The Cleveland Shale displays a characteristic and distinctive pattern of promontories and recessed intervals on weathered outcrops, which appears to represent cyclicity. This weathering pattern can be observed in other shales, both within and outside the Appalachian Basin; so determining the nature of these cycles may be critical for understanding the origin of, not only the Cleveland Shale, but also of black shales in general. Cyclicity in the Cleveland was examined on a decimeter-to-meter scale using lithologic characterization, gamma-ray stratigraphy and x-ray fluorescence, and on a millimeter-to-centimeter scale using organic petrography. Lithologic characterization and gamma-ray stratigraphy revealed Milankovitch-band fourth- and fifth-order cyclicity related to changes in the earth’s orbital eccentricity (100 ka) and obliquity of the earth’s axis (42 ka), respectively. Sedimentological changes associated with these cycles were identified through organic petrography and x-ray fluorescence. A depositional model was developed from these data sets, which suggests that cyclic changes in local climate — from cold and wet to warm and dry — controlled advancing and retreating glaciation in the adjacent Acadian mountains as well as concomitant sea-level rise and fall in the Black-Shale Sea. Such changes would have controlled sediment influx to the sea and are thought to be reflected in the cycles.

The majority of economic gold deposits in NSW are associated with Ordovician-aged igneous rocks and are examples of the Cu-Au porphyry-skarn-epithermal association commonly developed in convergent margin to orogenic settings. They are among the oldest porphyry Cu-Au deposits in the Pacific Rim region. They are similar to younger deposits in terms of tectonic setting and structure, but the largest are chemically distinct, being associated with shoshonite magmas (Cadia, Ridgeway and Northparkes). The Lachlan Fold Belt (LFB) porphyries are subdivided into four sub-groups based mainly on their age relative to development of the Lachlan Transverse Zone (LTZ) structure. Two subgroups pre-date the LTZ, one group is syn�LTZ and one group post-dates the LTZ. No mineralisation has been found or reported among pre-I.TZ porphyries. but it is common in post- . l Z_ porphyries. Petrographic analysis and microprobe results establish a wide range of primary and secondary features within the Ordovician rocks examined in this study. Cale alkaline to shoshonitic affinities are supported by the variable abundance of primary K-feldspars. Primary mineral phases such as pyroxenes and igneous magnetite provide an indication of fractioning mineral assemblages responsible for igneous trends in magma chemistry. The hydrothermal mineral assemblages documented in these LFB study areas are characteristic of younger Cu-Au Porphyry style mineralisation. As expected, the most pervasive alteration is associated with highly mineralised shoshonitic Ordovician rocks at Ridgeway, and Cadia. the less strongly mineralised calc alkaline Ordovician rocks at Cargo. Copper Ilill and Fairholme. are correspondingly less strongly altered overall. although secondary mineral assemblages are locally abundant. Many varieties of oxides and carbonates are observed at the different study localities. Most of the studied samples conform to igneous chemical trends because they are weakly altered, although post magmatic processes, such as veining, are detectable in certain trends. The K2O enrichment of the studied samples is consistent with subductionmoditied mantle wedge sources. A few effects, such as the high Fe203 contents of some Ridgeway samples, probably reflect porphyry-style hydrothermal alteration processes. Host rocks at the Cadia and Ridgeway are entirely alkalic on the K2O versus SiO2 plot and shoshonitic on the Total Alkalies versus SiO2 plot. Igneous rocks at the other deposits display a range of compositions between low K tholeiites to shoshonites that in some cases reflects multiple igneous suites. The LREE and L1LE enrichments, and HFSE depletions (Nb, Ta and Ti) of the magmas associated with these deposits are characteristics of a subduction-related tectonic setting. They all fall in the volcanic-arc granite and syn-collisional granite field of the Nb-Y tectonic discrimination diagram. Several magma types are identified by differences in the HFSE and REE trends. Differences in the extent and style of magma fractionation are evident in the trace element data. The Ridgeway samples define a wider range of trace element concentrations than the Cadia samples that may indicate a greater extent of fractionation during emplacement of the Ridgeway magmas. Fairholme samples display a high Nh and /If trends that are distinct from the main fields on Zr variation diagrams. Compositional differences between larger Cu-Au deposits, Cadia-Ridgeway and smaller deposits, Copper Ifill, Cargo and Fairholme are evident in terms of Nb-Ta depletion and variation. The smaller deposits show constant Nb/Ta or negative Nb/Ta trends that extend to high Nb. The larger deposits display positive Nb/Ta trends that do not extend to high Nb. This distinction reflects a difference of preferential incorporation of Nb in a mineral phase (magnetite). Comparisons between Cadia-Ridgeway and other shoshonite (altered samples of Bajo de la Alumbrera, Argentina), calc alkaline magmas from New Zealand and rocks from other areas indicate that Nb/Ta is not directly correlated with the shoshonitic classification, K2O vs. SiO2, and that the Cadia-Ridgeway Nb and Ta variation is not the result of alteration. The fact that the weakly altered LFB Capertee shoshonites exhibit a narrow range of Nb and low Nb/Ta suggest the shoshonite trend for the LFB as a whole is a steep one on the Nb/Ta versus Nb plot. The results of this study could provide important information for exploration within the LFB. Only the Cadia and Ridgeway deposits display a wide range of Nb/Ta values and lack the near-horizontal trend seen for other localities associated with smaller deposits. The tectonic evolution of the LFB is a major factor contributing to occurrence of large porphyry Cu-Au deposits. The sequence of important events, however, commences with sub-crustal generation of oxidised magma and finishes with efficient Cu-Au accumulation by hydrothermal processes at favourable structural sites. The increase in Au-Cu deposit size from small (Copper Hill-Cargo) to world class (Cadia-Ridgeway) indicates the importance of magma composition during this process. The most obvious differences between the Cadia-Ridgeway and New Zealand rocks is that the latter are volcanic in origin and associated with an arc-back arc system. Therefore, they did not form in a tectonic regime suitable for the evolution of porphyries and the focussed movement of hydrothermal fluids during dilatant episodes. As a result, they are not linked to mineralisation despite having Nb-Ta and Nb/Ta variations that are typical of the high oxidation states in Au-prospective magmas of the LFB.

Submitted by REJANE LIMA LUCIANO null (rejell@gmail.com) on 2016-05-11T13:16:32Z No. of bitstreams: 1 Tese_Rejane Luciano.pdf: 19192915 bytes, checksum: a962da38352827e62f035a8401c8eaf5 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-05-13T12:57:38Z (GMT) No. of bitstreams: 1 luciano_rl_dr_rcla.pdf: 19192915 bytes, checksum: a962da38352827e62f035a8401c8eaf5 (MD5) / Made available in DSpace on 2016-05-13T12:57:38Z (GMT). No. of bitstreams: 1 luciano_rl_dr_rcla.pdf: 19192915 bytes, checksum: a962da38352827e62f035a8401c8eaf5 (MD5) Previous issue date: 2016-03-18 / Este trabalho verificou que as rochas metacarbonatíticas do Complexo Metacarbonatítico de Angico dos Dias (CMCAD), constituídas principalmente por calcita, apatita, olivina, flogopita e magnetita dispõem-se em dois conjuntos: um localizado na mina de fosfato da Galvani (corpo principal, Campo Alegre de Lourdes-BA) e o outro na Fazenda Pimenteira (Caracol-PI). Variação no conteúdo de apatita, minerais ferro-magnesianos e magnetita configura um acamadamento cumulático e permite individualizar cinco fácies petrográficas (contatos graduais). Além disso, exibem manto intempérico, que resulta no minério de fosfato residual (apatitito). Registram pelo menos três fases deformacionais marcadas por estruturas primárias (acamamento reliquiar - S0) que devido aos processos de transposição (D1) da foliação S1 e da deformação D2 associada às zonas de cavalgamento (S2) se mantêm de forma escassa nas áreas menos deformadas. D2 evolui para um bandamento tectônico vertical (S3) nas zonas de cisalhamento (D3). Dados isotópicos indicam que as rochas metacarbonatíticas, datadas em 2.011±6Ma (U-PB em badeleíta e zircão), originaram-se de uma fonte mantélica enriquecida e que o enriquecimento em 18O é reflexo do reequilíbrio durante o metamorfismo/ hidrotermalismo relacionado ao Evento Brasiliano. Dados petrográficos e de química mineral apontam: que a olivina altera para serpentina, tremolita, antofilita e magnetita; que é comum a exsolução de dolomita em calcitas e de ilmenita em magnetitas e; que os carbonatitos foram parcialmente silicificados. As demais rochas do CMCAD, milonitizadas e metamorfizadas em fácies anfibolito alto (mesopertitas), exibem processo de potassificação (fenitização), metassienito e metassienogranito, além de processos de sericitização, saussuritização e epidotização dos plagioclásios. O evento metassomático/hidrotermal (fácies xisto verde médio a alto) tem caráter regional e atinge além das rochas do CMCAD as rochas do Complexo Sobradinho-Remanso. Dados geoquímicos classificam as rochas metacarbonatíticas principalmente como calciocarbonatitos. Aquelas intensamente hidrotermalizadas são classificadas como ferrocarbonatitos e magnesiocarbonatitos. Indicam filiação magmática comum para todos os cinco litofácies, associada a processos de diferenciação magmática por segregação mineral. / This study found that the metacarbonatite rocks of the Angico dos Dias Metacarbonatite Complex (CMCAD), consisting mainly of calcite, apatite, olivine, phlogopite and magnetite are arranged in two sets: one located at the phosphate mine Galvani (main body, Campo Alegre de Lourdes-BA) and the other at the Farm Pimenteira (Caracol-PI). Variation in the content of apatite, iron-magnesium minerals and magnetite sets up a cumulatic layering and allows individualize five petrographic facies (gradual contacts). Furthermore, exhibit weathering mantle, which results in the residual phosphate ore (apatite-rock). Register at least three deformational phases marked by primary structures (layering reliquiar - S0) that due to the transposition process (D1) of the foliation S1 and D2 deformation associated with thrust zones (S2) remain scantily the least deformed areas. D2 evolves into a tectonic vertical banding (S3) in the shear zones (D3). Isotopic data indicate that metacarbonatite rocks, dated at 2,011 ± 6Ma (U-PB in baddeleyite and zircon), originated from a mantle source enriched and the enrichment in 18O reflects the rebalancing during metamorphism/hydrothermalism related the Brasiliano Event. Petrography and mineral chemistry data point: the olivine changes to serpentine, tremolite, anthophyllite and magnetite; which it is common to exsolution of dolomite in calcite and ilmenite in magnetite and; that carbonatites were partially silicified. The other rocks CMCAD, mylonite and metamorphosed to amphibolite facies high (perthites) exhibit potassification process (fenitization), metasyenite and metasyenogranite, and sericitization, saussuritization and epidotization processes of plagioclase. The metasomatic/hydrothermal event (medium to high greenschist facies) has regional character and reaches beyond CMCAD rocks the rocks of Sobradinho-Remanso Complex. Geochemical data classify metacarbonatite rocks mainly as calcium carbonatites. Those intensely hydrothermalized are classified as iron metacarbonatites and magnesium carbonatites. Indicate common magmatic membership for all five lithofacies, associated with magmatic differentiation processes for mineral segregation.

Ce travail a été entrepris dans le but de déterminer les chaînes opératoires des matières colorantes néolithiques et de les intégrer dans une dynamique chrono-culturelle, à partir de deux sites-clés de l’arc liguro-provençal : Castellar – Pendimoun (5750-4900 cal. BCE) et Nice – Giribaldi (4550-4050 cal. BCE).L’étude technoéconomique montre des situations contrastées. Pendimoun voit, tout au long du VIe millénaire BCE, l’exploitation de trois roches locales aux caractéristiques physico-chimiques variées, traitées selon des schémas simples similaires pour fournir des produits adaptés à tous les besoins : hématite ou goethite, en quantité pour un usage technique ou de granulométrie fine pour exploiter les propriétés colorantes. Giribaldi est le siège d’une gestion dichotomique, où des matières colorantes locales préparées comme à Pendimoun, côtoient des matières exogènes, traitées à travers des actions spécifiques adaptées à leur cohérence.Enfin, de nombreux aspects symboliques ont été mis en évidence et caractérisés. Un bloc calcaire est sculpté et peint pour représenter un visage, selon une tradition peut-être héritée de pratiques proche-orientales. La teinte rouge est associée à la sphère funéraire. La coloration de productions céramiques techniquement très investies et vraisemblablement dédiées à des pratiques sociales particulières est aussi observée ; cette coloration est appliquée par incrustation de poudre durant les VBQ à Pendimoun et par peintures rouges ou noires et par incrustations blanches au Chasséen ancien à Giribaldi. / The aim of this research was to determine the “chaînes opératoires” of colouring materials in the north-western Mediterranean region during the Early and Middle Neolithic and to integrate them in chrono-cultural framework. Two major archaeological sites were selected: Castellar – Pendimoun rock-shelter (5750-4900 cal. BCE) and Nice – Giribaldi, an open-air site (4550-4050 cal. BCE).The techno-economic analysis reveals contrasting situations. At Pendimoun, three local colouring materials, presenting various physic-chemical properties, were used during the VI millennium BCE. They were processed identically according to simple schemes in order to provide a wide range of products: goethite or hematite, in quantities for utilitarian needs or in fine powder for colouring purposes.Giribaldi witnessed a dichotomous management. Some local geomaterials were crafted such as the ones in Pendimoun but exogenous rocks were also specifically processed depending on their cohesion. Furthermore, this overview is not diachronically uniform as bauxites progressively replaced other raw materials in Early Chassey stages.Last, several symbolical aspects have been highlighted and characterized. A calcareous block was carved and painted in red- and yellowed to portray an anthropomorphic “mask”. The colour red is associated with funeral activities. Starting at the SMP phases, the main use of color is aimed at the coloring of ceramics, the latter probably dedicated to specific social activities as suggested by the technical investment involved: red powder incrustation in ceramic (Pendimoun) and then by white powder incrustation in engraved decor, black and red painting (Giribaldi).

O Batólito Acandí é um corpo intrusivo com grandes variações de composição (Gonzalez e Londoño, 2002) que data do Oligoceno (Toussaint e Restrepo, 1976), por sua vez intruído por corpos de andesitos, dacitos, e diques de basalto. Devido às diferenças de composição deste corpo na Cordilheira Ocidental, a integração e interpretação dos dados da análise petrográficos, geoquímicos e isotópicos amostras coletadas no norte do Golfo de Urabá entre as cidades de Acandí e Unguía, no departamento foi feito. Para esta área, as rochas do Batólito são gabros: rochas melanocráticas, massivas, equigranulares de grão fino a meio, subhedrales, de textura fanerítica; e os corpos e diques são rochas leucocráticas, massivas, inequigranulares de grão fino a meio, subhedrales, com textura porfirítica e rochas melanocráticas afaníticas (basaltos). Petrografia detalhada mostra que as rochas do Batólito são compostas de plagioclásio, piroxênio e anfibólio, como acessórios pirita disseminada, apatita, magnetita e ilmenita. São rochas holocristalinas, melanocráticas, inequigranulares, subhedrales, de fino a groso granular, com a presença de texturas subofíticas e ofíticas, com coroas de reação e zoneamento em plagioclásios. As rochas subvulcânicas que intrudem o Batólito são basaltos afaniticos e andesitos e dacitos com texturas porfiríticas, com plagioclásio e hornblenda como principais minerais. São inequigranulares, de tamanho muito fino a grosso, com texturas cumulo-porfiríticas, vesiculares e amigdulares. Análises geoquímicas e isotópicas indicam que tanto as rochas do Batólito como os corpos que intrudem, são de afinidade sub-alcalina da série cálcio-alcalina de baixo para meio K, metaluminosas com ligeiro enriquecimento de elementos de terras raras em relação ao as terras raras pesadas. Dados de geoquímica e isotópicos de Nd e Sr sugerem que estas rochas são formadas a partir de processos em arcos insulares associados com zonas de subducção, sendo posteriormente acrecentadas à margem continental. / The Acandi’s batholith is a large intrusive body with a wide compositional variation (Gonzalez and Londoño, 2002) dating from the Oligocene (Restrepo y Toussaint, 1976), and intruded by andesites and dacites bodies and basalt dikes. Due to the compositional difference of this body in the Western Cordillera, it is performed integration and interpretation of new petrographic, geochemical and isotopic data from samples collected in the northern Gulf of Urabá between the towns of Acandí and Unguía it is done in Choco Department. For this area, batholith rocks are gabbros: melanocratic rocks, massive, equigranular fine to medium grained, subhedral, phaneritic texture; and the bodies and dikes are: leucocratic, massive and inequigranular rocks, fine to medium grained, subhedral, with sporphyritic texture and aphanitic melanocratic rocks (basalts).. Detailed petrography shows that the rocks from the Batolith are constituted by plagioclase, pyroxene and amphibole, with disseminated pyrite, apatite, magnetite and ilmenite as accessory phases. The batholith rocks are holocrystalline, melanocratic, inequigranular, subhedral, from fine to granular roughly, with the presence of ophitic and subophitic textures, with reaction rings (coronas) and zoning in plagioclase. The intrusive subvolcanic rocks that crosscut the Batholith are afanitic basalts, dacites, and andesites with porphiritic textures, having plagioclase and hornblende as main minerals. They are inequigranular, very fine to coarse grained, with glomeroporphyritic texture and also vesicular and amygdular textures. Geochemical and isotopic analyses indicate that both batholiths and intrusive rocks are sub-alkaline from the calc-alkaline series of low to medium K, metaluminous with light rare earth elements enrichment in relation to the heavy rare earth elements. The geochemical and Nd and Sr isotopic data suggest that these rocks are formed in island arcs, associated with subduction zones, being later added to a continental margin.

O Pórfiro Yarumalito está localizado na parte norte do Distrito Mineiro Marmato a oeste do vale do rio Cauca-Patía, no Departamento de Antioquia. Este distrito mineiro é reconhecido pela histórica exploração das mineralizações de ouro. Os depósitos de ouro na região estão associados a veios controlados por estruturas e em stockworks, que são desenvolvidos em rochas ígneas associadas a eventos magmáticos do miocénico superior como a Formação Cômbia. Nesta dissertação foram caracterizadas rochas porfiriticas de composição andesitica, dacítica mineralizada e dacítica estéril, junto com as alterações hidrotermais que afetaram principalmente as últimas, utilizando microscopia óptica convencional (luz transmitida e refletida) e equipamentos de MEV na Universidade Federal do Rio Grande do Sul. Os resultados da petrografia permitiram distinguir no pórfiro dacítico mineralizado estágios de alteração potássica, propilítica e fílica, que indicam intensa circulação de fluidos em um amplo intervalo de temperatura, enquanto no pórfiro dacítico estéril se distinguiu só sericitização. Nestas alterações se fez uma seleção criteriosa de exemplares de mica trioctaédrica, clorita e mica dioctaédrica que foram analisados por microssonda eletrônica na Universidade de Brasilia Os resultados da química mineral sugerem a ocorrência de diversas trocas catiônicas durante o estágio magmático–hidrotermal. Estas trocas têm lugar tanto no sitio VI como no sitio IV, incluindo elementos como Si, Al, Mg, Fe, Ti e Mn. Estas trocas afetaram a composição no sítio A (intercamada) e também têm efeito na quantidade de ânions de F e Cl presentes na estrutura dos minerais analisados. Tanto as micas trioctaédricas magmáticas do pórfiro dacítico mineralizado como as da alteração potássica correspondem com biotitas magnésias, no entanto as micas trioctaédricas hidrotermais têm tendência para flogopitas, mostrando o aumento de Mg no sistema. Nas micas dioctaédricas se observa uma tendência para fengita no estágio correspondente com o pórfiro dacíto mineralizado. Para as cloritas a maior parte dos exemplares analisados corresponde com ripidiolitas. / The Yarumalito Porphyry is located in the northern part of the Mining District Marmato to west of the Cauca-Patía river valley in the Department of Antioquia. This mining district is known for historical exploration of gold mineralization. The gold deposits in the region are associated with veins controlled by structures and stockworks, which are developed in igneous rocks associated with magmatic events of the late Miocene as Combia Formation. In this thesis were characterized porphyritic rocks of andesitic and dacitic (mineralized and barren) composition and the hydrothermal alteration that affected principally the last two, using conventional optical microscopy (transmitted and reflected light) and SEM equipment at the Federal University of Rio Grande do Sul. The results of petrography allowed distinguish in the mineralized dacitic porphyry mainly stages of potassic alteration, propylitic alteration and phyllic alteration, indicating intense circulation of fluids in a wide temperature range. Meanwhile barren dacitic porphyry only has phyllic alteration. In these alteration were made a careful selection of trioctahedral mica, chlorite and dioctahedral mica that were analyzed by electron microprobe at the University of Brasilia. The results of mineral chemistry suggest the occurrence of several cationic exchanges during magmatic-hydrothermal stage. These exchanges take place both on site VI and in the site IV, including elements such as Si, Al, Mg, Fe, Ti and Mn. These changes affected the composition of A site (interlayer) and also have effect on the amount of anions of F and Cl in the structure of analyzed minerals. Both, the magmatic trioctahedral micas of mineralized dacitic porphyry and that generated in potassic alteration correspond with magnesium biotites, however hydrothermal 8 trioctahedral micas have tendency to phlogopites indicating the rise in Mg content in the system, dioctahedral micas have a tendency for phengite in stages corresponding with the mineralized dacitic porphyry. Chlorites in most analyzed samples correspond to ripidiolitas.

O Batólito Acandí é um corpo intrusivo com grandes variações de composição (Gonzalez e Londoño, 2002) que data do Oligoceno (Toussaint e Restrepo, 1976), por sua vez intruído por corpos de andesitos, dacitos, e diques de basalto. Devido às diferenças de composição deste corpo na Cordilheira Ocidental, a integração e interpretação dos dados da análise petrográficos, geoquímicos e isotópicos amostras coletadas no norte do Golfo de Urabá entre as cidades de Acandí e Unguía, no departamento foi feito. Para esta área, as rochas do Batólito são gabros: rochas melanocráticas, massivas, equigranulares de grão fino a meio, subhedrales, de textura fanerítica; e os corpos e diques são rochas leucocráticas, massivas, inequigranulares de grão fino a meio, subhedrales, com textura porfirítica e rochas melanocráticas afaníticas (basaltos). Petrografia detalhada mostra que as rochas do Batólito são compostas de plagioclásio, piroxênio e anfibólio, como acessórios pirita disseminada, apatita, magnetita e ilmenita. São rochas holocristalinas, melanocráticas, inequigranulares, subhedrales, de fino a groso granular, com a presença de texturas subofíticas e ofíticas, com coroas de reação e zoneamento em plagioclásios. As rochas subvulcânicas que intrudem o Batólito são basaltos afaniticos e andesitos e dacitos com texturas porfiríticas, com plagioclásio e hornblenda como principais minerais. São inequigranulares, de tamanho muito fino a grosso, com texturas cumulo-porfiríticas, vesiculares e amigdulares. Análises geoquímicas e isotópicas indicam que tanto as rochas do Batólito como os corpos que intrudem, são de afinidade sub-alcalina da série cálcio-alcalina de baixo para meio K, metaluminosas com ligeiro enriquecimento de elementos de terras raras em relação ao as terras raras pesadas. Dados de geoquímica e isotópicos de Nd e Sr sugerem que estas rochas são formadas a partir de processos em arcos insulares associados com zonas de subducção, sendo posteriormente acrecentadas à margem continental. / The Acandi’s batholith is a large intrusive body with a wide compositional variation (Gonzalez and Londoño, 2002) dating from the Oligocene (Restrepo y Toussaint, 1976), and intruded by andesites and dacites bodies and basalt dikes. Due to the compositional difference of this body in the Western Cordillera, it is performed integration and interpretation of new petrographic, geochemical and isotopic data from samples collected in the northern Gulf of Urabá between the towns of Acandí and Unguía it is done in Choco Department. For this area, batholith rocks are gabbros: melanocratic rocks, massive, equigranular fine to medium grained, subhedral, phaneritic texture; and the bodies and dikes are: leucocratic, massive and inequigranular rocks, fine to medium grained, subhedral, with sporphyritic texture and aphanitic melanocratic rocks (basalts).. Detailed petrography shows that the rocks from the Batolith are constituted by plagioclase, pyroxene and amphibole, with disseminated pyrite, apatite, magnetite and ilmenite as accessory phases. The batholith rocks are holocrystalline, melanocratic, inequigranular, subhedral, from fine to granular roughly, with the presence of ophitic and subophitic textures, with reaction rings (coronas) and zoning in plagioclase. The intrusive subvolcanic rocks that crosscut the Batholith are afanitic basalts, dacites, and andesites with porphiritic textures, having plagioclase and hornblende as main minerals. They are inequigranular, very fine to coarse grained, with glomeroporphyritic texture and also vesicular and amygdular textures. Geochemical and isotopic analyses indicate that both batholiths and intrusive rocks are sub-alkaline from the calc-alkaline series of low to medium K, metaluminous with light rare earth elements enrichment in relation to the heavy rare earth elements. The geochemical and Nd and Sr isotopic data suggest that these rocks are formed in island arcs, associated with subduction zones, being later added to a continental margin.

AN ABSTRACT OF THE THESIS OF Amberly Hope Tobin, for the Master of Science degree in Organic Geochemistry, presented on August 4th 2016, at Southern Illinois University Carbondale. TITLE: OHD PROCESSING OF COAL WASTE MATERIALS MAJOR PROFESSOR: Dr. Susan M. Rimmer This research addresses coal-waste utilization via the OHD process and the implications for both economic and environmental impacts. The goal of this project is to determine if coal-waste products can be processed by the OHD technique. Furthermore, this project will determine what types of products are produced from the coal-waste materials and will compare these to those produced by the OHD processing of raw coal. This research has the potential to be beneficial to the coal industry as OHD would allow production of high-value products from what is currently viewed as a waste material; additionally, this research will provide a way to recycle what is considered a hazardous waste product and provide an incentive to reclaim coal slurry ponds that are an environmental concern. A preliminary suite of grab samples from an active coal slurry pond along with a stream reject sample were obtained in order to determine if these types of materials could be processed via OHD. After these samples were deemed viable in the OHD process, core samples were taken from a large slurry pond. These cores were then ii sampled at 2 ft (0.61 m) intervals. The key analyses performed were geochemical, petrographic, OHD, and GC-MS. Geochemical analysis included carbon, sulfur, moisture, volatile matter, ash, and fixed carbon content of the coal-waste samples before OHD, and provided a basis for comparison with raw coal samples. Petrographic analysis was performed to determine the maceral composition before the OHD processing. The OHD process is the core technique of this research project. The preliminary slurry pond samples were processed in a small semi-continuous OHD reactor. While the stream reject and slurry pond core samples were processed using a continuous OHD reactor, as this type of reactor is best suited for fine-grained slurries. GC-MS was used to examine the OHD liquid products analysis in order to determine the types of compounds present in the final liquefied product; these products were then compared to raw coal OHD products in order to determine their economic potential. Petrography of the coal-waste materials showed that these samples did contain a notable amount of coal; predominantly vitrinites and inertinites were observed in the samples. Geochemical analysis proved that there were significant amounts of organic carbon in these materials, ranging between 25 and 37%. OHD processing was successful on all coal-waste materials, although the continuous OHD reactor tended to work better with the fine-grained slurries than the semi-continuous OHD reactor. The GC-MS analysis of the coal-waste OHD product showed very similar suites of compounds to that of a bulk coal OHD product; in general, almost all major compounds that are found in a typical coal OHD product were also found in the coal-waste OHD products. This suggests that these slurry ponds, which are typically regarded as waste products, could be viable feedstocks for OHD processing.

Constraining the behaviour of small fractions of partial melt in a solid silicate matrix has been the focus of numerous experimental petrology studies over several decades, and is an important factor in constraining upper mantle rheology, melt extraction at mid-ocean ridges and mechanisms of core formation in the early solar system. Deformation of partially molten rock has been observed to change melt geometry, and may enhance permeability and interconnectivity of melt otherwise trapped in a solid silicate matrix, although it is uncertain how applicable results of high strain-rate laboratory experiments are to the real Earth. The addition of deformation precludes attainment of textural equilibrium, complicating textural analysis, which has previously relied on extrapolation of 3D textures from quenched and polished 2D sections for hydrostatically annealed samples. X-ray computed tomography gives the potential to visualise sample textures directly in three dimensions, and is becoming popular as a complementary technique for textural analysis in petrologic studies. The aim of this project has been to develop techniques to improve visualisation of small fractions of partial melt within a solid silicate matrix using X-ray CT, to examine textures of various partially molten systems at high PT in hydrostatic, and dynamically deforming systems. Experiments carried out in the FeS-melt, solid olivine system have examined the potential for deformation-enhanced percolation of core forming melts before the onset of silicate melting. Access to the newly designed rotational Paris-Edinburgh Cell (roPEC/rotoPEC) equipment has allowed us to carry out controlled, torsional deformation experiments under PT conditions applicable to planetary interiors. Experiments conducted at lower strain-rates over longer duration than in previously published studies show that deformation enhances connectivity at low melt fractions, at strain-rates down to 10-6s-1. This is in contrast to earlier work suggesting melt textures are unaffected at strain-rates below 10-5s-1. Quenched melt networks have been fully characterised in 3D using multi-scale CT, with voxel sizes down to 70nm for small sample sub-volumes. Results suggest segregation of metallic melt below the silicate solidus could be an efficient process, and should be taken into account in geochemical models of planetary evolution. Experiments on basaltic melt in a solid silicate matrix were conducted in application to upper mantle melting. A heavy element, hafnium, was added to the basaltic glass starting composition to enhance contrast between the basalt and olivine phases during CT scans. In-house micro-CT equipment was used to visualise post-quench run products of hydrostatic and deformation experiments. The doping technique was successful for long-duration, high temperature hydrostatic experiments. Some issues with undissolved / re-precipitated HfO¬2 crystals complicated tomographic imaging of partial melt textures in a number of experiments, particularly those carried out on the rotoPEC equipment, limiting comparison between samples. The doping technique requires further adjustment, but is shown to be a viable way to improve visibility of basaltic melt without significantly affecting melt texture. The X-ray transparent design and fully rotating top and bottom anvils of the rotoPEC allow X-ray tomography to be carried out in-situ while experiments are in progress, enabling collection of 4D datasets. During this project, the rotoPEC equipment was incorporated into two different synchrotron beamlines, to carry out time-resolved studies of textural development within samples of varying composition. The migration of gold melt along fractures with a BN matrix was imaged using 2D radiography, in combination with repeated 3D tomography to fully characterise the 3D fracture geometry. This allowed melt migration velocity to be estimated directly from in-situ observations. These techniques could be developed further to constrain melt migration processes quantitatively for a number of geological systems in the near future.

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No. of bitstreams: 1 lima_fg_dr_rcla.pdf: 11693401 bytes, checksum: 59035a53f9dd97177924619aae57fda8 (MD5) Previous issue date: 2017-09-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho apresenta os resultados dos estudos petrogenéticos detalhados realizados nos serpentinitos que constituem do Morro do Níquel, maciço ultrabásico mineralizado em níquel laterítico, situado na Faixa Brasília Meridional, ao norte da Zona de Sutura de Alterosa, localizado no Município de Pratápolis (MG), sul/sudoeste do Estado de Minas Gerais, Brasil. Os serpentinitos possuem cor verde escuro a preto, aspecto maciço e é constituído por mais de 95% de lizardita/crisotilo, com ocorrências localizadas de antigorita. O padrão estrutural do maciço é compatível com aqueles gerados pela deformação de em um corpo rígido em matriz dúctil dentro de zona de cisalhamento. Os dados mineralógicos, petrográficos e geoquímicos, em associação com os de campo e de descrição de testemunho de sondagem rotativa, apontam que o protólito destas rochas seria um corpo dunítico de granulação média a grossa e textura granular, suas dimensões seriam superiores a 800 x 400 metros e com mais de 350 metros de espessura. Os dados obtidos indicam que o dunito é mantélico e possibilitou propor um modelo evolutivo desde a exumação do manto até a colocação sobre embasamento TTG e serpentinização. A exumação se inicia com o adelgaçamento da crosta continental durante a instalação de um sistema rifte, que teria evoluído ao ponto de atingir a “super extensão” da crosta e o desenvolvimento de uma crosta oceânica. Com o fechamento do oceano decorrente de colisão continental, no neoproterozóico, o corpo dunítico foi alojado sobre o embasamento cristalino, na margem passiva da placa que contém o Cráton São Francisco. A serpentinização do dunito ocorreu tardi-pós aloctonia, catalisada pela atuação do Cinturão de Cisalhamento do Campo do Meio, em condições de fácies visto verde, fácies prehnita-pumpelyíta, com baixa fugacidade de oxigênio e enxofre e alta atividade de H2(aq.). / This work presents results from detailed petrogenetic studies performed on the Morro do Níquel (Nickel Hill) serpentinites, an ultrabasic massif mineralized in lateritic nickel, located in the Southern Brasília Belt, north of the Alterosa Suture Zone, Municipality of Pratápolis (MG), southwest of the State of Minas Gerais-Brazil. The serpentinite has a dark color, apparently massive aspect and consist of more than 95% lizardite / chrysotile, with localized occurrences of antigorite. The structural pattern of the massif is compatible with those generated by the shear of a rigid body in a ductile matrix within a shear zone. The mineralogical, petrographic and geochemical data, in association with the field and drill hole logs description, indicate that the protolith of these rocks would be a dunitic body of medium to large granulation and granular texture, with dimensions superior to 800 x 400 meters and with more than 350 meters of thickness. The obtained data indicate that the dunite is mantellic and it was possible to propose an evolutionary model from the exhumation of the mantle dunitc body to the emplacement on the TTG basement and serpentinization. The exhumation begins with the thinning of the continental crust during the installation of a rift system, evolving to allow the hyper-extension of the crust until the development of an oceanic crust. With the continental collision, in the Neoproterozoic, the dunite was hosted on the crystalline basement, in the passive margin of the plate that contains the San Francisco Craton. The dunite serpentinization occurred late-post aloctonia, catalyzed by the Campo do Meio Shear Belt, under conditions of green facies, prehnite-pumpelyite facies, with low fugacity of oxygen and sulfur and high H2 (aq.) activity.