégradation in situ du benzène a été mise en évidence via des mesures isotopiques. / On August 7, 2009 a pipeline transporting crude oil broke in the heart of the Nature Reserve of Coussouls de Crau, and 5,100 m3 of oil were spilled over 5 hectares. Oil infiltrated through the subsurface and reached the most important regional aquifer where it formed a LNAPL that created a plume of dissolved compounds. Among these compounds, benzene is of particular concern because of its toxicity and high solubility. This thesis aims at showing that biodegradation of crude oil, especially of dissolved compounds, is a good option for long-term management of risks for the water resource. A first study in microcosms demonstrated biodegradation of targeted compounds, including benzene, even under the most reducing conditions. This study also revealed that the availability of electrons acceptors was a limiting factor and that phosphate was a powerful lever to stimulate bacterial growth. An on-site study proved the feasibility of biostimulation by nitrate and phosphate injection in the aquifer and showed that biostimulation was efficient to reduce concentrations of dissolved compounds. Naturally occurring radon was used as a tracer to estimate oil saturation in the saturated zone in a third study. The ease of implementation of this method and the results offer interesting perspectives to optimize the yield of pump-and-skim systems in LNAPL-contaminated sites. The last study focused on the implementation of redox processes and degradation in the saturated zone after the spill. This study showed that processes quickly evolved and that conditions were favorable to natural attenuation. In situ benzene degradation was proven by the measurements of stable isotopes of carbon.

[pt] Este trabalho teve como proposta o desenvolvimento de uma metodologia para determinação de Se e As em amostras de óleo cru, através da técnica de espectrometria de massas com plasma indutivamente acoplado e célula de reação dinâmica. A vantagem do método proposto está na etapa de preparação das amostras, na qual se emprega a diluição direta em solvente orgânico xileno, eliminando tratamentos prévios, como a digestão. Com isso, a análise fica mais fácil e rápida. Em seguida, foi feita a otimização da célula de reação, empregando o metano como gás de reação. Realizou-se um estudo univariado dos parâmetros de operação da célula, como a vazão do gás de reação e o parâmetro de rejeição q, a fim de reduzir as interferências sobre os isótopos 80Se e 75As. Padrões orgânicos de selênio e arsênio diluídos em xileno foram empregados para este estudo e observou-se uma eficiência de redução de interferentes no 80Se de 100%. No caso do 75As, observou-se que o uso da célula não se fez necessário, uma vez que a presença de cloro não foi detectada nas soluções orgânicas. Com os parâmetros da célula apropriados, as condições experimentais foram otimizadas a partir de um estudo univariado. As condições utilizadas foram potência de 1350 W, vazão de argônio de nebulização em 0,40 L min(-1) e argônio auxiliar de 0,7 L min(-1). A técnica de adição padrão foi empregada para calibração e os limites de detecção (LODs) instrumentais foram de 0,23 (80Se) e 0,018 (75As) ug kg(-1). A fim de avaliar a exatidão da metodologia aplicada, analisou-se o material certificado NIST 1634c e obtiveram-se boas recuperações, de 97,3% e 93,5%, respectivamente, para Se e As. Os intervalos de confiança mostraram que os resultados encontrados para o MRC estão dentro da faixa certificada para os dois elementos. A metodologia foi aplicada para análise de nove amostras de petróleo brasileiro. Utilizou-se a técnica de geração de hidretos como forma de comparação com o método proposto. As amostras foram decompostas em bloco de aquecimento e pré-reduzidas com HCl 6 mol L(-1). Curvas de calibração externa foram utilizadas na determinação dos isótopos 78Se, 82Se e 75As, resultando em LODs de aproximadamente 0,04 ug L (-1) para a determinação de Se total e 0,0022 ug L(-1) para o As. A exatidão foi avaliada com o NIST 1634c, obtendo boas recuperações de 99,7% (78Se); 99,2% (82Se) e 100,4% (75As). Um tratamento estatístico foi aplicado e mostrou que os resultados obtidos para selênio em todas as nove amostras de óleo foram concordantes pelas duas técnicas empregadas, a um nível de confiança de 95%. No entanto, somente quatro óleos tiveram resultados de arsênio concordantes pelas duas técnicas. Os outros óleos apresentaram concentrações inferiores para a metodologia de geração de hidretos em relação às concentrações encontradas pela técnica de introdução direta, possivelmente devido a perdas ocorridas durante as etapas de digestão e evaporação. Isto mostra a importância da metodologia desenvolvida para avaliações exatas das concentrações totais de Se e As em petróleos e derivados. / [en] A methodology was developed for the determination of Se and As in samples of crude oil using inductively coupled plasma mass spectrometry with a dynamic reaction cell. The proposed technique of sample preparation showed the advantage of direct dilution in organic solvent, xylene, eliminating previous treatments, such as digestion of samples, and resulting in an easy and fast analytical method. The cell reaction was optimized using methane as the reaction gas. An univariate study was performed with the operating parameters of the cell, the reaction gas flow rate and rejection parameter q, in order to reduce the interferences on isotopes 80Se and 75As. Organic standards for arsenic and selenium dissolved in xylene were used for this study and a 100% reduction efficiency was observed for 80Se. In the case of 75As, it was observed that the use of the cell was not necessary, since the presence of chlorine was not detected in the organic solutions. With the appropriate experimental conditions for the cell, the experimental conditions were optimized by an univariate study. The conditions used were 1350 W (RF power), 0.40 L min(-1) (Ar-nebulizer flow rate) and 0.7 L min(-1) (Ar-auxiliary flow rate). The standard addition technique was employed for calibration and the instrumental limits of detection (LOD) were 0.23 (80Se) and 0.018 (75As) mg kg(-1). In order to validate the methodology, the residual fuel oil certified reference material (CRM) NIST 1634c was analyzed and recoveries of 97% and 94% were obtained for Se and As, respectively. The confidence intervals showed that the results were within the CRM´s range for both elements. The methodology was applied to the analysis of nine samples of Brazilian crude oil. A hydride generation methodology was used for comparison with the proposed methodology. The samples were decomposed in a heated block and pre-reduced with HCl 6 mol L(-1). External calibration curves were used to determine 78Se, 82Se e 75As, resulting in LODs of approximately 0.04 ug L(-1) to determine total Se and 0.0022 ug L (-1) for the As. The accuracy was evaluated also with NIST 1634c, obtaining recoveries of 99.7% (78Se); 99.2% (82Se) e 100.4% (75As). The Snedecor statistical test showed that the results for selenium in all nine oil samples were in agreement by the two techniques at a 95% confidence level. However, only four oils had concordant results for arsenic by both techniques, the other oils showed lower concentrations for the hydride generation methodology in relation to concentrations found by the direct introduction technique. These results were attributed to losses during the digestion and evaporation steps, and this observation showed the importance of the purposed methodology for accurate assessments of total concentrations of Se and As in crude oil and refined products.

The purpose of this thesis is to analyze how the world market price of crude oil, coal and natural gas affects the demand of and dependency on energy imports from the Russian Federation of key European countries[1]. We achieve our objective through econometric estimations of import demand equations concerning imports from the Russian Federation of crude oil, coal and natural gas for seven EU key countries during 1990-2014.Three out of twenty-one models were found to be statistically significant for both the spot price- and income elasticity. The spot price elasticities for the models where: coal import demand for Finland (-0.49), crude oil import demand for Italy (-0.44) and the Netherlands (-0.42). The income elasticities for the aforementioned models were found to be: Finland (2.58), Italy (5.85) and the Netherlands (7.62). The remaining models were statistically insignificant presumably due to different internal structures in the data or due to the assumption of perfect substitute model. [1] EU key countries include: Austria, Finland, France, Germany, Italy, Netherlands, and the United Kingdom. / Syftet med denna uppsats är att analysera hur världsmarknadspriset på råolja, kol och naturgas påverkar den europeiska efterfrågan på och beroendet av energiimport från Ryssland. Ekonometriska uppskattningar av importefterfrågan för råolja, kol och naturgas som produceras av Ryska Federationen för sju EU nyckelländer kommer att produceras. Huvudsyftet är att uppskatta elasticiteter hos importefterfrågan som kännetecknar de handelsförbindelserna mellan Ryssland och sju EU nyckelländerna med avseende på de tre energiresurser.  Tre av tjugoen modeller visade sig vara signifikanta för både världsmarknadspriset och inkomstelasticiteten. Följande variabler och elasticiteter för priset var signifikant; Kol Importefterfrågan för Finland (-0,49), Olje Importefterfrågan för Italien (-0,44) och Nederländerna (-0,42). Inkomstelasticitet för de nämnda modellerna estimeras vara; Finland (2,58), Italien (5,85) och Nederländerna (7,62). Den statistiska insignifikansen hos de övriga modellerna härstamma troligtvis från den interna strukturen på datat eller antagandet om den perfekta substitut modellen

This master thesis investigates and answers three fundamental questions regarding structural changes of a future market. This has been done by analysing and comparing three commodity markets with the Nordic electricity market. Examined commodity markets are LME steel billet, CME lean hogs and WTI &amp; Brent crude oil. The report consists of a literature review with a theoretical background, CATWOE and a case analysis of each commodity market. The markets are thereafter analysed, compared and discussed regarding the research questions. It is concluded that the Nordic electricity market is in many ways comparable to other commodities, although it has some special characteristics. Key factors determining market success have been identified as (1) correlation between perceived risk and derivative risk, (2) trust for and experience of trading institutions and trading environment and (3) expectations. Based on the findings a new conceptual measure for market liquidity, Relative Market Liquidity, is introduced and discussed. The comparison in this thesis is based on the Nordic electricity market, but much of the results are applicable to other commodity markets. The thesis has been written during spring 2013 at the Royal Institute of Technology Department of Energy Technology in co-operation with Vattenfall AB.

This study aims at analysing how African oil benchmarks within the OPEC Reference Basket relative to the WTI and Brent benchmarks which are considered as global pricing benchmarks for the period starting from 1997-2008. The Nigerian Bonny Light and Algerian Saharan blend were the two benchmarks used for this study. A time series analysis was applied to the weekly price data series set and with the aid of a breakpoint unit root test and Cusum of Squared test to determine if there was a change in the persistence of the spread of each African benchmark relative to the global benchmarks. The results for from the unit root test indicated the presence of a structural break in the price spread in 2004 for the Bonny Light benchmark and in 2005 for the Saharan blend relative to both global benchmarks. The Cusum Squared test for the four benchmark pairings indicated a change in persistence of the price spreads. The null hypothesis was rejected for the alternative hypothesis of the price spread process having a relatively high persistence value after a while. The Cusum Test results showed a change in persistence for both African benchmarks relative to the WTI benchmark and no change in persistence relative to the Brent benchmark. The results of from the Time series analysis indicated the competitive nature of African benchmarks relative to global benchmarks and this could benefit exporting countries by virtue of setting up derivative markets. The derivative markets would allow for the trade of benchmark spreads, futures contracts, options and other financial instruments for African oil producers.

The dissertation deals with prediction of crude oil price and is tailor-made for such companies which are heavily crude oil related. The main dissertation target is to make sure that such companies can get ready for price changes and safeguard themselves against negative consequences. Crude oil prices are the main factor which affects prices of such final products as petrol. It is a well known fact that quantitative predictions are not reliable and all those who are forced to real on such vague data set for their decision-making are reluctant to use them. That’s how we would like to have at least the correct trend information. The dissertation introduces some concepts originally developed within artificial intelligence theory for the crude oil predictions. Specifically common sense algorithms and qualitative interpretation of some aspects of theory of chaos are the main contribution towards expanding of available prediction tools described by the dissertation. A systematic analysis of a sequence of qualitative solutions is the key part of the dissertation.

This study has conducted an OLS-regression to examine the relationship between gasoline and crude oil prices in the Swedish petroleum market, focusing on potential asymmetry, where gasoline prices respond more quickly to increases in crude oil prices compared to decreases. Additionally, we examine the impact of individual petroleum stations' competitiveness on this asymmetry, applying the distance to the nearest station as a measure of competitiveness. To explore this relationship, we utilise two datasets: one comprises unique user-generated data for individual gas stations spanning the period from 2019 to 2022, while the other includes recommended prices covering the period from 2001 to 2020. The findings provide some evidence supporting the existence of asymmetry, indicating the presence of inefficiencies within the market. However, no evidence suggesting larger asymmetry concerning individual competitiveness was discovered. Overall, this research offers novel insights into the dynamics of the Swedish fuel market in recent years.