Submitted by Maike Costa (maiksebas@gmail.com) on 2016-01-06T14:43:43Z No. of bitstreams: 1 arquivototal.pdf: 3084404 bytes, checksum: a557c23387b1239e1ed610d310cf09ee (MD5) / Made available in DSpace on 2016-01-06T14:43:43Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3084404 bytes, checksum: a557c23387b1239e1ed610d310cf09ee (MD5) Previous issue date: 2015-03-31 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This study aimed to analyze environmental, chemical and mineralogical parameters of Recycled Aggregates (RA), classified as Recycled Concrete Aggregate (RCA), generated at the Plant for Improvement of Construction Solid Waste (USIBEN), in João Pessoa / PB, as well as some Natural Aggregates (NA). Environmental analyses were performed, through solubilization and leaching tests, as well as the characterization of its chemical and mineralogical composition by X-ray fluorescence, X-ray diffraction, differential thermal and thermogravimetric analyses, and infrared spectrometry. In Step I, for the solubilized extract, the aggregates Gravel 12 RA, Gravel 25 RA, Fine Aggregate RA, Gravel 12 NA and Stone Dust NA had values above the limits set out in Annex G of the standard ABNT NBR Nº 10004/2004 for some chemical parameters, such as sulfate (250 mg / L), iron (0.30 mg / L) and aluminum (0.20 mg / L). This study also investigated the presence of heavy metals (As, Cd, Cr, Ni, Al, Cu, Fe, Ni, Se, Zn), and, in accordance with the aforementioned standard, Gravel 12 RA exceeded the allowable limit for Cadmium. According to these results, the aggregates mentioned above changed their classification from Class II B – Inert – to Class II A – Non-Inert. In Step II, only four aggregates were selected to continue the study: Sand NA and RA; Gravel 12 NA and RA. The pH behavior of the aggregates chosen was investigated, and all of them suffered decay, stabilizing at alkaline pH (pH> 7). The chemical and mineralogical analyses (XRF, XRD, DTA / TG and IV) revealed the presence of quartz (SiO2) in the four samples, being the greater quantity in the NA ones. It was confirmed that the RA samples had compounds also found in mortar and concrete, such as calcium carbonate (CaCO3), alumina (Al2O3), iron oxide (Fe2O3), magnesium oxide (MgO) and cement hydration products, such as portlandite [Ca(OH)2] and plaster [CaSO42H2O]. It was concluded that the RA studied are viable for several uses, in relation to environmental, chemical and mineralogical analyses, since most compounds found in them are also part of NA used daily in civil construction. / Este trabalho teve como objetivo analisar os parâmetros ambientais, químicos e mineralógicos de Agregados Reciclados (AR), classificados como Agregado Reciclado de Concreto (ARC), gerados na Usina de Beneficiamento de Resíduos Sólidos da Construção Civil (USIBEN) em João Pessoa/PB, como também alguns Agregados Naturais (AN). Foi realizada análise ambiental, através de ensaios de lixiviação e solubilização, bem como a caracterização da sua composição química e mineralógica, por fluorescência de raios X, difração de raios X, análise térmica diferencial e termogravimétrica e espectrometria de infravermelho. Na Etapa I, para o extrato solubilizado, os agregados brita 12 AR, brita 25 AR, agregado miúdo AR, brita 12 AN e pó de pedra AN apresentaram valores superiores ao limite definido no anexo G da ABNT NBR Nº 10004/2004 para alguns parâmetros químicos como sulfato (250 mg/L), ferro (0,30 mg/L) e alumínio (0,20 mg/L). Também investigou-se a presença de metais pesados (As, Cd, Pb, Cr, Ni, Al, Cu, Fe, Ni, Se, Zn) e de acordo com a referida norma, a brita 12 AR ultrapassou o limite permitido para o metal cádmio. De acordo com esses resultados, os agregados supracitados mudam sua classificação de Classe II B - Inertes, para Classe II A - não Inertes. Na Etapa II foram definidos apenas 4 agregados para continuidade: areia AN e AR; brita 12 AN e AR. Investigou-se o comportamento do pH dos 4 agregados e todos tiveram decaimento, estabilizando-se em pH alcalino (pH > 7). Para as análises químicas e mineralógicas (FRX, DRX, DTA/TG e IV) observou-se a presença de quartzo (SiO2) nas 4 amostras sendo em maior quantidade nos AN. Para as amostras AR foram comprovadas a presença de compostos presentes em argamassa e concreto, como carbonato de cálcio (CaCO3), alumina (Al2O3), óxido de ferro (Fe2O3), óxido de magnésio (MgO) e produtos da hidratação do cimento, como a portlandita [Ca(OH)2] e gesso [CaSO42H2O]. Portanto os AR estudados são viáveis em relação a análise ambiental, química e mineralógica, para diversas utilizações, pois a maioria dos compostos encontrados neles também fazem parte dos AN, usados diariamente na construção civil.

A Mina de Santa Rita, situada no complexo máfico-ultramáfico Fazenda Mirabela, é uma intrusão máfica-ultramáfica, mineralizada a sulfetos de níquel e cobre, situada no sudeste do Estado da Bahia, município de Itagibá. Esse depósito é composto por rochas de idade Paleoproterozóica, metamorfizadas em fácies granulito. Os sulfetos de níquel e cobre ocorrem disseminados e, preferencialmente, associados a harzburgitos, olivina ortopiroxenitos e ortopiroxenitos. O minério é composto por uma grande variedade de Mg-silicatos, sendo que o níquel ocorre essencialmente como pentlandita nos peridotitos, além de se apresentar como elemento menor em silicatos e espinélios em rochas mais máficas. Informações de processo demonstram a impossibilidade de se estabelecer uma correlação robusta entre a composição química do minério e seu comportamento na etapa de beneficiamento mineral. Desta forma, o conhecimento da variabilidade mineralógica no depósito é de fundamental importância para o planejamento de lavra e processamento mineral. Mais de 300 amostras do plano de mineração de curto prazo (2013-2017) relativas a intervalos de furos de sondagem considerados no estudo de viabilidade econômica (período de 1985-2004) foram agrupadas em domínios mineralógicos, utilizando a análise estatística multivariada de dados de difração de raios X (DRX-AEM). Dezessete domínios mineralógicos inicialmente definidos são essencialmente diferenciados com base na presença e conteúdos relativos dos principais minerais de ganga: serpentina, olivina e piroxênio. Amostras representativas dos principais domínios mineralógicos, pré-definidos por DRX-AEM, foram submetidas a estudos de caracterização mineralógica de detalhe por análise de imagens (MEV-MLA). Os resultados indicam que os grupos com composições mais peridotíticas e/ou carbonáticas, com maiores conteúdos de serpentina, apresentam menor tempo de moagem para atingir P95 igual a 0,15 mm; maior alteração dos grãos de pentlandita; maior parcela de total de níquel associado a silicatos; menor grau de liberação dos sulfetos; e maior quantidade de sulfetos abaixo de 10 ?m, em relação aos grupos de composição mais piroxenítica. / The Santa Rita mine, located in the mafic-ultramafic complex Fazenda Mirabela, is a mafic-ultramafic intrusion mineralized to nickel and copper sulphides located in the southeast of Bahia state, Itagibá municipality. The nickel sulphide deposit comprises a portion of a mafic-ultramafic layered complex under granulite metamorphism facies. Disseminated Ni and Cu sulphides form a stratiform body parallel to the lithostratigraphic contacts extending upwards essentially from the harzburgite unit and through the olivine orthopyroxenite unit. The nickel content is mainly associated to pentlandite in peridotitic rocks but also enriched in silicates and spinels in mafic rocks (dunites). Industrial plant benchmark data have shown the unfeasibility of establishing a strong relation between the ore chemical composition and its behavior in the mineral beneficiation process. Therefore, the knowledge of the mineralogical variability in the deposit is crucial for mine planning and mineral/metallurgical processing. More than 300 samples from drill core samples from the feasibility studies (period of 1985-2004) included in the short-term mining plan (2013-2017) were clustered into geological domains applying multivariate statistical analysis (MSA) of X-ray diffraction data (XRD). Results discriminated seventeen initial mineralogical domains considering the content of major gangue minerals: serpentine, olivine and pyroxene. Representative samples of the main mineralogical domains pre-defined by XRD-MSA ore-types were later subject to sieve size analysis followed by detailed mineralogical studies by automated SEM image analysis (MLA). The results indicate that groups with more peridotite and / or carbonatic compositions, with higher content of serpentine, have less time of grinding to reach P95 equal to 0,15 mm; high level of pentlandite alteration; greater portion of nickel associated into silicates; lower sulphides liberation degree; and a higher amount of sulphides below 10 ?m; in relation to the most pyroxenic composition groups.

La faïence est une céramique caractérisée par son revêtement vitreux blanc opaque, grâce à l’adjonction d’oxyde d’étain ; sur ce fond on peut apposer les décors polychromes. Résultant d’une technologie abbaside (VIIIe siècle), elle connait son apogée en France au XVIIIe siècle. Les précédentes études menées sur la faïence moderne ont mis en évidence la nécessité de procéder à une approche pluridisciplinaire pour appréhender ce matériau complexe, ses techniques de fabrication, et cerner les enjeux de sa production. Ce travail de recherche s’inscrit dans la continuité pour s’élargir aux productions faïencières du Sud Ouest de la France quelques peu délaissées du point de vue archéométrique. La manufacture Babut, première faïencerie établie à Bergerac, fut sélectionnée dans ce but. La production perdure sur cinquante ans environ, jusqu’à la Révolution Française.En prenant en considération ces observations, cette thèse a permis tout d’abord d’identifier la production du point de vue des matériaux et des techniques, de mettre en place un référentiel géochimique, ainsi qu’établir un corpus stylistique de base pour cette manufacture. Ensuite l’étude a porté sur l’évaluation du potentiel de méthodes d’analyses non destructives pour l’attribution de provenance directe à partir de la surface des glaçures. Et enfin ce travail a permis d’examiner la place de la faïence bergeracoise et de sa production au sein du tissu industriel régional, et les replacer dans le contexte plus général de la production faïencière française à l’aube de la Révolution industrielle. / Faiences are ceramics defined by a white and opaque glaze, due to the addition of tin oxide decorated or not. This technology appeared during the Abbasid period (VIIIth) and was imported in France around the XIIIth century; they peaked in the XVIIIth century. The previous studies realized on the modern faïences, underline the importance of proceeding to a pluridisciplinarity approach to comprehend this complex material, in the frame of a more global research program on faiences, this work focuses on the production of the South West of France, which have only received limited archaeometrics studies over the last years. The manufacture selected is the fabric of Jean Babut established in the city of Bergerac. The production lasted fifty years until the French Revolution. By analysing all the different results, this work establishes the possibility to proceed to the identification of the production site from technical and material standpoints, to establish a reference group based on the chemical analysis and to design a stylistic reference corpus. A non-destructive methodological approach was developed to evaluate the potential of non-destructive methods to reattribute faiences to a center of production. In addition, this work also reestablishes the production of faiences in the local industrial context and in the french production before the Industrial Revolution.

The Postmasburg Manganese Field (PMF), located in the Northern Cape Province of South Africa, once represented one of the largest sources of manganese ore worldwide. However, the discovery of the giant manganese deposits of the Kalahari Manganese Field (KMF) led to the gradual decline in manganese mining activity in the PMF. Two belts of manganese ore deposits have been distinguished in the PMF, namely the Western Belt of ferruginous manganese ores and the Eastern Belt of siliceous manganese ores. Prevailing models of ore formation in these two belts invoke karstification of manganese-rich dolomites and residual accumulation of manganese wad which later underwent diagenetic and low-grade metamorphic processes. For the most part, the role of hydrothermal processes in ore formation and metasomatic alteration is not addressed. The identification of an abundance of common and some rare Al-, Na-, K- and Ba-bearing minerals, particularly aegirine, albite, microcline, banalsite, sérandite-pectolite, paragonite and natrolite in the PMF ores studied in this thesis, is indicative of the influence of hydrothermal activity. Enrichments in Na, K and/or Ba in the ores are generally on a percentage level for the majority of samples analysed through bulk-rock techniques. The discovery of a Ba-Mn arsenate/vanadate similar to gamagarite may also indicate that the hydrothermal fluid affecting the ores was not only alkali-rich but also probably contained some As and V. The fluid was likely to be oxidized and alkaline in nature and is thought to have been a mature basinal brine. Various replacement textures, particularly of Na- and Krich minerals by Ba-bearing phases, suggest sequential deposition of gangue as well as oreminerals from the hydrothermal fluid, with Ba phases being deposited at a later stage. The stratigraphic variability of the studied ores and the deviation of their character from the pigeon-hole-type classification of ferruginous and siliceous ores in the literature, suggests that a re-evaluation of genetic models is warranted. The discovery of hydrothermallydeposited alkali-rich assemblages in the PMF and KMF provides grounding for further investigation into a possible regional-scale hydrothermal event at least re-constituting the ores. Some shortcomings in previous works include disregard for the highly variable nature of the PMF deposits, the effects of hydrothermal activity of the ores and the existence of stratigraphic discrepancies. This study provides a single, broad model for the development of all manganese deposits of the PMF. The source of metals is attributed to all formations that stratigraphically overly the Reivilo Formation of the Campbellrand Subgroup (including the Reivilo Formation itself). The main process by which metals are accumulated is attributed to karstification of the dolomites. The interaction of oxidized, alkaline brines with the ores is considered and the overlying Asbestos Hills Subgroup BIF is suggested as a potential source of alkali metals.

Although clays are generally considered stable materials under seismic conditions, recent failures initiated in clay layers after earthquakes have emphasized the need to study the cyclic and post-cyclic behavior of these materials. Moreover, if strength loss as a result of cyclic loading were to occur in the material comprising the dam and/or dam foundation, the consequences of failure could be substantial. The objective of this study is to evaluate the effect of plasticity characteristics, mineralogical composition, and accumulated energy on the cyclic behavior, post-cyclic shear strength and the degradation in shear strength due to cyclic loading in normally consolidated clays. Seventeen soil samples prepared in the laboratory from kaolinite, montmorillonite, and quartz were tested using static and cyclic simple shear apparatuses. In addition, the results of cyclic simple shear tests on twelve natural samples were provided by Fugro Consultants, Inc. in Houston, TX. Using the results, cyclic strength curves were developed to represent 2.5%, 5% and 10% double amplitude shear strains. These curves were used to examine the influences of mineralogical composition, plasticity characteristics and shear strain on the cyclic resistance of soil samples. A power function was used to represent the cyclic strength curves. The samples were found to become increasingly resistant to cyclic loading as the plasticity index increased. Moreover, the soils with montmorillonite as the clay mineral were noted to have consistently higher cyclic resistances than the soils with kaolinite as the clay mineral. By examining the power functions, it was found that the cyclic strength curve approaches linearity as the plasticity index increases in soils having kaolinite as the clay mineral. However, the opposite trend is observed in soils having montmorillonite as the clay mineral. The study shows that the post-cyclic shear strength increases with increasing plasticity index. Moreover, the post-cyclic shear strengths of soils with montmorillonite as the clay mineral were significantly higher than the post-cyclic shear strengths of soils with kaolinite as the clay mineral. The degradation in shear strength due to cyclic loading appeared unaffected by mineralogy, but a greater reduction in strength was noted with decreasing plasticity index. The post-cyclic shear strength was also found to reduce as the number of cycles required to cause 10% double amplitude shear strain increased. The energy approach considering the accumulated energy per unit volume in the soil mass as a result of cyclic loading was also utilized in this study. The results from the energy approach were independent of the cyclic wave form, but were still dependent on the amplitude of the cyclic load used during the testing. An increase in the amplitude of the cyclic loading function results in a decrease in the accumulated energy per unit volume. Furthermore, an increase in the liquid limit and/or plasticity index of the soils containing kaolinite as the clay mineral shows an increase in the accumulated energy, whereas an increase in plasticity of the soils containing montmorillonite as the clay mineral results in a decrease in the amount of accumulated energy. In both types of materials, the amount of accumulated energy per unit volume is found to increase with increasing double amplitude shear strain. Relationship between the ratio of post-cyclic undrained shear strength to the baseline undrained shear strength and the accumulated energy is also determined. / Ph. D.

Thesis (PhD)--University of Stellenbosch, 2004. / ENGLISH ABSTRACT: The Gamsberg Zn-Pb deposit is a metamorphosed and multiply deformed sediment-hosted base metal deposit in the central Namaqua Province of South Africa. The deposit is hosted by the Bushmanland Group, a late Palaeoproterozoic (2000-1600 Ma) supracrustal succession of quartzite, metapelitic schist and interbedded metavolcanic rocks. Mineralisation occurs within the central part of the Gams Formation, a heterogeneous sequence of metamorphosed metalliferous sediments and fine-grained organic-rich shales. The ore horizon is subdivided into a lower unit of metapelite-hosted ore, an intermediate layer of phosphorite-hosted ore, and an upper unit of banded garnet-apatite ore. The ore body is enveloped by unmineralised silicate-, carbonate- and oxide-facies metalliferous rocks, which originally represented mixtures of Fe-Mn-rich hydrothermal precipitates, authigenic carbonate, and variable concentrations of detrital material. Based on mineralogical and geochemical characteristics, the metalliferous host rocks are subdivided into iron formations, coticules, Fe-Mn silicates, impure marbles and barite/Ba-rich quartzite. Minerals of the Gams Formation mostly represent solid solution between the Fe and Mn end-members of garnet, pyroxene, pyroxenoid, amphibole, olivine, spinel and ilmenite. Calcium-rich rock types are a typical feature and characterized by the occurrence of manganoan calcite, clinopyroxene, andradite-rich garnet and titanite. A successive increase in the (Mn+Ca):Fe value of rocks and minerals is evident with increasing distance from the ore horizon. Amphibole is restricted to Fe-rich ore-bearing assemblages, whereas orthopyroxene, clinopyroxene, Fe-rich pyroxenoid and olivine are present in intermediate assemblages, and Mn-rich rhodonite and pyroxmangite in the most manganiferous assemblages. These variations are mimicked by an increase in the Mn:Fe value of coexisting garnet and ilmenite group minerals with increasing distance from ore. LA-ICP-MS analyses have been used to constrain the REE patterns of garnet and apatite. In the ore-body, these minerals display a positive Eu anomaly, which is interpreted to reflect a distinct hydrothermal signature. In contrast, garnet and apatite in unmineralised metalliferous rocks display nil or a negative Eu anomaly. Primary features of the Gams Formation, such as REE patterns, the banded nature of garnet-apatite ore, the presence of diagenetic apatite nodules, and the distribution of the redox-sensitive elements Ba and Mn have been used to constrain palaeo-environmental conditions. The results indicate that metapelitehosted ore has been deposited in a stratified ocean that was characterised by anoxic bottom waters and precipitation of Fe and Zn sulphides into organic matter-rich shales. These rocks were superceded by phosphorite-hosted ore, garnet-apatite ore and metalliferous host rocks that developed in a suboxic to oxic environment. The large size of the deposit, the internal lamination of the ores and the predominance of sphalerite and barite are consistent with a vent-distal setting and precipitation of the ore-forming constituents from dense and reduced hydrothermal fluids, which originated due to reactivation of dormant growth faults. Collectively, the geological evidence indicates that Gamsberg is bridging the gap betweenthe SEDEX and BHT classifications. The relationships demonstrate that differences between these two classes of sediment-hosted Zn-Pb deposits are predominantly related to environmental conditions within localised third order basins and not to fundamental differences in ore-forming processes. / AFRIKAANSE OPSOMMING: Die Gamsberg Zn-Pb afsetting is ‘n meerfasig vervormde en gemetamorfiseerde sedimentgesetelde onedel metaal afsetting in die sentrale Namakwa Provinsie van Suid Afrika. Die afsetting word geherberg deur die Boesmanland Groep, ‘n laat Paleoproterosoïse (2000 – 1600 Ma) bokors-opeenvolging van kwartsiet, metapelitiese skis en tussengelaagde metavulkaniese gesteente. Mineralisasie word gevind in the sentrale deel van die Gams Formasie. Die Gams Formasie is ‘n heterogene opeenvolging van gemetamorfiseerde metaalhoudende sediment en fynkorrelrige organiese skalie. Die erts horison word onderverdeel in ‘n onderste laag van metapeliet-gesetelde erts, n sentrale laag van fosforiet-gesetelde erts, en ‘n boonste laag van gebande granaat-apatiet erts. Die erts-liggaam word omhuls deur ongemineraliseerde silikaat-, karbonaat- en oksied-fasies metal-ryke rotse. Hierdie gesteentes word geinterpreteer as oorspronklike mengsels van Fe-Mn-ryke hidrotermale partikels, outigeniese karbonaat, en verskeie hoeveelhede detritale materiaal. Gebaseer op mineralogiese en geochemiese kenmerke word hierdie rotse onderverdeel in ysterformasies, „coticules“, Fe-Mn silikate, onsuiwer marmer en barite/Ba-ryke kwartsiet. Minerale van die Gams Formasie form meestal soliede oplossingsreekse tussen die Fe en Mn endlede van granaat, pirokseen, piroksenoid, amfibool, olivien, spinel en ilmeniet. Kalsium-ryke rots tipes is ‘n tipiese kenmerk van die Gams Formasie en word gekenmerk deur mangaan-ryke kalsiet, klinopirokseen, andradiet-ryke granaat en sfeen. Daar word ‘n stapsgewyse vergroting van die (Mn+Ca):Fe verhouding in gesteentes en minerale gevind met toeneemende afstand van die erts horison. Amfibool is beperk tot Fe-ryke ertsdraende gesteentes, ortopirokseen, klinopirokseen, Fe-ryke piroksenoid en olivien tot intermediêre gesteentes, en Mn-ryke rodoniet en piroksmangiet tot Mn-ryke gesteentes. Hierdie variasies gaan gepaard met vergroting van die Mn:Fe verhouding in granaat en ilmeniet-groep minerale met toeneemende afstand van die erts. LA-ICP-MS analises was gebruik om die skaars-aarde element patrone van granaat en apatiet te bepaal. In die erts-liggaam wys hierdie minerale ‘n positiewe Eu anomalie, wat geinterpreteerd word as ‘n hidrotermale kenmerk. In ongemineraliseerde gasheer gesteentes wys granaat en apatiet geen of ‘n negatiewe Eu anomalie. Primêre kenmerke van die Gams Formasie, soos skaars-aarde patrone, the gebande voorkoms van granaat-apatiet erts, die teenwoordigheid van diagenetiese apatiet knolle, en die verspreiding van die redox-sensitiewe elemente Ba en Mn, was gebruik om afleidings oor die paleo-omgewing te maak. Die resultate het gewys dat metapeliet-gesetelde erts afgeset was onder anoksiese bodem water deur presipitasie van Fe en Zn sulfiedes in organiese skalie. Hierdie erts gaan oor in fosforiet-gesetelde erts, granaat-apatiet erts en metaal-ryke gasheer gesteente wat in ‘n suboksiese tot oksiese omgewing ontstaan het. Die grootte van die afsetting, die interne gelaagdheid van die erts, asook die teenwoordigheid van sfaleriet en bariet dui op ‘n distale omgewing relatief tot die hidrotermale bron en presipitasie van die ertsuit digte en gereduseerde hidrotermale vloeistowwe, wat ontstaan het deur die heraktiveering van rustende groeiverskuiwings. Gesaamentlik bewys die geologiese kenmerke van Gamsberg dat gemetamorfiseerde SEDEX en Broken Hill-tipe mineralisasie binne die perke van ‘n enkele afsetting kan voorkom. Die geologiese verhoudings dui aan dat verskille tussen hierdie twee tipes van sedimentgesetelde afsettings meestal veroorsaak word deur omgewings-toestande binne in gelokaliseerde derde orde komme en nie deur fundamentele verskille in ertsvormende prosesse nie.

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.

Quantifier la totalité des apports atmosphériques, notamment particulaires, est nécessaire pour mieux comprendre les cycles biogéochimiques en vue d'une gestion durable des écosystèmes forestiers. En effet, l'intensification des récoltes de bois-énergie induit une pression nutritive supplémentaire sur les forêts. Le but de ce travail est de combler les lacunes concernant le dépôt atmosphérique particulaire (taux de dépôt, composition minéralogique et chimique), ainsi que d'étudier son influence sur les cycles biogéochimiques forestiers. Pour ce faire, un échantillonnage de 2 ans a été mis en place dans 4 hêtraies de la moitié Nord de la France. Un développement métrologique a été nécessaire pour concevoir les capteurs hors et sous canopée et pour séparer les particules de la phase dissoute puis compartimenter le dépôt particulaire en fonction du modèle conceptuel organo-minéral établi dans cette étude. Les résultats obtenus valident ce modèle et montrent (i) un taux de dépôt annuel de 19±3 kg.ha-1.an-1 de minéraux peu solubles témoignant d'origines diverses, (ii) des flux de nutriments inférieurs à ceux des dépôts dissous et de l'altération des minéraux du sol mais qui contribuent à améliorer la fertilité des forêts, (iii) un captage supplémentaire induit par la canopée et (iv) une dissolution des particules minérales lors de leur transport atmosphérique qui enrichit les précipitations en nutriments. Un échantillonnage optimisé sur le long terme est indispensable pour confirmer et préciser les tendances observées, en particulier concernant les épisodes de très fort dépôt particulaire et le dépôt sous la canopée / Quantifying the little-known inputs of atmospheric particulate deposition (APD) is critically important for a sustainable management of forest ecosystems. Indeed, harvesting and subsequent nutrient losses are going to increase so as to meet the demand in renewable energy, including fuel-wood. This work aims at filling this gap by (i) describing the deposition rate, mineralogical and chemical compositions of APD and (ii) evaluating the influence of APD nutrient inputs on forest biogeochemical cycles. To do so, 4 beech stands in North French forests were equipped for a 4-week sampling. After a metrological development, samplers out of and below canopy were used for a 2-year sampling, as well as methods to separate APD from atmospheric dissolved deposition. These methods were conceived to separate the organic and mineral fractions of APD according to the conceptual model designed in this work. My results validated this model and indicated (i) a quite constant deposition rate of 19±3 kg.ha-1.year-1 of hardly soluble minerals over the North of France, made of various minerals suggesting heterogeneous sources of particles, (ii) nutrient inputs inferior to those of atmospheric dissolved deposition and soil weathering, but improving ecosystem fertility, (iii) an interception effect of the canopy, and (iv) the dissolution of mineral particles in the atmosphere which enriched atmospheric dissolved deposition in nutrients. Extending and optimizing the sampling would allow confirming and clarifying these results, especially concerning high atmospheric load periods and APD below canopy

Made available in DSpace on 2017-07-24T19:38:07Z (GMT). No. of bitstreams: 1 FABIOMALINOSKI.pdf: 1967487 bytes, checksum: a8c89b1d9584a90151895d2cdcb1b6d6 (MD5) Previous issue date: 2012-05-07 / This work presents the compilation and analysis of several analytical data obtained in the characterization of shale fine and lime schist, two abundant residuals in the Petrosix process. In order to ensure better representativeness of results, samples of lime schist extracted from complete vertical cuts of the layer were analyzed, and indirect analysis procedure was adopted for the shale fine residual, which basically consists of the characterization of samples obtained from complete vertical sections of superior and inferior shale layers in the Mine Rio das Pedras pit, within the Irati formation, in São Mateus do Sul PR. Analytical results obtained though Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) revealed that the lime schist layer presents mass predominance of the elements: Calcium, Silicon and Magnesium, and that this predominance, as indicated by the X-Ray Diffraction analysis (XRD), is due to the significant presence of Dolomite (CaMg(CO3)2) and Quartz (SiO2), and that the great reduction of mass after the Fixed Mineral Residue analysis is mainly related to CO2 elimination, in the dolomite thermal decomposition process. In the shale fine characterization, analytical results obtained through ICP-AES demonstrated that superior and inferior shale layers presented mass predominance of the elements silicon and iron, and this predominance, as indicated by the XRD is mainly due to the presence of Quartz (SiO2) and Pyrite (FeS2), and that the mass reduction after Fixed Mineral Residue analysis is related to the elimination of organic matter and the Pyrite thermal decomposition, with the former as the most relevant factor. Shale layers also presented Albite, Microcline and Muscovite, particle density similar values, crude oil with chromatographic profile of relative elevation in mass between the Heptane and Undecane peaks, uniform distribution between Dodecane and Octacosane peaks, decreasing distribution between the Nonacosane and C72 peaks, with normal spare paraffins in an unresolved complex organic mixture. These results indicate that the fine shale residue has a composition that oscillates between the narrow parameters of superior and inferior shale. / Neste trabalho apresentamos a compilação e a análise de diversos dados analíticos obtidos na caracterização do Finos de Xisto e do Calcário de Xisto, dois resíduos abundantes do processo Petrosix. Para garantir maior representatividade de resultados, analisam s amostras de Calcário de Xisto extraídas de cortes verticais completos da camada, e adotamos um procedimento de análise indireta para o resíduo denominado Finos de Xisto, que consiste basicamente na caracterização de amostras obtidas de secções verticais completas das camadas de Xisto Superior e Xisto Inferior das cavas da Mina Rio das Pedras, dentro da Formação Irati, na cidade de São Mateus do Sul – PR. Os resultados analíticos obtidos por Espectrometria de Emissão Atômica por Plasma Indutivamente Acoplado (EEA-PIA) demonstraram que a camada denominada Calcário de Xisto apresenta predomínio mássico dos elementos: Cálcio, Silício e Magnésio, que este predomínio, conforme indicado na análise de Difração de Raios X (DRX), deve-se a presença expressiva de Dolomita (CaMg(CO3)2) e Quartzo (SiO2), e que a grande redução de massa após a análise de Resíduos Minerais Fixos está relacionada principalmente a eliminação de CO2, no processo de decomposição térmica da Dolomita. Na caracterização do Finos de Xisto, os resultados analíticos obtidos por EEA-PIA demonstraram que as camadas de Xisto Superior e Xisto Inferior apresentam predomínio mássico dos elementos Silício e Ferro, que este predomínio, conforme indicado na análise de DRX, deve-se em grande parte a presença de Quartzo (SiO2) e Pirita (FeS2), que a redução de massa após a análise de Resíduos Minerais Fixos está relacionada a eliminação da matéria orgânica e a decomposição térmica da Pirita, sendo o primeiro fator muito mais relevante. As camadas de Xisto também apresentaram Albita, Microclínio e Muscovita, valores semelhantes de massa específica de partículas, óleo bruto com perfil cromatográfico de relativa elevação em massa entre os picos de Heptano e Undecano, distribuição uniforme entre os picos de Dodecano e Octacosano, distribuição decrescente entre os picos de Nonacosano e C72, com normais parafinas sobressalentes numa mistura orgânica complexa não resolvida. Estes resultados indicam que o resíduo Finos de Xisto tem composição oscilante entre os estreitos parâmetros do Xisto Superior e do Xisto Inferior.

Les sismologues ont révélé l'existence d'une anisotropie sismique complexe dans la graine terrestre. Cette thèse, en deux parties, présente deux approches différentes pour, d'une part, expliquer l'existence de cette anisotropie avec des modèles de graine numérique et, d'autre part, étudier l'effet des transformations de phase sur cette anisotropie.Dans un premier temps, nous avons construit un outil de simulation de la propagation des rais sismiques à travers une graine numérique, afin d'étudier la possibilité de reproduire numériquement les données sismologiques et de contraindre la dynamique et la minéralogie de la graine. Nous concluons qu'aucune structure du fer cubique ne permet de développer une anisotropie sismique significative. Seule la structure hexagonale compacte permet de le faire. Parmi les modèles géodynamiques quadripolaires étudiés, la croissance équatoriale préférentielle est le processus dynamique qui présente le meilleur accord avec les observations de dépendance à la profondeur et d'anisotropie polaire. L'ajout d'une stratification chimique permet d'amplifier d'environ 40% l'anisotropie globale mais augmente la dispersion des résidus sismiques, ce qui n'est pas conforme aux observations de dépendance à la profondeur. Enfin, une croissance dendritique (texture de solidification) est peu compatible avec une anisotropie principale Nord-Sud. Il apparaît clairement qu'aucun de ces modèles géodynamiques ne permet d'obtenir une amplitude d'anisotropie suffisante en utilisant les propriétés élastiques publiées pour le fer dans la graine. A l'issue de ce travail, de nombreux autres processus dynamiques restent encore à étudier, tels que les forces de Lorentz et la translation-convection thermique, processus bipolaire qui présente un fort intérêt pour la caractérisation de la composante hémisphérique de l'anisotropie sismique.Dans un deuxième temps, nous avons procédé à des expériences de transition de phase α-ε (fer cubique centré vers fer hexagonal compact) dans le fer pur. Nous avons simulé les textures résultantes à l'aide du mécanisme de Burgers. Nous avons confronté nos simulations aux résultats expérimentaux. Nous avons pu confirmer la validité du mécanisme de transformation de Burgers. Nous avons trouvé une forte sélection de variant sous l'effet de la contrainte non-hydrostatique dans le sens direct α→ε, produisant de fortes textures. Dans le sens inverse ε→α, on observe des textures finales très faibles, voire aléatoires. Appliqués avec prudence au cas de la graine terrestre, nos résultats indiquent que la transformation de phase du fer hexagonal à cubique ne peut pas expliquer la forte anisotropie observée. Nous avons aussi noté une mémoire de texture partielle, déjà documentée pour d'autres métaux de transition. Enfin, nous avons procédé à des tests préliminaires en cellule diamant en rotation. Les résultats de ces expériences de cisaillement ont également montré un très bon accord avec les simulations fondées sur le mécanisme de Burgers. En revanche, nous avons pu constater de grands écarts entre nos résultats expérimentaux et les simulations en cisaillement présentées dans la littérature [Levitas et al., 2010], notamment en termes de gradient de contraintes. / Seismologists revealed the existence of a complex seismic anisotropy in the Earth's inner core. In this thesis we took two different approaches in order to characterize the anisotropy: in a first part, we tried to explain this anisotropy using formation models of inner core and, in a second part, we considered the impact of eventual phase transitions on anisotropy.Firstly, we simulate the propagation of seismic rays through a numerically grown inner core, in order to measure the seismic anisotropy to compare with actual observations and to constrain the dynamics and mineralogy of the inner core. We conclude that no cubic structure of iron may produce a significant global anisotropy. Only the hexagonal compact phase of iron may produce a measurable signal. Considering a panel of quadripolar geodynamical models, we observe that simple preferential equatorial growth is the most consistent with seismological observations of a polar anisotropy and depth dependence of seismic residuals. Chemical stratification amplifies the global anisotropy by about 40%, but at the same time increases the scatter of residuals in a way that is poorly compatible with the observed depth dependence. Finally the addition of dendritic growth (solidification texture) prohibits the emergence of a first order North-South anisotropy. Independently of the geodynamical model it appears clearly that none of these geodynamical models the development of an anisotropy consistent with observations when using the published elastic properties of iron at inner core conditions. Following this work, several geodynamical models remain to be studied such as magnetic forcing (Lorentz forces). Models involving translation-thermal convection are of great interest as they may account for the hemispherical component of the seismic anisotropy.Secondly, we performed experiments on the α-ε (cubic centered to hexagonal compact iron) phase transition in pure iron. We compare our experimental texture results with our simulations of the transformation considering Burgers mechanism. We confirm here the Burgers atomic path as the mechanism activated during the α-ε transformation in iron. We find direct evidence of a strong variant selection controlled by non-hydrostatic stresses in the diamond anvil cell during the forward α→ε transformation, producing strong textures. The opposite will occur with the reverse ε→α phase transition where an almost complete randomization is to be expected. Our observations can be applied with some caution to the Earth's inner core and show that the strong seismic anisotropy in the inner core may not be explained by the occurrence of a hexagonal to cubic phase transition in the inner core. A limited texture memory effect was brought into light, already documented for other transition metals. At last, we performed a preliminary study on the effect of shear on the α-ε phase transition in pure iron using a rotational cell. Again the α-ε phase transformation in iron can be modelized by the Burgers mechanism. We find that simulations in the literature [Levitas et al., 2010] fail to reproduce our experimental results, particularly in terms of stress field.