Different aspects of natural organic matter composition and cycling have been studied using solid-state 13C and 31P Nuclear Magnetic Resonance (NMR) spectroscopy. Depending on the specific study, complementary analytical techniques such as elemental, isotopic and molecular analyses have also been applied. Samples from a variety of environments were examined including ocean waters, marine sediments and atmospheric aerosols. Studies from all these environments illustrate differences in natural organic matter composition resulting from various factors such as sources, cycling mechanisms and redox conditions. In the marine water column, organic matter of two different size fractions (dissolved and particulate) is found to have distinctly different bulk chemical and isotopic compositions. Overall, this indicates that particulate organic matter does not form from the simple physical aggregation of dissolved organic matter, and dissolved organic matter is not the primary source for particulate organic matter. Comparison of carbon and phosphorus compositional changes with depth in the ocean within the dissolved and particulate fractions reveals differences in cycling mechanisms. In the marine water column, selective mineralization of specific carbon compounds such as carbohydrates and amino acids occurs relative other species such as lipids. Whereas for phosphorus, the relative proportion of the different functional groups are unvarying with depth. In marine sediments, NMR spectroscopy reveals P cycling for specific phases such as polyphosphates is a function of sediment redox conditions. In atmospheric aerosols 13C NMR spectroscopy shows differences in water-soluble organic carbon composition from urban versus biomass burning sources. Urban aerosols have higher aliphatic and lower aromatic compound contents relative to samples derived from biomass burning. The results of these studies provide new insights into carbon and phosphorus cycling in the environment and demonstrate the capabilities of solid-state NMR as a tool for investigating natural organic matter composition.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / O estudo geoquímico detalhado em dois poços (A e B) na porção oeste da Bacia do Amazonas visou o entendimento da quantidade, fonte e evolução térmica da matéria orgânica presente nas Formações Ererê, Barreirinha e Curiri. Foram efetuadas análises de Carbono Orgânico Total (COT), pirólise Rock-Eval e biomarcadores. Os teores de carbono orgânico total da Formação Barreirinha (Membro Abacaxis) que variam de 1,43% a 8,39%, indicaram que este intervalo possui quantidade de matéria orgânica necessária para ser considerado potencialmente gerador de óleo e gás. As outras unidades litoestratigráficas apresentaram teores de COT pouco significativos. Com base nos dados de pirólise, identificou-se que o intervalo com o melhor potencial gerador corresponde ao Membro Abacaxis. Esta seção no poço A possui índice de hidrogênio (IH) ligeiramente superior a 200 mg HC/gCOT e um potencial gerador (S2)variando de 4 a 17,76 mg de HC/g de rocha, indicando um bom à excelente potencial adequado à geração de gás e condensado. Já no poço B, em decorrência do aumento da evolução térmica, os valores de S2 e IH são mais baixos(variando de 5 a 10 mgHC/g de rocha e com valores entre 50 e 150 mg HC/gCOT, respectivamente), apenas indicando um bom potencial à geração de gás. Segundo diagrama tipo Van Krevlen, a matéria orgânica deste intervalo é heterogênea e se comporta como querogênio tipo II e III no poço A e do tipo III e IV no poço B. As características dos biomarcadores encontrados no Membro Abacaxis indicam uma origem algal e ambiente marinho. O Membro Urariá e a Formação Curiri apresentam indicadores sugestivos de aporte de matéria orgânica de origem terrestre, sendo que o Membro Urariá ainda mostra algumas assinaturas semelhantes com o Membro Abacaxis. Devido a baixa concentração dos biomarcadores cíclicos nas amostras do Poço B, não foi possível realizar uma caracterização da fonte da matéria orgânica da Formação Ererê. A avaliação dos parâmetros utilizados para a interpretação da evolução térmica, como Tmax, taxa de transformação (TT), índice de produção (IP), reflectância da vitrinita calculada (Roc) e razões entre alcanos lineares e ramificados (P/nC17 e F/nC18), indicaram que no intervalo gerador do Poço A houve geração de hidrocarbonetos, mas ainda não correu a migração. No caso do Poço B, os dados mostram que neste intervalo já houve geração e migração de hidrocarbonetos. / The detailed geochemical study in two wells (A and B) at the west portion of the Amazonas Basin aimed the understading of the source, origin and thermal evolution of the organic matter presented in the Barreirinha Formation, encompassing the samples of the Ererê and Curiri Formations too. Analyzes of Total Organic Carbon (TOC), pyrolyse "Rock-Eval" and biomarkers were carried out. The organic carbon content of Barreirinha Formation (Abacaxis Member) range from 1,43% to 8,39% and indicate that this interval has enough organic matter and a good potential for oil and gas generation. The other lithoestratigraphic units showed not significant levels of TOC. Based on the pyrolyse data, it was identified that the interval with the better potential for generation is the Abacaxis Member. This section of the well A has the hydrogen index (HI) slightly higher to 200 mg HC/gTOC and a generating potential (S2) ranging from 4 to 17,76 mg of HC/g of rock, indicating a good to excellent potential for generation of gas and condensed. On the other hand, the well B, as a result of the higher thermal evolution, the values of S2 and HI are lower (ranging from 5 to 10 mg of HC/g of rock in S2 and values between 50 and 150 mg HC/gTOC in HI), just indicating a slightly potential to the generation of gas. In according to the Van Krevlen Diagram, the organic matter of this interval is heterogeneous and behave like a kerogen type II and III at the well A and type III and IV at the well B. The biomarkers data at Abacaxis Member indicate algal origin and marine environment. The Urariá Member and the Curiri Formation show suggestive indicators of terrestrial organic matter contribution, but the Urariá Member show some evidences similar to the Abacaxis Member too. Due to the low concentration of the cyclic biomarkers in the samples of the weel B, the characterization of the origin of the organic matter of Erere Formation was not possible. The assessment of the parameters utilized for the interpretation of the themal evolution, such as Tmax, transformation ratio (TR), production index (IP), calculated vitrinite reflectance (Roc) and the ratios pristane/nC17 and phytane/nC18, indicate that the source rock of Well A had generation of hydrocarbon, but still does not happened the migration. In case of Well B, the data shows that in this interval already had generation and migration of hydrocarbon.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / O estudo geoquímico detalhado em dois poços (A e B) na porção oeste da Bacia do Amazonas visou o entendimento da quantidade, fonte e evolução térmica da matéria orgânica presente nas Formações Ererê, Barreirinha e Curiri. Foram efetuadas análises de Carbono Orgânico Total (COT), pirólise Rock-Eval e biomarcadores. Os teores de carbono orgânico total da Formação Barreirinha (Membro Abacaxis) que variam de 1,43% a 8,39%, indicaram que este intervalo possui quantidade de matéria orgânica necessária para ser considerado potencialmente gerador de óleo e gás. As outras unidades litoestratigráficas apresentaram teores de COT pouco significativos. Com base nos dados de pirólise, identificou-se que o intervalo com o melhor potencial gerador corresponde ao Membro Abacaxis. Esta seção no poço A possui índice de hidrogênio (IH) ligeiramente superior a 200 mg HC/gCOT e um potencial gerador (S2)variando de 4 a 17,76 mg de HC/g de rocha, indicando um bom à excelente potencial adequado à geração de gás e condensado. Já no poço B, em decorrência do aumento da evolução térmica, os valores de S2 e IH são mais baixos(variando de 5 a 10 mgHC/g de rocha e com valores entre 50 e 150 mg HC/gCOT, respectivamente), apenas indicando um bom potencial à geração de gás. Segundo diagrama tipo Van Krevlen, a matéria orgânica deste intervalo é heterogênea e se comporta como querogênio tipo II e III no poço A e do tipo III e IV no poço B. As características dos biomarcadores encontrados no Membro Abacaxis indicam uma origem algal e ambiente marinho. O Membro Urariá e a Formação Curiri apresentam indicadores sugestivos de aporte de matéria orgânica de origem terrestre, sendo que o Membro Urariá ainda mostra algumas assinaturas semelhantes com o Membro Abacaxis. Devido a baixa concentração dos biomarcadores cíclicos nas amostras do Poço B, não foi possível realizar uma caracterização da fonte da matéria orgânica da Formação Ererê. A avaliação dos parâmetros utilizados para a interpretação da evolução térmica, como Tmax, taxa de transformação (TT), índice de produção (IP), reflectância da vitrinita calculada (Roc) e razões entre alcanos lineares e ramificados (P/nC17 e F/nC18), indicaram que no intervalo gerador do Poço A houve geração de hidrocarbonetos, mas ainda não correu a migração. No caso do Poço B, os dados mostram que neste intervalo já houve geração e migração de hidrocarbonetos. / The detailed geochemical study in two wells (A and B) at the west portion of the Amazonas Basin aimed the understading of the source, origin and thermal evolution of the organic matter presented in the Barreirinha Formation, encompassing the samples of the Ererê and Curiri Formations too. Analyzes of Total Organic Carbon (TOC), pyrolyse "Rock-Eval" and biomarkers were carried out. The organic carbon content of Barreirinha Formation (Abacaxis Member) range from 1,43% to 8,39% and indicate that this interval has enough organic matter and a good potential for oil and gas generation. The other lithoestratigraphic units showed not significant levels of TOC. Based on the pyrolyse data, it was identified that the interval with the better potential for generation is the Abacaxis Member. This section of the well A has the hydrogen index (HI) slightly higher to 200 mg HC/gTOC and a generating potential (S2) ranging from 4 to 17,76 mg of HC/g of rock, indicating a good to excellent potential for generation of gas and condensed. On the other hand, the well B, as a result of the higher thermal evolution, the values of S2 and HI are lower (ranging from 5 to 10 mg of HC/g of rock in S2 and values between 50 and 150 mg HC/gTOC in HI), just indicating a slightly potential to the generation of gas. In according to the Van Krevlen Diagram, the organic matter of this interval is heterogeneous and behave like a kerogen type II and III at the well A and type III and IV at the well B. The biomarkers data at Abacaxis Member indicate algal origin and marine environment. The Urariá Member and the Curiri Formation show suggestive indicators of terrestrial organic matter contribution, but the Urariá Member show some evidences similar to the Abacaxis Member too. Due to the low concentration of the cyclic biomarkers in the samples of the weel B, the characterization of the origin of the organic matter of Erere Formation was not possible. The assessment of the parameters utilized for the interpretation of the themal evolution, such as Tmax, transformation ratio (TR), production index (IP), calculated vitrinite reflectance (Roc) and the ratios pristane/nC17 and phytane/nC18, indicate that the source rock of Well A had generation of hydrocarbon, but still does not happened the migration. In case of Well B, the data shows that in this interval already had generation and migration of hydrocarbon.

Thesis (M.S.)--Joint Program in Oceanography and Oceanographic Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), June 1996. / "May 1996." / Includes bibliographical references (leaves 66-68). / This thesis details two years of research conducted with the guidance and support of three advisors: Dr. J. K. Whelan, Dr. J. S. Seewald and Dr. T. I. Eglinton. Each of the three chapters represents a different, self-contained research project. All of the projects are related to the organic geochemistry of marine sediments, however, this is a fairly encompassing area of study. Chapters 1 and 2 stem from the same experimental study -- the use of hydrous-pyrolysis to investigate mechanisms leading to the production of petroleum-related products during kerogen maturation. Chapter 3, on the other hand, utilizes a recently developed technique of isolating and AMS-14C dating individual compounds from complex sedimentary organic mixtures. The samples used in each investigation came from all over the world. The first two chapters utilize ancient marine sediment samples obtained from an outcrop in California (Chpts. 1 and 2) and from a well in Alabama (Chpt. 2). In contrast, recent marine sediment samples were obtained from the Arabian and Black Seas for the third chapter. Several preparative and analytical methods are common to all three studies. Nevertheless, each employ techniques totally unique from one another and from previous investigations. In Chapter 1, for example, X-ray absorption spectroscopy (XANES) is used to determine the speciation of organic sulfur present in kerogen, bitumen, and bulk sediment samples. While Chapter 3 represents the first study in which the "4C ages of individual, known hydrocarbon biomarkers are determined after isolation by Preparative Capillary Gas Chromatography (PCGC). The insights gained by these investigations are discussed in detail in the following chapters. The common thread between the three chapters is that the source of organic matter, the rate at which it is delivered to marine sediments and the depositional environment, all set the stage for kerogen formation and eventual petroleum generation. / by Bryan C. Benitez-Nelson. / M.S.

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