No description available.

[pt] O objetivo do trabalho foi desenvolver métodos analíticos capazes de especiar mercúrio, determinando metilmercúrio (CH3Hg), etilmercúrio (CH3CH2Hg), mercúrio inorgânico (Hg2+, Hg0), em água de produção (AP), e tiomersal (C9H9HgNaO2S), em urina e em efluente de uma indústria farmacêutica. Apesar de existir muitos métodos para quantificar espécies de mercúrio, poucos estudos abordam a especiação em AP, amostras conhecidas por ter altos teores de óleo e sal. Além disso, o uso de nanomateriais, como pontos quânticos de grafeno (GQDs), sozinho ou dopados de nanopartículas de dióxido de titânio (GQDs-TiO2 NPs), foram usados como agentes fotocatalíticos para produzir o mercúrio elementar detectado. As técnicas analíticas utilizadas para a detecção de mercúrio total e para especiação por mercúrio foram espectrometria de absorção atômica com vapor frio em cela multipasso (multipath-CV-AAS) e espectrometria de fluorescência atômica com vapor frio acoplado ao sistema de cromatografia gasosa (GC-CV-AFS). No primeiro trabalho, a foto-degradação do tiomerosal foi alcançada utilizando luz visível e GQDs, obtidos a partir da hidroexfoliação de ácido cítrico e glutationa, como foto-catalisador. O Hg0 gerado (usando condições experimentais ajustadas) foi detectado por multipath-CV-AAS, permitindo a quantificação de tiomersal em concentrações equivalentes a 20 ng L-1, mesmo em amostras complexas como efluentes aquosos da indústria farmacêutica e em urina. A cinética de reação (pseudo-primeira ordem com k = 0,11 min-1) foi determinada. O segundo trabalho relata o método de especiação de mercúrio em AP usando o sistema CV-AAS. Sob condições ajustadas de concentrações de sal e óleo (por diluição e centrifugação), uma alíquota de amostra foi tratada com SnCl2, levando ao Hg0 quantificado como mercúrio inorgânico original. Uma segunda alíquota de amostra foi exposta a UV (sob condições otimizadas) que promoveu a oxidação de CH3Hg a Hg2+, formando Hg2+ que foi posteriormente reduzido, com SnCl2, produzindo o Hg0 referente ao teor total de mercúrio na amostra. O teor de CH3Hg foi obtido pela diferença nos resultados alcançados para as duas alíquotas. O efeito matriz imposto por óleo e sal foram estudados e, apesar de afetar a intensidade do perfil do tempo de mercúrio, a quantificação foi alcançada com sucesso com padrões ajustados (assemelhamento de matriz) combinando quantidades de NaCl e óleo mineral. As medições de condutividade (estimativa de teor de sal) e turbidimétrica (estimativa de teor de óleo) foram feitas para as amostras de PW, a fim de permitir o ajuste adequado da amostra aos padrões correspondentes (contendo óleo mineral a 5 mg L-1 e NaCl a 5 g L-1). O método de adição de analito também foi utilizada e o limite de quantificação foi de 12 ng L-1. / [en] The aim of the present work was to develop analytical methods capable of determining mercury species such as methylmercury (CH3Hg), ethylmercury (CH3CH2Hg), inorganic mercury (Hg2+, Hg0), in produced water (PW) and urine, as well as thiomersal C9H9HgNaO2S) in effluent from a pharmaceutical industry and in urine. Despite many methods for quantifying mercury species are reported, few studies address speciation in PW, sample known to have high oil and salt contents. Besides, the use of nanomaterials such as graphene quantum dots (GQDs) alone or decorating titanium dioxide nanoparticles (GQDs-TiO2 NPs) were used as photocatalytic agents to produce the detected elemental mercury. The analytical techniques used for total mercury detection and mercury speciation were multipath cold vapor atomic absorption spectrometry (multipath˗CV˗AAS) and gas chromatography cold vapor atomic fluorescence spectrometry (GC˗CV˗AFS). In the first work, the photo-degradation of thiomersal has been achieved using visible light and GQDs, obtained from hydro-exfoliation of citric acid and glutathione, as catalysts. The generated Hg0 (using adjusted experimental conditions) was detected by multipath-CV-AAS, enabling quantification of thiomersal at values as low as 20 ng L-1 even in complex samples as aqueous effluents from the pharmaceutical industry and in the urine. The reaction kinetic (pseudo-first-order with k = 0.11 min-1 ) was determined. The second work provided a speciation method for mercury in PW using multipath-CV-AAS. Under adjusted salt and oil contents (by dilution and centrifuging), a sample aliquot was treated with SnCl2, leading to the Hg0 quantified as the original inorganic mercury. A second sample aliquot was exposed to UV (under optimized conditions) that promoted oxidation of CH3Hg to Hg2+, which was then reduced, with SnCl2, producing the Hg0 relative to the total mercury content in the sample. The CH3Hg content was obtained by the difference in results achieved for both aliquots. Matrix effects imposed by oil and salt were studied, and although affecting the intensity of the mercury time profile, quantification was successfully achieved by matrix-matched standards containing NaCl and mineral oil.

Made available in DSpace on 2014-12-17T14:08:46Z (GMT). No. of bitstreams: 1 ZildianyIM_DISSERT.pdf: 2328964 bytes, checksum: cce13a45c02b28ab140a7f90a8548746 (MD5) Previous issue date: 2011-07-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Boron is a semi-metal present in certain types of soils and natural waters. It is essential to the healthy development of plants and non-toxic to humans, depending on its concentration. It is used in various industries and it s present in water production coming from oil production. More specifically in Rio Grande do Norte, one of the largest oil producers on shore of Brazil, the relationship water/oil in some fields becomes more than 90%. The most common destination of this produced water is disposal in open sea after processing to meet the legal specification. In this context, this research proposes to study the extraction of boron in water produced by microemulsion systems for industrial utilization. It was taken into account the efficiency of extraction of boron related to surfactant (DDA and OCS, both characterized by FT-IR), cosurfactant (butanol and isoamyl alcohol), organic phase (kerosene and heptanes) and aqueous phase (solution of boron 3.6 ppm in alkaline pH). The ratio cosurfactant/ surfactant used was four and the percentage of organic phases for all points of study was set at 5%. It was chosen points with the highest percentage of aqueous phase. Each system was designed for three points of different compositions in relation to the constituents of a pseudoternary diagram. These points were chosen according to studies of phase behavior in pseudoternary diagrams made in previous studies. For this research, points were chosen in the Winsor II region. The excess aqueous solution obtained in these systems was separated and analyzed by ICP OES. For the data set obtained, the better efficiency in the extraction of boron was obtained using the system with DAC, isoamyl alcohol and heptanes, which extracted 49% in a single step. OCS was not viable to the extraction of boron by microemulsion system in the conditions defined in this study / O boro ? um semi-metal presente em determinados tipos de solos e ?guas naturais. ? essencial ao desenvolvimento sadio de esp?cies vegetais e at?xico ao homem, dependendo de sua concentra??o. ? utilizado em v?rias ind?strias e est? presente em ?guas de produ??o oriundas da atividade petrol?fera. Mais especificamente no Rio Grande do Norte, um dos maiores produtores de petr?leo on shore do Brasil, a mistura ?gua/?leo produzida em alguns campos chega a ser superior a 90% em ?gua. O destino mais comum a essa ?gua produzida ? o descarte no mar aberto ap?s especifica??o. Com isso, o objeto a que se prop?e este trabalho ? o estudo da extra??o do boro em ?gua produzida por sistema microemulsionado (SME) para seu aproveitamento industrial. Nesse estudo foi levado em considera??o a efici?ncia de extra??o de boro quanto ao tensoativo (DDA e OCS, ambos caracterizados por FT-IV), cotensoativo (butanol e ?lcool isoam?lico), fase org?nica (querosene e heptano) e fase aquosa (solu??o de boro 3,6 ppm em pH b?sico). A raz?o cotensoativo/tensoativo utilizada foi quatro e o percentual das fases org?nicas para todos os pontos de estudo foi fixada em 5%. Foram escolhidos pontos com maior percentual de fase aquosa. Cada sistema foi montado para tr?s pontos de composi??es diferentes em rela??o aos constituintes de um diagrama pseudotern?rio. Estes pontos foram escolhidos de acordo com estudos do comportamento de fases em diagramas pseudotern?rios realizados em estudos anteriores. Para esse estudo os pontos escolhidos localizaram-se na regi?o de Winsor II. A solu??o aquosa em excesso obtida nesses sistemas foi separada e analisada por ICP OES. Do conjunto de dados obtidos, o sistema que apresentou melhor efici?ncia na extra??o de boro foi o que utilizou DAC, ?lcool isoam?lico e heptano, com aproximadamente 49% de extra??o numa ?nica etapa. O OCS n?o se mostrou favor?vel a extra??es de boro por sistema microemulsionados nas condi??es do estudo

Made available in DSpace on 2014-12-17T14:08:46Z (GMT). No. of bitstreams: 1 ShirleyFMS_DISSERT_parcial.pdf: 156702 bytes, checksum: 946fe2ea3a673657c92a1d9cf7dbf34a (MD5) Previous issue date: 2011-02-28 / Petr?leo Brasileiro SA - PETROBRAS / Waste generated during the exploration and production of oil, water stands out due to various factors including the volume generated, the salt content, the presence of oil and chemicals and the water associated with oil is called produced water. The chemical composition of water is complex and depends strongly on the field generator, because it was in contact with the geological formation for thousands of years. This work aims to characterize the hydrochemical water produced in different areas of a field located in the Potiguar Basin. We collected 27 samples from 06 zones (400, 600, 400/600, 400/450/500, 350/400, A) the producing field called S and measured 50 required parameter divided between physical and chemical parameters, cations and anions. In hydrochemical characterization was used as tools of reasons ionic calculations, diagrams and they hydrochemical classification diagram Piper and Stiff diagram and also the statistic that helped in the identification of signature patterns for each production area including the area that supplies water injected this field for secondary oil recovery. The ionic balance error was calculated to assess the quality of the results of the analysis that was considered good, because 89% of the samples were below 5% error. Hydrochemical diagrams classified the waters as sodium chloride, with the exception of samples from Area A, from the injection well, which were classified as sodium bicarbonate. Through descriptive analysis and discriminant analysis was possible to obtain a function that differs chemically production areas, this function had a good hit rate of classification was 85% / Dos res?duos gerados durante a explora??o e produ??o de petr?leo, a ?gua se destaca devido a v?rios fatores, entre eles o volume gerado, o conte?do salino, a presen?a de ?leo e de produtos qu?micos e essa ?gua associada ao petr?leo ? denominada ?gua produzida. A composi??o qu?mica dessa ?gua ? complexa e depende fortemente do campo gerador, pois a mesma esteve em contato com a forma??o geol?gica por milhares de anos. Esse trabalho tem como objetivo caracterizar hidroqu?micamente a ?gua produzida em diferentes zonas de um campo localizado na Bacia Potiguar. Foram coletadas 27 amostras provenientes de 06 zonas (400, 600, 400/600, 400/450/500, 350/400, A) produtoras do campo denominado S e medidos 50 par?mentos divididos entre par?metros f?sico-qu?micos, c?tions e ?nions. Na caracteriza??o hidroqu?mica foi utilizado como ferramentas c?lculos de raz?es i?nicas, diagramas de classifica??o hidroqu?mica sendo eles o diagrama de Piper e o diagrama de Stiff e tamb?m a estat?stica que auxiliou nas identifica??es de assinaturas padr?es de cada zona de produ??o inclusive a zona que fornece a ?gua injetada nesse campo para a recupera??o secund?ria de petr?leo. O erro do balan?o i?nico foi calculado para avaliar a qualidade dos resultados das an?lises que foi considerada boa, pois 89% das amostras apresentaram erro abaixo de 5%. Os diagramas hidroqu?micos classificaram as ?guas como Cloretadas S?dicas, com exce??o das amostras da zona A, proveniente do po?o injetor, que foram classificadas como Bicarbonatadas S?dicas. Atrav?s da an?lise descritiva e da an?lise de discriminante foi poss?vel a obten??o de uma fun??o que distingue quimicamente as zonas de produ??o, essa fun??o apresentou uma boa taxa de acerto de classifica??o que foi de 85%

Made available in DSpace on 2014-12-17T15:01:15Z (GMT). No. of bitstreams: 1 MagnaASB.pdf: 1635517 bytes, checksum: df420c88397a6cd630a5381fcef348b7 (MD5) Previous issue date: 2004-09-02 / The production of petroleum is frequently accomplished with great volumes of water, that it is carried of the underground with the oil. It is a challenge of the present century the development of technologies that allow the use of waste water for purposes that consume great amounts of water and don't demand as rigid as the one of the drinking water requirements. The solar distillation has been configuring as an alternative of clean technology for desalination of brine and saline. Besides causing the minimum possible damage to the environment, it takes advantage of an abundant and free energy source: the solar energy. That study aims to develop a Solar Distillator for treatment of the produced water of the oil wells, to obtain an efluent to use in agriculture and vapor generation. The methodology for collection, conservation and analysis of the physical-chemical parameters obeyed the norms in APHA (1995). The sampling was of the composed type. Experiments were accomplished in the solar distillation pilot and simulation in thermostatic bathing. The operation was in batch system and for periods of 4, 6 and 12 h. The developed Distillator is of the type simple effect of two waters. It was still tested two inclination angles for covering; 20? and 45?. The Distillator presented minimum of 2,85 L/m2d revenues and maximum of 7,14 L/m2d. The removals of salts were great than 98%. The removal of TOC in the simulation was great than 90%. In agreement with the data of energy and mass balance, it was verified that the developed solar Distillator presented compatible revenues with those found in literature for similar types. It can be inferred that the obtained distilled water assists to the requirements CONAMA in almost all the points and could be used for irrigation of cultures such as cotton and mamona. As the distilled water has characteristics of fresh water it can be used in the generation of vapor / A produ??o de petr?leo ? realizada freq?entemente com grandes volumes de ?gua, que ? carreada do subsolo junto com o ?leo. ? desafio do presente s?culo o desenvolvimento de tecnologias que possibilitem ou uso ou reuso de efluentes para outros fins. A destila??o solar ? uma alternativa de tecnologia limpa para dessaliniza??o de ?guas salobras e salinas. Esse estudo visa desenvolver um Destilador Solar para tratamento da ?gua de produ??o de petr?leo, com vistas a se obter um efluente pass?vel de utiliza??o na agricultura e gera??o de vapor. A metodologia para conserva??o e an?lise dos par?metros f?sico-qu?micos obedeceu preconiza??o do APHA (1995). A amostragem foi do tipo composta. Foram realizados experimentos no destilador solar piloto e simula??o em banho termost?tico. A opera??o foi em sistema de batelada e por per?odos de 4, 6 e 12 h. O destilador desenvolvido ? do tipo simples efeito de duas ?guas. Testou-se ainda dois ?ngulos de inclina??o para cobertura; 20? e 45?. O destilador apresentou rendimentos m?nimo de 2,50 L/m2d e m?ximo de 7,5 L/m2d. As remo??es de sais foram superiores a 98%. A remo??o de TOC na simula??o foi superior a 90%. De acordo com os dados dos balan?os energ?tico e de massa, verificou-se que o destilador solar desenvolvido apresentou rendimentos compat?veis com os encontrados na literatura para seus similares. Enfatiza-se que o isolamento utilizado n?o estava nas condi??es de otimiza??o, logo, esse rendimento pode ser melhorado. Pode-se inferir que a ?gua destilada obtida atende aos requisitos CONAMA em quase todos os pontos, podendo ser utilizada, com ressalvas, na irriga??o de culturas n?o comest?veis como o algod?o e a mamona. Como a ?gua destilada tem caracter?sticas de ?gua doce pode ser utilizada na gera??o de vapor

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The oil and gas industry produces huge amounts of produced water (PW), a complex effluent. This product is one of the main constituents of polycyclic aromatic hydrocarbons (PAH), which exhibit high toxicity. Therefore, this study aims at developing and validating a method for determining PAH (Benz(a)anthracene, Benzo(b)fluoranthene, Benzo(k)fluoranthene, Benzo(a)pyrene, and Dibenzo (a,h)anthracene) in PW by using magnetic solid phase extraction (MSPE) and high-performance liquid chromatography with fluorescence detector. We synthesized three new adsorbents: FeCt (with ferric chloride and water rich in natural organic matter); FeCc (with ferric chloride, distilled water, and coconut husk), and FeSt (with ferric sulfate and water rich in natural organic matter). The x-ray diffraction and infrared spectroscopy confirmed obtaining the hybrid materials. The best extraction conditions were obtained by using ultrasonic cleaning as a mixing mechanism with time set to 2.5 minutes for adsorption and 2.5 minutes for desorption, using 10 mL of ethyl acetate as an extractor and 20 mg of hybrid FeSt; the values of PAH recovery varied from 84.3 to 92.3 %. The capacity of reusing the material was assessed and the results exhibited a great recovery with up to 4 cycles of adsorption/desorption. The methodology we propose was applied to two PW samples. The recovery values for samples PWW1 (produced water at well 1) enriched with 100μg L-1 were of 81 – 104%, without the presence of B(a)P standard. As for the PAH concentrations in the sample, they varied from 0.63 to 1.66 μg L-1 for PWW1 from 0.54 to 1.62 μg L-1 for PWW2 (produced water at well 2). The validation of the method was performed for the following parameters: linearity, which exhibits a correlation coefficient (r) above 0.9943 within the interval of 0.5 - 25 μg L-1 ; accuracy and precision, with recovery values between 98.2 – 108.9 %, and coefficient of variation 0.64 – 6.72 % for the concentration levels of 3.8 and 15 μg L-1 (n=3), respectively. LODs varied from 0.012 and 0.02 μg L-1 and LOQs, from 0.036 to 0.06 μg L-1. / A indústria de petróleo e gás produz grandes quantidades de água produzida (AP), que é um efluente complexo, sendo que um dos seus principais constituintes são os Hidrocarbonetos Policíclicos Aromáticos (HPA), os quais apresentam elevada toxicidade. Assim, o presente trabalho tem por objetivo desenvolver e validar um método de determinação de HPA (Benzo(a)Antraceno, Benzo(b)Fluoranteno, Benzo(k)Fluoranteno, Benzo(a)Pireno e Dibenzo(ah)Antraceno) em AP utilizando a extração em fase sólida magnética (MSPE) e cromatografia líquida de alta eficiência com detector de fluorescência. Foram sintetizados três novos adsorventes FeCt (com cloreto férrico e água com alto teor de MON), FeCc (com cloreto férrico, água destilada e bagaço de coco) e FeSt (com sulfato férrico e água com alto teor de MON). A difração de raios X e a espectroscopia de infravermelho confirmaram a obtenção dos materiais híbridos. As melhores condições de extração foram obtidas em banho de ultrassom como mecanismo de agitação, com tempo estipulado em 2,5 min para a adsorção e 2,5 min para a dessorção, utilizando 10 mL de acetato de etila como extrator e 20 mg do híbrido FeSt. Os valores de recuperação dos HPA variaram de 84,3 – 92,3 %. A capacidade de reutilização do material foi avaliada e os resultados apresentaram ótima recuperação com até 4 ciclos de adsorção/dessorção. A metodologia proposta foi aplicada em duas amostras de AP e os valores de recuperação para a amostra de APP1 (água produzida poço 1), enriquecida com 100 μg L-1, foram de 81 – 104 %, sem a presença do padrão do B(a)P, e a concentração dos HPA na amostra variou de 0,63 – 1,66 μg L-1 para o APP1, e de 0,54 – 1,62 μg L-1 para o APP2 (água produzida poço 2). A validação do método foi realizada para os parâmetros: linearidade, com o coeficiente de correlação (r) acima de 0,9943 no intervalo de 0,5 - 25 μg L-1; exatidão e precisão, com valores de recuperação entre 98,2 - 108,9 % e coeficiente de variação 0,64 - 6,72 % para os níveis de concentração 3, 8 e 15 μg L-1 (n=3), respectivamente. Os limites de detecção (LD) variaram entre 0,012 a 0,02 μg L-1 e os limites de quantificação (LQ) entre 0,036 a 0,06 μg L-1. / São Cristóvão, SE

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-04-14T16:10:05Z No. of bitstreams: 1 Dissertação - Aline Soares Freire - FINAL.pdf: 4503064 bytes, checksum: 1e469a75225eda50cf3c49c6ab32c87a (MD5) / Made available in DSpace on 2016-04-14T16:10:05Z (GMT). No. of bitstreams: 1 Dissertação - Aline Soares Freire - FINAL.pdf: 4503064 bytes, checksum: 1e469a75225eda50cf3c49c6ab32c87a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A análise de amostras hipersalinas ainda é um problema analítico a ser resolvido, tendo em vista que a presença de sais dissolvidos é fonte freqüente de interferências em espectrometria atômica. Atualmente, tem ocorrido um grande aumento da demanda para caracterização de águas de alta salinidade, como as águas produzidas, pelo fato de estas serem um dos maiores descartes da indústria de petróleo. Devido a isto, metodologias analíticas para sua caracterização têm sido amplamente desenvolvidas para a determinação de metais-traço em amostras salinas e dentre as técnicas analíticas destaca-se a Espectrometria de Absorção Atômica de Alta Resolução com Fonte Contínua, uma renovação da AAS convencional. Contudo, para a obtenção de resultados acurados, é imprescindível que se faça a remoção dos sais presentes nessas matrizes hipersalinas. Essa separação prévia pode ser realizada através do emprego de resinas qualantes, que pré-concentram o analito e permitem a remoção da matriz. Sendo assim, este trabalho visa à avaliação do uso da resina quelante comercial Chelex-100® na préconcentração de Co, Cu, Mn, Ni e Pb e posterior determinação destes por Espectrometria de Absorção Atômica de Alta Resolução com Fonte Contínua e Forno de Grafite (HR-CS GF AAS). A metodologia foi validada através do uso dos materiais de referência certificados para água do mar CASS-4, CASS-5 e NASS-5. Os limites de detecção obtidos, em μg L-1, foram de 0,006; 0,070; 0,024; 0,074; e 0,018 para Co, Cu, Mn, Ni e Pb, respectivamente. Amostras de água produzida oriundas de plataformas de petróleo offshore foram analisadas e os resultados mostraram que essas águas possuem baixas concentrações dos elementos determinados ou os mesmos não foram detectados. Os valores encontrados são muito inferiores aos limites preconizados pela legislação brasileira através da Resolução CONAMA 357/05 / The analysis of hypersaline samples is still an analytical problem to be solved, once the presence of dissolved salts is a frequent source of interferences in atomic spectrometry. Actually, there is a large increase in the interest in the caracterization of this kind of sample, as produced waters are one of the largest discharges of petroleum industry. Hence, analytical methodologies to produced water caracterization have been widely developed to trace metals determination in saline samples and among the analytical techniques, there is High Resolution Continuum Source Atomic Absorption Spectrometry, a renovation of conventional AAS. However, to obtain accurated results, it's necessary to remove the salts present in this high salinity matrices. This previous separation can be done employing a chelating resin, that preconcentrates the analyte(s) and allows matrix removal. In this way, the aim this work is to evaluate the use of chelating resin Chelex-100® to preconcentrate Co, Cu, Mn, Ni and Pb, for the later determination by High Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry (HR-CS GF AAS). The methodology was validated by the use of sewater certified reference materials CASS-4, CASS-5 e NASS-5. The detection limits in μg L-1, were 0,006; 0,070; 0,024; 0,074; and 0,018 for Co, Cu, Mn, Ni and Pb, respectively. Produced water samples from offshore petroleum platforms were analysed and results showed that this waters have low concentrations of these studied elements or could not be detected. Found values are much lower when compared to limits from Brazilian legislation, in this case CONAMA 357/05 Resolution

Hydraulic fracturing operations utilized for shale gas production result in the generation of a large volume of flowback and produced water that contain suspended material, salts, hydrocarbons, metals, chemical additives, and naturally-occurring radioactive material. The water is impounded at drilling sites or treated off-site, resulting in significant generation of residual solids. These are either buried on site or are disposed in lined landfills. The objective of this study was to determine the levels of heavy metals and other elements of concern that will leach from these residual solids when placed in typical disposal environments. For this purpose, laboratory leaching experiments were employed wherein representative samples were brought into contact with a liquid to determine the constituents that would be leached by the liquid and potentially released into the environment. The samples used included sludge resulting from the physicochemical treatment of process water (TS), sludge solidified with cement kiln dust (SS), raw solids obtained by gravity separation of process water (RS), and drilling mud (DM). The samples were subjected to both single extraction (i.e. Shake Extraction Test, SET) and multiple extraction (i.e. Immersion Test, IT) leaching tests. For the shake extraction test, samples were mixed with a specific amount of leaching solution without renewal over a short time period. In the immersion test, samples were immersed in a specific amount of leaching solution that was periodically renewed over a longer period of time. For both these tests, analyses were performed on the filtered eluate. The tests were performed as per standards with modifications. Distilled de-ionized water, synthetic acid rain (pH ~ 4.2), weak acetic acid (pH ~ 2.88), and synthetic landfill leachate were used as leaching solutions to mimic specific disposal environments. Alkali metals (Li, K, Na), alkaline earth metals (Ba, Ca, Mg, Sr) and a halide (Br), which are typically associated with Marcellus shale and produced waters, leached at high concentrations from most of the residual solids sample. The SS sample, due to its stabilization with CKD, had a lower extraction efficiency as compared to the unconsolidated TS and RS samples. In EF 2.9 and EF SLL, the leaching took place under acidic conditions, while for EF DDI and EF 4.2, the leaching occurred in alkaline conditions. EF 2.9 and EF SLL were determined to be the most aggressive leaching solutions, causing the maximum solubility of most inorganic elements. Thus, high amounts of most EOCs may leach from these residual solids in MSW landfills disposed under co-disposal conditions. Agitation, pH and composition of the leaching solution were determined to be important variables in evaluating the leaching potential of a sample. The results of this study should help with the design of further research experiments being undertaken to develop environmentally responsible management/disposal strategies for these residual solids and also prove useful for regulatory authorities in their efforts to develop specific guidelines for the disposal of residuals from shale gas production operations. / Master of Science

No description available.

The need for energy and the associated economic benefits from the oil and gas deposits found mainly in the Niger Delta region of Nigeria necessitated the exploration and exploitation activities being carried out by the oil and gas Companies. However, these exploration and exploitation activities due to their unpredictable nature have a huge potential for environmental pollution as been experienced in the form of oil spills, gas flaring, irresponsible disposal of waste and several other activities that have resulted in the environmental degradation of the Niger Delta region. In the light of these, the Federal Government of Nigeria having experienced the consequences of pollution of the environment during the Koko Toxic Waste Dump incident in the then Bendel State in 1987 established a regulatory body tasked with the responsibility of harmonizing the economic interest from the oil and gas exploration and exploitation activities with the sustainability of the natural environment by developing well structured and articulated policies aimed at guiding the operations of the oil and gas operators, track their compliance and administer appropriate punitive measures for non compliance. However, this research work which is aimed at evaluating the impact of the environmental protection policies in upstream oil and gas activities in the Niger Delta region, involved the use of questionnaires and interviews. These questionnaires were completed by the management and staff of three major oil and gas companies operating within the area, the Department of Petroleum Resources and members of the Host communities. The interview was carried out to provide relevant feedback on their assessment of the impact made by the environmental protection policies on the upstream oil and gas activities in their operational areas/host communities. The study however concluded that “Although there is a regulatory body tasked with the responsibility to develop, implement and track compliance of the environmental protection policies in the upstream oil industry, the body is ineffective and as such the impact of the environmental protection policies is inadequate. Appropriate informed recommendations on the improvement strategies to the identified gaps that resulted in the unfavorable conditions were also provided. / Thesis (M.Ing. (Development and Management Engineering))--North-West University, Potchefstroom Campus, 2011