Σκοπός της εργασίας είναι η μελέτη της ωριμότητας της οργανικής ύλης ορισμένων σχηματισμών της Ιόνιας Ζώνης, όπως οι αργιλικοί σχίστες του ανώτερου και κατώτερου Ιουρασικού, ο Ανώτερος Πυριτικός Ορίζοντας της Βίγλας του Κρητιδικού και οι βιτουμενιούχοι Ψαμμίτες του Τριτογενούς, χρησιμοποιώντας τεχνικές Οργανικής Πετρολογίας. Τα δείγματα συλλέχθηκαν από επιφανειακές εμφανίσεις στην Ήπειρο. Αρχικά χρησιμοποιήθηκαν οξέα (HCl-HF) για να απομακρυνθεί το μεγαλύτερο μέρος των ανθρακικών και πυριτικών ορυκτών. Το συμπύκνωμα που προέκυψε, αναμίχθηκε με ZnCl2 συγκεκριμένης πυκνότητας, ώστε να επέλθει βαρυτικός διαχωρισμός του πετρώματος σε ελαφρύ και βαρύ κλάσμα. Το οργανικό μέρος οξειδώθηκε χημικά για να υπολογιστεί η περιεκτικότητα σε Ολικό Οργανικό Άνθρακα. Στιλπνές τομές παρασκευάστηκαν με ανάμιξη του οργανικού υλικού με διάλυμα εποξικής ρητίνης και μελετήθηκαν στο ανθρακοπετρογραφικό μικροσκόπιο. Έμφαση δόθηκε στην ανακλαστικότητα βιτρινίτη και τον προσδιορισμό των maceral. Εφαρμόστηκε επίσης περιθλασιμετρία ακτίνων Χ για να προσδιοριστεί η ορυκτολογική σύσταση των πετρωμάτων. Διαπιστώθηκε ότι οι αργιλικοί σχίστες του κατώτερου Ιουρασικού περιέχουν οργανική ύλη (TOC: 4,74%), ο βαθμός ωριμότητας (Rr 0,68%) της οποίας βρίσκεται εντός του παραθύρου πετρελαίου. Ωστόσο περαιτέρω έρευνα εστιασμένη στους Κατω-Ιουρασικούς αργιλικούς σχίστες με Posidonia, με τη βοήθεια της Οργανικής Πετρολογίας και της πυρόλυσης Rock-Eval είναι αναγκαία, προκειμένου να διαπιστωθεί η ποιότητά τους ως μητρικά πετρώματα υδρογονανθράκων. / The main objective of this paper is to study by means of Organic Petrology techniques, the maturity of the dispersed organic matter from certain sedimentary formations of the Ionian Zone, such as the Bituminous Shale, the Upper Siliceous Vigla Formation and the Bituminous Sandstone. The samples were collected from outcropping sites located in the region of Epirus. Initially they were treated with acids (HCl-HF) to remove most of the carbonate and silicate minerals. Then a ZnCl2 solution was used to concentrate the organic-rich fraction. Total Organic Carbon (TOC) content was determined applying dichromate oxidation. Polished blocks were prepared from the concentrated organic matter mounted in epoxy resin and examined under the coal-petrography microscope. Emphasis was given to maceral identification and vitrinite reflectance (Rr) measurements, which provide information regarding the quality and the maturity of the organic matter respectively, with implications for the petroleum generation potential regardless the level of alteration. The TOC and Rr values (4.74% and 0.68%, respectively) confirm to the oil potential of the Lower Jurassic Posidonia Shale. Nevertheless, it is suggested that detailed and higher resolution sampling focusing on the Lower Posidonia Shale, as well as organic petrography analyses coupled with Rock-Eval pyrolysis should be carried out in order to accurately determine its quality as petroleum source rocks.

Σκοπός της παρούσας εργασίας είναι ο προσδιορισμός της ρύπανσης των ιζημάτων του Αλφειού ποταμού από στερεά σωματίδια, που προέρχονται από την εξόρυξη και την καύση του λιγνίτη Μεγαλόπολης. Βασικό αντικείμενο έρευνας αποτέλεσε η μικροσκοπική εξέταση του οργανικού μέρους, που είναι παρόν στα ιζήματα του Αλφειού ποταμού και η οργανική γεωχημική εξέταση επιλεγμένων δειγμάτων για την ανίχνευση πολυκυκλικών αρωματικών υδρογονανθράκων (polycyclic aromatic hydrocarbons, PAHs). Επιπλέον σε δείγματα λιγνίτη, ιπτάμενης τέφρας, τέφρας εστίας και τέφρας απόθεσης από το Λιγνιτικό Κέντρο Μεγαλόπολης πραγματοποιήθηκε μία σειρά εργαστηριακών προσδιορισμών, που περιέλαβε προσεγγιστική και άμεση ανάλυση, ανθρακοπετρογραφική εξέταση του λιγνίτη, καθώς και ορυκτολογικές και στοιχειακές αναλύσεις. Με βάση τις περιεκτικότητες του λιγνίτη και των παραπροϊόντων της καύσης του σε κύρια στοιχεία και ιχνοστοιχεία μπορεί να εκτιμηθεί η κινητικότητά τους κατά την καύση και το κατά πόσο αυτά διαφεύγουν στο περιβάλλον ή παραμένουν στο χώρο καύσης. Τα πιο ευκίνητα στοιχεία, που περιέχονται στο λιγνίτη Μεγαλόπολης, είναι τα Ba, Li, Mg, Rb και Sn, τα οποία μαζί με τα As και Pb, που συμμετέχουν στο λεπτόκοκκο τμήμα της ιπτάμενης τέφρας αποτελούν δυνητικούς ρυπαντές. Αντίθετα τα στοιχεία Ge, Mn, Th, Ti και Y είναι περιβαλλοντικά λιγότερο επικίνδυνα, καθώς συμμετέχουν στο τμήμα των παραπροϊόντων, που παραμένει στην τέφρα των ατμοηλεκτρικών σταθμών. Από μικροσκοπική παρατήρηση προέκυψε ότι το οργανικό υλικό, που είναι παρόν στα συγκεκριμένα ιζήματα αποτελείται κατά 78,4% κ.ό. από ανθρωπογενή σωματίδια, ενώ το υπόλοιπο 21,6% αποτελείται από φρέσκα φυτικά υπολείμματα. Το 81,5% κ.ό. του συνόλου των ανθρωπογενών σωματιδίων αποτελείται από κόκκους λιγνίτη και το 19,5% κ.ό. συνίσταται από εξανθρακώματα, που μεταφέρονται με την ιπτάμενη τέφρα και αποτίθενται στα ιζήματα. Τα ανθρακούχα σωματίδια στα ιζήματα του Αλφειού αντικατοπτρίζουν την ανθρακοπετρογραφική σύσταση του λιγνίτη Μεγαλόπολης, από την οποία εξαρτάται επίσης και η μορφή των εξανθρακωμάτων. Το επίπεδο των συγκεντρώσεων PAHs στα ιζήματα του Αλφειού είναι σχετικά χαμηλό (10-100 ng/g), ωστόσο η καύση του λιγνίτη συνεισφέρει σε ποσοστό 39,5% στην εκπομπή τους, ενώ το 23,5% προέρχεται από τον ίδιο το λιγνίτη. Η συμμετοχή των PAHs στα συγκεκριμένα ιζήματα φαίνεται να σχετίζεται ως ένα βαθμό με την παρουσία εξανθρακωμάτων, γεγονός που υποδεικνύει διεργασίες ρόφησης. Με την παρούσα εργασία αποδεικνύεται ότι η Οργανική Πετρολογία σε συνδυασμό με δεδομένα Οργανικής και Ανόργανης Γεωχημείας, μπορεί να αποτελέσει σημαντικό εργαλείο σε ό,τι αφορά στον προσδιορισμό της ρύπανσης ιζημάτων και εδαφών από την εκμετάλλευση γαιανθράκων. / The main target of the present study is the assessment of the contamination degree of Alfeios River sediments with solid particles deriving from mining and combustion of Megalopolis lignite. The objectives of the study were the microscopical examination of the organic matter present in these sediments, as well as the determination of the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in selected samples. Additionally in lignite, fly ash, bottom ash and ash deposit samples, were conducted a string of analyses including, proximate and ultimate analyses along with mineralogical and elemental determinations. The mobility of major and trace elements during the combustion of lignite can be estimated according to the concentration of these elements in bulk lignite and its combustion by-products. Based on these results the most mobile and thus more environmentally "sensitive" elements in Megalopolis lignite are As, Ba, Li, Mg, Pb, Rb and Sn, while Ge, Mn, Th, Ti and Y are the less mobile elements participating mostly in bottom ash. From the microscopical study of the organic matter present in Alfeios sediments it is evident that it consists of 78,4% of anthropogenic particles, while the remaining 21,6% consists of fresh plant remnants. The 81,5% of the anthropogenic particles consists of lignite particles deriving from mining and transportation processes and the remaining 19,5% consists of char particles transported and deposited as portion of the fly ash produced in Megalopolis Lignite Centre. The coal-petrographic composition of lignite particles is similar to the coal-petrographic composition of Megalopolis lignite. The latter is also responsible for the shape and texture of the char particles. The PAHs concentration level is rather low, ranging from 10-100 ng/g. Nevertheless lignite combustion along with the Megalopolis lignite itself are the main emission sources of such compounds accounting for 39,5% and 23,5% respectively. The presence of PAHs is related to the presence of char particles, probably via sortion procedures. The results of this study show that Organic Petrology can be a useful tool in environmental science and particularly in the field of contamination of soils and sediments from coal exploitation, if combined with Organic and Inorganic Geochemical data.

Igneous intrusion can change the geochemical and petrographic properties of sedimentary organic matter (such as coals and organic-rich clays or shales) including vitrinite reflectance, maceral petrographic composition, mineralogy, stable isotope composition, trace element composition, and bulk geochemistry. Igneous intrusions into coals and organic-rich rocks may have contributed to global warming in the geologic past by causing the release of greenhouse gases. Evidence for the release of large amounts of thermogenic CH4 from the organics would include significant;13Corg enrichment in the residual organic matter. However, 13Corg of thermally altered organic matter in coals and shales adjacent to intrusions often show negative shifts and, in some cases, ambiguous or positive trends. Previous studies have evaluated 13Corg of bulk samples rather than that of individual components, or macerals. As different macerals have different isotopic compositions, maceral-specific trends may be masked by variations in maceral composition of the whole-coal samples. It is important to explain the evolution of different geochemical and petrographic signatures in coals, coals macerals, and organic-rich sedimentary rocks close to an intrusion. This study evaluates the following three hypotheses: (1) thermally altered coals show different geochemical trends compared with coals that have undergone normal burial maturation; (2) if a large-scale release of 13C-depleted thermogenic CH4 resulted from intrusion of the coal, then it should have produced 13C-enriched coal and vitrinite macerals (the most abundant components of the coal) adjacent to the intrusion due to the release of light gases; and (3) 13Corg gets heavier with the increase in heat alteration approaching an intrusion due to the release of isotopically light gases. The current study reports petrographic, bulk geochemical (proximate, and ultimate), 13Corg data (whole-coal/shale samples and vitrinite macerals separated via density-gradient centrifugation, (DGC)), density data (vitrinite macerals), and Rock-Eval pyrolysis data for occurrences of thermally altered Springfield (No. 5) Coal (Pennsylvanian), Danville (No. 7) Coal (Pennsylvanian), and an organic-rich shale in the southern part of the Illinois Basin. Petrographic analysis shows an increase in vitrinite reflectance (Rm) from background levels of 0.55% up to ~4.80% in the Springfield (No. 5) Coal, 0.66% to 4.40% in the Danville (No. 7) Coal, and 0.71% to 4.78% for organic-rich shale; a loss of liptinite macerals, formation of isotropic coke and, at the intrusion contact, even development of fine-grained mosaic anisotropic coke texture. Volatile matter (VM) content decreases and fixed carbon (FC) content, ash, and mineral matter increase approaching the coal/intrusion contact. Carbon increases whereas nitrogen, hydrogen, and oxygen decrease approaching the intrusions. The presence of carbonate minerals (confirmed by X-ray diffraction and petrographic analysis) has a significant impact on proximate and ultimate data. However, even after removal of carbonates, trends for VM vs. vitrinite reflectance, %C vs. Rm, and H vs. C do not follow typical trends associated with normal burial coalification. Approaching the contacts, free oil content (S1), remaining hydrocarbon potential (S2), carbon dioxide from pyrolysis of the organic matter (S3), and hydrogen (HI) and oxygen (OI) indices decrease whereas thermal maturity (Tmax, ⁰C) increases. In addition, HI vs. VM, S2 vs. Rm, and Tmax vs. Rm diverge from pathways seen in previous studies. Trends in most of the Rock-Eval parameters in the organic-rich shale studied here are less clear due to the degree of variation in organic matter content, but a clear increase in thermal maturity (Tmax, C) is seen. There are no significant changes in 13Corg in the whole-coal samples (WCM) of the Springfield (No. 5) Coal (-25.28 / to -24.88 /), Danville (No. 7) whole coals (-25.37 / to -24.76 /), and in the DGC-separated vitrinites (-25.33 / to -24.96 /) of the Springfield (No. 5) Coal approaching the intrusion. However, the organic-rich shale transect shows a 1.31 / positive shift in 13C (from -25.06 / to -23.87 /) approaching the intrusion. DGC-separated vitrinite densities range from 1.268 g/mL in the unaltered coal to 1.523 g/mL at the coal/intrusion contact. For the vitrinite concentrates, density shows a clear correlation with Rm, %Cdaf, Hdaf, H/C, TOC, and 13Corg. These geochemical data suggest that these coals may have followed a different maturation track because of the geologically rapid heating associated with the intrusive event. It is also suggested here that the natural coke textures produced by such rapid geological heating may differ from those observed for metallurgical cokes produced under standard industrial coking conditions. Typically, in an industrial coke oven, a coal of this initial rank (Ro = ~ 0.6%) would produce an isotropic coke, rather than the fine-grained circular anisotropic coke seen here. The development of this texture may reflect differences due to heating rates or, alternatively, may indicate "pre-heating" of the coal during the intrusion event. Changes in the isotopic signatures are not of a magnitude that would be expected if significant thermogenic CH4 had been generated by the intrusive event. Moreover, there is no petrographic evidence for condensed or immobilized thermal products due to rapid pyrolysis (12C-rich pyrolytic carbon) close to the intrusion. These geochemical and petrographic data suggest there was only minimal CH4 generation associated with the rapid heating of the coals and organic-rich sedimentary rocks by the intrusion. In addition, there is no evidence for 13C-depleted condensed gas or pyrolytic carbon at the intrusion contact that could have moderated the isotopic signature. These data agree with previously reported data from this laboratory (Rahman et al., 2014, in review) and others (Gröcke et al., 2009; Yoksoulian, 2010) that indicate no clear evidence for large-scale CH4 generation due to the rapid heating or igneous intrusion in coals or sedimentary rocks.

A Bacia de Santos é uma das principais bacias brasileiras para exploração e produção de hidrocarbonetos, e vem recebendo grandes investimentos em pesquisa nos últimos anos. O estudo das rochas geradoras serve como importante ferramenta para o estudo de modelos de geração, explusão e migração de hidrocarbonetos e na identificação de sistemas petrolíferos. O principal objetivo deste trabalho é a identificação de intervalos e áreas com maior potential para a geração de hidrocarbonetos dentro do pacote sedimentar estudado (Cretáceo-Terciário). As amostras de calha de 6 poços exploratórios, obtidas junto à Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP), foram analisadas através da geoquímica orgânica (Carbono Orgânico Total (COT), Pirólise Rock Eval e análise de Biomarcadores) e da petrologia orgânica (Reflectância da Vitrinita e Palinofácies) e foram interpretadas juntamente com os resultados do estudo de outros 10 poços exploratórios, obtidos pela Geochemical Solutions International cedidos para este trabalho. Esses 16 poços formam um perfil strike SW-NE que recobre praticamente toda a extensão da bacia. Amostras das formações Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá e Florianópolis foram analisadas, apresentando resultados semelhantes para o tipo de matéria orgânica, sua origem e ambiente deposicional (querogênio tipo II e III, originado pela mistura de material de origem terrestre e marinha depositado em ambiente transicional levemente oxidante). Os perfis analisados identificaram dois intervalos de maior conteúdo de carbono orgânico, maturação e potencial de geração de petróleo, um entre 2500 e 3000 metros de profundidade, que pode estar relacionado a eventos transgressivos do Terciário, e outro entre 4000 a 5000 metros de profundidade, possivelmente relacionado a um importante evento transgressivo de caráter regional ocorrido durante o Turoniano. A matéria orgânica encontrada nos poços situados na região sudoeste do perfil foi a que apresentou as melhores condições para a geração de hidrocarbonetos, tornando-se mais empobrecida na direção nordeste. Com base nos resultados geoquímicos e petrográficos obtidos, a matéria orgânica presente na Formação Itajaí-Açu possui o melhor potencial para geração de hidrocarbonetos, principalmente na porção basal do intervalo, na região sudoeste da bacia. / The Santos Basin is one of the main Brazilian sedimentary basin for hydrocarbon exploration and production and has been the focus of major geological research on hydrocarbon occurrences in recent years. Source rock studies are important tools for construction of hydrocarbon generation, expulsion and migration models of the basin and for identifying petroleum systems. The main objective of the present study is to identify areas and intervals with hydrocarbon generation potential inside the sedimentary sequence studied (Cretaceous-Tertiary). Cutting samples from 6 petroleum exploration wells obtained from the National Agency of Petroleum, Natural Gas and Biofuels (ANP) were analysed by organic geochemical methods (Total Organic Carbon (TOC), Rock Eval Pyrolysis and Biomarkers analysis) and organic petrography (Vitrinite Reflectance and Palynofacies) and were interpreted together with results from organic geochemical studies on samples from 10 addictional petroleum exploratory wells obtained from Geochemical Solution International (GSI), provided for this study. These 16 wells form a SW-NE strike section, that covers the basin almost completely in this direction. The samples from Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá and Florianópolis formations show similar results in regard to organic matter type, its origin and depositional paleoenvironment (type II-III kerogen, indicating a contribution of terrestrial and marine material, deposited in a transitional and slightly oxic environment). The stratigraphic profiles analysed identify two intervals with relatively high organic matter content, maturation and hydrocarbon generation potential, one between 2500 and 3000 meters depth, perhaps related to a Tertiary transgressive event and the other one between 4000 and 5000 meters depth, possibly related to an important regional transgressive event, which occurred during the Turonian. The organic matter encountered in the well samples located in the southwest of the SW-NE section has the best potential for hydrocarbon generation, whereas the organic matter of well samples located in the northwest direction has less potential to form hydrocarbons. Based on the results of the present study, the organic matter present in the Itajaí-Açu Formation has the best potential for hydrocarbon generation, in particular in the basal part of the formation in the southwest region of the basin.

A Bacia de Santos é uma das principais bacias brasileiras para exploração e produção de hidrocarbonetos, e vem recebendo grandes investimentos em pesquisa nos últimos anos. O estudo das rochas geradoras serve como importante ferramenta para o estudo de modelos de geração, explusão e migração de hidrocarbonetos e na identificação de sistemas petrolíferos. O principal objetivo deste trabalho é a identificação de intervalos e áreas com maior potential para a geração de hidrocarbonetos dentro do pacote sedimentar estudado (Cretáceo-Terciário). As amostras de calha de 6 poços exploratórios, obtidas junto à Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP), foram analisadas através da geoquímica orgânica (Carbono Orgânico Total (COT), Pirólise Rock Eval e análise de Biomarcadores) e da petrologia orgânica (Reflectância da Vitrinita e Palinofácies) e foram interpretadas juntamente com os resultados do estudo de outros 10 poços exploratórios, obtidos pela Geochemical Solutions International cedidos para este trabalho. Esses 16 poços formam um perfil strike SW-NE que recobre praticamente toda a extensão da bacia. Amostras das formações Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá e Florianópolis foram analisadas, apresentando resultados semelhantes para o tipo de matéria orgânica, sua origem e ambiente deposicional (querogênio tipo II e III, originado pela mistura de material de origem terrestre e marinha depositado em ambiente transicional levemente oxidante). Os perfis analisados identificaram dois intervalos de maior conteúdo de carbono orgânico, maturação e potencial de geração de petróleo, um entre 2500 e 3000 metros de profundidade, que pode estar relacionado a eventos transgressivos do Terciário, e outro entre 4000 a 5000 metros de profundidade, possivelmente relacionado a um importante evento transgressivo de caráter regional ocorrido durante o Turoniano. A matéria orgânica encontrada nos poços situados na região sudoeste do perfil foi a que apresentou as melhores condições para a geração de hidrocarbonetos, tornando-se mais empobrecida na direção nordeste. Com base nos resultados geoquímicos e petrográficos obtidos, a matéria orgânica presente na Formação Itajaí-Açu possui o melhor potencial para geração de hidrocarbonetos, principalmente na porção basal do intervalo, na região sudoeste da bacia. / The Santos Basin is one of the main Brazilian sedimentary basin for hydrocarbon exploration and production and has been the focus of major geological research on hydrocarbon occurrences in recent years. Source rock studies are important tools for construction of hydrocarbon generation, expulsion and migration models of the basin and for identifying petroleum systems. The main objective of the present study is to identify areas and intervals with hydrocarbon generation potential inside the sedimentary sequence studied (Cretaceous-Tertiary). Cutting samples from 6 petroleum exploration wells obtained from the National Agency of Petroleum, Natural Gas and Biofuels (ANP) were analysed by organic geochemical methods (Total Organic Carbon (TOC), Rock Eval Pyrolysis and Biomarkers analysis) and organic petrography (Vitrinite Reflectance and Palynofacies) and were interpreted together with results from organic geochemical studies on samples from 10 addictional petroleum exploratory wells obtained from Geochemical Solution International (GSI), provided for this study. These 16 wells form a SW-NE strike section, that covers the basin almost completely in this direction. The samples from Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá and Florianópolis formations show similar results in regard to organic matter type, its origin and depositional paleoenvironment (type II-III kerogen, indicating a contribution of terrestrial and marine material, deposited in a transitional and slightly oxic environment). The stratigraphic profiles analysed identify two intervals with relatively high organic matter content, maturation and hydrocarbon generation potential, one between 2500 and 3000 meters depth, perhaps related to a Tertiary transgressive event and the other one between 4000 and 5000 meters depth, possibly related to an important regional transgressive event, which occurred during the Turonian. The organic matter encountered in the well samples located in the southwest of the SW-NE section has the best potential for hydrocarbon generation, whereas the organic matter of well samples located in the northwest direction has less potential to form hydrocarbons. Based on the results of the present study, the organic matter present in the Itajaí-Açu Formation has the best potential for hydrocarbon generation, in particular in the basal part of the formation in the southwest region of the basin.

A Bacia de Santos é uma das principais bacias brasileiras para exploração e produção de hidrocarbonetos, e vem recebendo grandes investimentos em pesquisa nos últimos anos. O estudo das rochas geradoras serve como importante ferramenta para o estudo de modelos de geração, explusão e migração de hidrocarbonetos e na identificação de sistemas petrolíferos. O principal objetivo deste trabalho é a identificação de intervalos e áreas com maior potential para a geração de hidrocarbonetos dentro do pacote sedimentar estudado (Cretáceo-Terciário). As amostras de calha de 6 poços exploratórios, obtidas junto à Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP), foram analisadas através da geoquímica orgânica (Carbono Orgânico Total (COT), Pirólise Rock Eval e análise de Biomarcadores) e da petrologia orgânica (Reflectância da Vitrinita e Palinofácies) e foram interpretadas juntamente com os resultados do estudo de outros 10 poços exploratórios, obtidos pela Geochemical Solutions International cedidos para este trabalho. Esses 16 poços formam um perfil strike SW-NE que recobre praticamente toda a extensão da bacia. Amostras das formações Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá e Florianópolis foram analisadas, apresentando resultados semelhantes para o tipo de matéria orgânica, sua origem e ambiente deposicional (querogênio tipo II e III, originado pela mistura de material de origem terrestre e marinha depositado em ambiente transicional levemente oxidante). Os perfis analisados identificaram dois intervalos de maior conteúdo de carbono orgânico, maturação e potencial de geração de petróleo, um entre 2500 e 3000 metros de profundidade, que pode estar relacionado a eventos transgressivos do Terciário, e outro entre 4000 a 5000 metros de profundidade, possivelmente relacionado a um importante evento transgressivo de caráter regional ocorrido durante o Turoniano. A matéria orgânica encontrada nos poços situados na região sudoeste do perfil foi a que apresentou as melhores condições para a geração de hidrocarbonetos, tornando-se mais empobrecida na direção nordeste. Com base nos resultados geoquímicos e petrográficos obtidos, a matéria orgânica presente na Formação Itajaí-Açu possui o melhor potencial para geração de hidrocarbonetos, principalmente na porção basal do intervalo, na região sudoeste da bacia. / The Santos Basin is one of the main Brazilian sedimentary basin for hydrocarbon exploration and production and has been the focus of major geological research on hydrocarbon occurrences in recent years. Source rock studies are important tools for construction of hydrocarbon generation, expulsion and migration models of the basin and for identifying petroleum systems. The main objective of the present study is to identify areas and intervals with hydrocarbon generation potential inside the sedimentary sequence studied (Cretaceous-Tertiary). Cutting samples from 6 petroleum exploration wells obtained from the National Agency of Petroleum, Natural Gas and Biofuels (ANP) were analysed by organic geochemical methods (Total Organic Carbon (TOC), Rock Eval Pyrolysis and Biomarkers analysis) and organic petrography (Vitrinite Reflectance and Palynofacies) and were interpreted together with results from organic geochemical studies on samples from 10 addictional petroleum exploratory wells obtained from Geochemical Solution International (GSI), provided for this study. These 16 wells form a SW-NE strike section, that covers the basin almost completely in this direction. The samples from Marambaia, Juréia, Santos, Itajaí-Açu, Itanhaem, Guarujá and Florianópolis formations show similar results in regard to organic matter type, its origin and depositional paleoenvironment (type II-III kerogen, indicating a contribution of terrestrial and marine material, deposited in a transitional and slightly oxic environment). The stratigraphic profiles analysed identify two intervals with relatively high organic matter content, maturation and hydrocarbon generation potential, one between 2500 and 3000 meters depth, perhaps related to a Tertiary transgressive event and the other one between 4000 and 5000 meters depth, possibly related to an important regional transgressive event, which occurred during the Turonian. The organic matter encountered in the well samples located in the southwest of the SW-NE section has the best potential for hydrocarbon generation, whereas the organic matter of well samples located in the northwest direction has less potential to form hydrocarbons. Based on the results of the present study, the organic matter present in the Itajaí-Açu Formation has the best potential for hydrocarbon generation, in particular in the basal part of the formation in the southwest region of the basin.

Coal seam gas has been recognised as a new, potential energy resource in New Zealand. Exploration and assessment programmes carried out by various companies have evaluated the resource and indicated that this unconventional gas may form a part of New Zealand's future energy supply. This study has delineated some of the controls between coal properties and gas content in coal seams in selected New Zealand locations. Four coal cores, one from Huntly (Eocene), two from Ohai (Cretaceous) and one from Greymouth (Cretaceous), have been sampled and analysed in terms of gas content and coal properties. Methods used include proximate, sulphur and calorifc value analyses; ash constituent determination; rank assessment; macroscopic analysis; mineralogical analysis; maceral analysis; and gas analyses (desorption, adsorption, gas quality and gas isotopes). Coal cores varied in rank from sub-bituminous B-A (Huntly); sub-bituminous C-A (Ohai); and high volatile bituminous A (Greymouth). All locations contained high vitrinite content (~85 %) with overall relatively low mineral matter observed in most samples. Mineral matter consisted of both detrital grains (quartz in matrix material) and infilling pores and fractures (clays in fusinite pores; carbonates in fractures). Average gas contents were 1.6 m3/t in the Huntly core, 4.7 m3/t in the Ohai cores, and 2.35 m3/t in the Greymouth core. The Ohai core contained more gas and was more saturated than the other cores. Carbon isotopes indicated that the Ohai gas composition was more mature, containing heavier 13C isotopes than either the Huntly or Greymouth gas samples. This indicates the gas was derived from a mixed biogenic and thermogenic source. The Huntly and Greymouth gases appear to be derived from a biogenic (by CO2 reduction) source. The ash yield proved to be the dominant control on gas volume in all locations when the ash yield was above 10 %. Below 10 % the amount of gas variation is unrelated to ash yield. Although organic content had some influence on gas volume, associations were basin and /or rank dependant. In the Huntly core total gas content and structured vitrinite increased together. Although this relationship did not appear in the other cores, in the Ohai SC3 core lost gas and fusinite are associated with each other, while desmocollinite (unstructured vitrinite) correlated positively with residual gas in the Greymouth core. Although it is generally accepted that higher rank coals will have higher adsorption capacities, this was not seen in this data set. Although the lowest rank coal (Huntly) contains the lowest adsorption capacity, the highest adsorption capacity was not seen in the highest rank coal (Greymouth), but in the Ohai coal instead. The Ohai core acted like a higher rank coal with respect to the Greymouth coal, in terms of adsorption capacity, isotopic signatures and gas volume. Two hypothesis can be used to explain these results: (1) That a thermogenically derived gas migrated from down-dip of the SC3 and SC1 drill holes and saturated the section. (2) Rank measurements (e.g. proximate analyses) have a fairly wide variance in both the Greymouth and Ohai coal cores, thus it maybe feasible that the Ohai cores may be higher rank coal than the Greymouth coal core. Although the second hypothesis may explain the adsorption capacity, isotopic signatures and the gas volume, when the data is plotted on a Suggate rank curve, the Ohai coal core is clearly lower rank than the Greymouth core. Thus, pending additional data, the first hypothesis is favoured.

Στην παρούσα διατριβή διερευνώνται οι διεργασίες που λαμβάνουν χώρα στο τυρφογενές στρώμα, έτσι ώστε να ανιχνευθούν οι μεταβολές των φυσικών, πετρογραφικών και χημικών χαρακτηριστικών των οργανικών ιζημάτων συναρτήσει των παραμέτρων τυρφογένεσης, όπως το κλίμα και οι τοπικές γεωλογικές συνθήκες. Απώτερο στόχο συνιστά η μοντελοποίηση παλαιοπεριβαλλόντων γένεσης των γαιανθράκων. Τέλος αξιολογείται η συμπεριφορά των ορυκτών, η γεωχημική συγγένεια και η κινητικότητα των ιχνοστοιχείων σε ενδεχόμενη αξιοποίηση της τύρφης για ενεργειακούς σκοπούς. Η έρευνα εστιάστηκε στους τυρφώνες Φιλίππων (Ν. Καβάλας) και Νησιού (Ν. Πέλλας) στη Βόρεια Ελλάδα και στον παράκτιο τυρφώνα του Κεριού (Ν. Ζακύνθου). Εξετάστηκαν τα ποιοτικά και ποσοτικά χαρακτηριστικά των οργανικών και ανοργάνων ιζημάτων που πληρούν τους τυρφώνες, αλλά και τα αντίστοιχα τυρφογενετικά φυτικά είδη, που αναπτύσσονται στους ενεργούς τυρφώνες Νησιού και Κεριού. Συγκεκριμένα πραγματοποιήθηκαν προσεγγιστική και στοιχειακή ανάλυση, ορυκτολογικοί προσδιορισμοί, εξέταση στιλπνών τομών με ηλεκτρονική μικροσκοπία σάρωσης, αναλύσεις τόσο της ανόργανης χημικής σύστασης (XRF, ICP/OES, ICP/MS), όσο και της οργανικής χημικής σύστασης (13C CP/MAS NMR, FTIR, py-GC/MS), όπως επίσης και ανθρακοπετρογραφικοί προσδιορισμοί. Αναφορικά με τους ορυκτολογικούς προσδιορισμούς εφαρμόστηκε μέθοδος πλήρους ποσοτικοποίησης των ορυκτών φάσεων με εφαρμογή περιθλασιμετρίας ακτίνων Χ σε ξηρό δείγμα, συνυπολογίζοντας την επίδραση του οργανικού υλικού. Αξιολογήθηκε επίσης η εφαρμογή περιθλασιμετρίας ακτίνων Χ σε υπολείμματα οξείδωσης της τύρφης. Οι τυρφώνες Φιλίππων και Νησιού συνιστούν παρόμοια περιβάλλοντα τυρφογένεσης, καθώς και οι δύο αναπτύσσονται σε ενδοηπειρωτικές λεκάνες, των οποίων η βύθιση ελέγχεται κυρίως από τεκτονικούς παράγοντες, με την ανάπτυξη παρόμοιων τυρφογενετικών φυτικών ειδών, όπως Cyperaceae και ειδικότερα το ασβεστόφιλο Cladium mariscus και διάφορα Carex spp., ενώ επηρεάζονται στη σύγχρονη εξέλιξή τους τουλάχιστον και οι δύο από καρστικούς υδροφόρους, συνιστώντας τοπογενείς ποωτυρφώνες, με κύριο μορφολογικό χαρακτηριστικό την παρουσία εξάρσεων (hummocks). Αντίθετα στο Κερί η τυρφογένεση αναπτύχθηκε σε παράκτιο περιβάλλον με τη βύθιση (δηλ. το πλημμύρισμα) να ελέγχεται τόσο από τεκτονικούς παράγοντες, όσο και από τις ευστατικές κινήσεις της θάλασσας, και το πεδίο χαρακτηρίζεται ως υφάλμυρος ποωτυρφώνας. Στο Κερί πέρα από ελόφυτα γλυκών νερών, αναπτύσσονται και είδη υφάλμυρων οικολογικών συνθηκών, όπως Scirpus maritimus και Juncus maritimus, λόγω της υφαλμύρινσης του υδροφόρου ορίζοντα. Με βάση τα χαρακτηριστικά τυρφογένεσης στους τρεις τυρφώνες τροποποιήθηκαν οι δείκτες φάσεων, που χρησιμοποιούνται στη γεωλογία γαιανθράκων, έτσι ώστε να αντανακλούν καλύτερα τις συγγενετικές διεργασίες στο ακρότελμα. Επιπρόσθετα περιγράφονται τόσο ποιοτικά, όσο και ποσοτικά τα χαρακτηριστικά των ιζημάτων στο τελματικό και το λιμνοτελματικό πεδίο, ενώ εκτιμάται επίσης και η πορεία της ενανθράκωσης των υπό μελέτη οργανογενών ιζημάτων, έτσι ώστε να εξαχθούν διαγνωστικές παράμετροι εφαρμογής στα παλαιοπεριβάλλοντα τυρφογένεσης. / The present study focuses on the processes taking place in the peatigenic layer (acrotelma), in order to trace the alteration of physical, chemical and petrographical features of the organic sediments in connection with the peat-forming factors. The ulterior aim is to propose a model for interpreting the coal-forming palaeoenvorinmental conditions. Finally, the mobility of the toxic trace elements is evaluated, in case of peat utilization for power generation in the future. Cores from the peatlands of Philippi (Prefecture of Kavala) and Nissi (Prefecture of Pella) in Northern Greece and of Keri (Zakynthos Island) in Southern Greece, were examined. The objective was to determine the qualitative and quantitative characteristics of the organogenic sediments hosted in the peatlands and additionally, of the peat-forming plants that grow on the surface of the Nissi and Keri mires. A series of laboratory examinations were performed on the collected samples, including proximate and ultimate analyses, mineralogical determinations by applying X-ray diffraction and SEM, inorganic geochemical analyses using XRF, ICP-OES and ICP-MS, organic geochemical analyses using 13C CP/MAS NMR, FTIR and py-GC/MS techniques and organic petrographical examinations on intact samples. Regarding the mineralogical determinations a method for full quantification of the mineral phases has been developed taking into account the pattern of the organic phases. Additionally the application of X-ray diffraction in oxidized peat residues has been evaluated. The Philippi and Nissi peatlands comprise similar peat-forming environments, since: (a) both developed in intermontane basins, the subsidence of which is controlled mainly by the tectonic activity, (b) Cyperaceae, mainly Cladium mariscus and various Carex spp., constitutes the main peat-forming plants, (c) whereas both are affected by karstic waters. They are fens for most of the peat accumulation period. On the contrary, in Keri the peat accumulation developed in a coastal environment due to paludification controlled both by the tectonic activity and the eustatic sea level changes, and the environment is characterized as a brackish mire, where additionally Scirpus maritimus και Juncus maritimus thrive. Taking in consideration the peat-forming features in the three studied peatlands the coal facies indices were modified in order to reflect more precisely the syngenetic processes in the acrotelma. Additionally a model is provided that describes both qualitatively and quantitatively the characteristics of the organogenic sediments deposited in the telmatic and the limnotelmatic fields. Furthermore, the coalification pathways of the studied sediments are interpreted, in order to obtain diagnostic parameters that can be applied to coal palaeoenvironmental studies.

Coal seam gas has been recognised as a new, potential energy resource in New Zealand. Exploration and assessment programmes carried out by various companies have evaluated the resource and indicated that this unconventional gas may form a part of New Zealand's future energy supply. This study has delineated some of the controls between coal properties and gas content in coal seams in selected New Zealand locations. Four coal cores, one from Huntly (Eocene), two from Ohai (Cretaceous) and one from Greymouth (Cretaceous), have been sampled and analysed in terms of gas content and coal properties. Methods used include proximate, sulphur and calorifc value analyses; ash constituent determination; rank assessment; macroscopic analysis; mineralogical analysis; maceral analysis; and gas analyses (desorption, adsorption, gas quality and gas isotopes). Coal cores varied in rank from sub-bituminous B-A (Huntly); sub-bituminous C-A (Ohai); and high volatile bituminous A (Greymouth). All locations contained high vitrinite content (~85 %) with overall relatively low mineral matter observed in most samples. Mineral matter consisted of both detrital grains (quartz in matrix material) and infilling pores and fractures (clays in fusinite pores; carbonates in fractures). Average gas contents were 1.6 m3/t in the Huntly core, 4.7 m3/t in the Ohai cores, and 2.35 m3/t in the Greymouth core. The Ohai core contained more gas and was more saturated than the other cores. Carbon isotopes indicated that the Ohai gas composition was more mature, containing heavier 13C isotopes than either the Huntly or Greymouth gas samples. This indicates the gas was derived from a mixed biogenic and thermogenic source. The Huntly and Greymouth gases appear to be derived from a biogenic (by CO2 reduction) source. The ash yield proved to be the dominant control on gas volume in all locations when the ash yield was above 10 %. Below 10 % the amount of gas variation is unrelated to ash yield. Although organic content had some influence on gas volume, associations were basin and /or rank dependant. In the Huntly core total gas content and structured vitrinite increased together. Although this relationship did not appear in the other cores, in the Ohai SC3 core lost gas and fusinite are associated with each other, while desmocollinite (unstructured vitrinite) correlated positively with residual gas in the Greymouth core. Although it is generally accepted that higher rank coals will have higher adsorption capacities, this was not seen in this data set. Although the lowest rank coal (Huntly) contains the lowest adsorption capacity, the highest adsorption capacity was not seen in the highest rank coal (Greymouth), but in the Ohai coal instead. The Ohai core acted like a higher rank coal with respect to the Greymouth coal, in terms of adsorption capacity, isotopic signatures and gas volume. Two hypothesis can be used to explain these results: (1) That a thermogenically derived gas migrated from down-dip of the SC3 and SC1 drill holes and saturated the section. (2) Rank measurements (e.g. proximate analyses) have a fairly wide variance in both the Greymouth and Ohai coal cores, thus it maybe feasible that the Ohai cores may be higher rank coal than the Greymouth coal core. Although the second hypothesis may explain the adsorption capacity, isotopic signatures and the gas volume, when the data is plotted on a Suggate rank curve, the Ohai coal core is clearly lower rank than the Greymouth core. Thus, pending additional data, the first hypothesis is favoured.