Les sulfates de sodium sont admis comme étant les sels les plus destructeurs pour les pierres naturelles et autre matériaux poreux. Les processus de cristallisation de ces sels demeurent encore mal compris, plus particulièrement les relations entre l'heptahydrate (SS7, Na2SO4-7H2O) et la mirabilite (SS10, Na2SO4-10H2O). L'heptahydrate, métastable, a longtemps été négligée dans les travaux scientifiques portant sur l'altération saline jusqu'à récemment, et son rôle dans l'altération des roches n'est toujours pas établi à ce jour. Afin de mieux comprendre le rôle des différentes phases dans l'altération, il est important de pouvoir identifier quelle phase cristallise sous des conditions environnementales spécifiques. La cristallisation du sel se produit le plus souvent dans les matériaux poreux où les processus de cristallisation ne peuvent pas être observés directement in situ. Dans cette étude, nous utilisons le suivi de la température pour détecter et identifier la cristallisation des hydrates au cours de cycles de refroidissement/chauffage d'une solution de sulfate de sodium et de l'échantillon de calcaire saturé de cette même solution. En parallèle, d'autres approches expérimentales consistent à mesurer la réponse électrique et élastique des processus de cristallisation / dissolution se produisant dans le milieu poreux. Ces méthodes permettent d'identifier les différentes transitions de phases se produisant au cours de cycles de température et peuvent être utilisées dans des études expérimentales de vieillissement accéléré, afin d'estimer le rôle respectif des différents hydrates de sulfate de sodium dans l'altération des pierres par les sels. / Sodium sulfates are well known to be the most damaging salts in building materials and rocks. The crystallization processes of sodium sulfates are not completely understood, and more specifically the transition between the heptahydrate (SS7, Na2SO4-7H2O) and the mirabilite (SS10, Na2SO4-10H2O). The metastable heptahydrate has long been neglected in scientific works on salt damage until recently, and its role in rock weathering has not been established so far. In order to better understand the role of the different phases in damaging process, it is important to be able to identify which phase crystallizes under specific environmental conditions. Unfortunately, salt crystallization occurs very often within porous material and crystallization processes cannot be observed directly in situ. In this study, we use temperature monitoring to detect and identify the hydrates crystallization during cooling/heating cycles a sodium sulfate solution and limestone samples saturated with the same solution. In parallel, other experimental approaches consist to measure the electrical and elastic responses of the crystallization/dissolution processes occurring in the porous media. These methods enable to characterize the different phases occurring during temperature cycle and can be used in further experimental studies about ageing test in order to estimate the role of the different sodium sulfate hydrates involved in the salt weathering of rocks.

Os revestimentos curáveis por radiação ultravioleta (UV) ou feixe de elétrons (EB) são sistemas líquidos reativos compostos por resinas, diluentes (monômero) e aditivos, capazes de formar compostos poliméricos termorrígidos por reações de polimerização e reticulação induzidas por radiação. Esta tecnologia tem sido empregada como alternativa aos processos convencionais no desenvolvimento de uma variada gama de produtos. Um dos grandes desafios da aplicação da tecnologia de cura UV/EB em produtos a serem submetidos ao intemperismo é a manutenção de suas propriedades físicas e de sua aparência. Este trabalho apresenta informações sobre o comportamento de quatro vernizes com e sem aditivos estabilizantes à luz-curados por radiação UV ou EB quando submetidos ao processo de envelhecimento acelerado. Os vernizes foram caracterizados por técnicas termoanalíticas como termogravimetria (TG), calorimetria exploratória diferencial (DSC) e fotocalorimetria diferencial (foto-DSC); espectroscopia de absorção no infravermelho e no ultravioleta, e propriedades mecânicas. Os vernizes sob a forma de filmes de 50 µm de espessura foram curados com diferentes doses de radiação UV ou EB. A cura por radiação UV foi conduzida em túnel de luz, provido de uma lâmpada de mercúrio de média pressão e esteira rolante com velocidade variável. As diferentes doses de radiação UV de 50 a 1500 mJ cm-2 foram obtidas variando-se a velocidade da esteira. A cura por EB foi realizada utilizando-se acelerador de elétrons de energia de 1,5 MeV, sob atmosfera de nitrogênio, aplicando-se doses no intervalo de 1,6 a 300 kGy. O grau de cura dos diferentes filmes foi calculado por meio dos valores das entalpias de reação da cura residual obtidos por DSC. Os testes de envelhecimento acelerado dos filmes curados foram feitos em câmara de envelhecimento do tipo Weather-Ometer por períodos de exposição de 100 a 3000 horas. Os dados obtidos experimentalmente foram avaliados em função da composição dos vernizes, da dose e do tipo de radiação empregada na cura e do tempo de permanência na câmara de envelhecimento. Os resultados indicam que os filmes curados por EB apresentam maior durabilidade frente ao intemperismo do que os seus pares curados por radiação UV. Os filmes não estabilizados (sem aditivos) apresentam grande instabilidade nas condições do teste de envelhecimento. O efeito do envelhecimento foi observado por meio de dados de dureza, brilho, rugosidade, índice de amarelecimento e alteração das bandas de absorção dos espectros FTIR. / The materials curable by ultraviolet (UV) or electron beam (EB) radiation such as inks, adhesives and coatings are reactive compounds made up of resin, monomer, photoinitiator and additives which undergo polymerization and crosslinking under irradiation producing thermoset products. This technology has been used in a great variety of industrial applications, replacing the conventional curing process in the development of new products. One of the challenging applications has been to design weatherable radiation cured coating which maintain their desirable physical properties and aesthetic appearance. This research reports information about the behavior of four UV and EB curable clear coatings -with or without light stabilizer additives- under accelerated weathering. Thermogravinietry, differential scanning calorimetry, differential photocalorimetry, infrared and ultraviolet spectroscopy and tensile properties were used to evaluate these formulations. Clear coating 50 µm thick films were cured with UV and EB radiation at different doses. The UV curing process was carried out at room temperature using an UV tunnel, with a medium pressure mercury lamp and a transport belt with variable speed. The ultraviolet radiation doses were in the range of 50 to 1500 mJ cm-2. The EB curing process was performed under N2 atmosphere, with doses in the range from 1,6 to 300 kGy using the IPEN-CNEN/SP Dynamitron electron beam accelerator with energy of 1.5 MeV. The cure degree was determined by means of the residual reaction heat of the undercured samples obtained from photo-DSC or DSC measurements. The accelerated aging tests were carried out using a Weather-Ometer chamber with exposition times in the range of 100 to 3000 hours. The experimental data obtained from the photo-aged samples were evaluated and correlated to the formulation composition, type of radiation - UV or EB, radiation dose and residence time in the aging chamber. The results have shown that the EB cured films have a better resistance to photoinduced weathering effects than UV cured ones. UV/EB films with light stabilizers have shown larger stability than those counterparts with no additives. The aging effects were evaluated by parameters such as hardness, gloss, surface roughness, yellowness index and changes in the FTIR absorption bands.

The revision of the CEN/TR 15522-2:2012 methodology contains new biomarkers to facilitate forensic fingerprinting of the variety of oil types that can be a part of different crimes and the purpose of this project is to validate the biomarkers of the new methodology. Biomarkers were validated by examining corresponding diagnostic ratios compatibility with the internationally used sampling cloth, discriminating power, correlation and simulated weathering sensibility through GC-SIM-MS analysis followed by statistical evaluation with t-tests, diagnostic power, Pearson correlation matrices and MS-PW plots respectively. Results based on most of the diagnostic ratios showed good compatibility with the internationally used sampling cloth, expected patterns of biodegradation and photo-oxidation except for observed photo-oxidation of hydro PAHs and that normative ratios and informative ratios with high diagnostic powers, but with strong correlations for some of the tested ratios, could be identified in diesel oils. Due to delimitations however such as the limited number of oils with similar origins that were analyzed the results should be regarded as guidelines that can be expanded.

Esta pesquisa teve por objetivo avaliar a suscetibilidade a ensaios de intemperismo acelerado de cinco rochas usadas no patrimônio histórico e cultural das cidades do Rio de Janeiro e São Paulo, para determinar suas resistências frente a: ambientes quimicamente agressivos por meio de exposições em câmaras saturadas de SO2 e NaCl; imersão parcial em soluções ácidas e alcalina (H2SO4, HCl, HNO3 e NaOH); e ciclagens de choque térmico. As rochas abordadas no estudo foram: Granito Itaquera, Granito Cinza Mauá e Monzonito Preto Piracaia, de São Paulo; Gnaisse Facoidal do Rio de Janeiro e um mármore branco do Espírito Santo. Com exceção do mármore, incluído no estudo devido aos diversos monumentos históricos feitos em mármores dos mais variados, todas as rochas tiveram larga utilização na construção de edifícios e monumentos das duas cidades. Nas rochas submetidas às alterações foram feitas determinações, previamente e posteriormente aos ensaios, de suas características físicas: densidade, porosidade, absorção de água, absorção de água por capilaridade, absorção de água por tubo de Karsten, índice de resistência ao carregamento pontual, velocidade de propagação de ondas ultrassônicas, resistência superficial por martelo de rebote (martelo de Schmidt) e cor por espectrofotometria. Foram efetuadas também análises petrográficas das rochas e difratometria de raios X em sais gerados nos corpos parcialmente imersos em soluções. A caracterização das rochas sãs foi catalogada com o intuito de contribuir com estudos de conservação-restauração futuros, considerando que o acesso a pedreiras e disponibilidade das mesmas tendem a diminuir, devido à urbanização e exaustão de pedreiras. Dentre as alterações impostas, a que mais impactou as rochas foi a do choque térmico. As alterações de caráter químico foram mais agressivas sobre o mármore, gerando alterações mais sutis nos outros litotipos, conforme era esperado. Os métodos de velocidade de propagação de ondas ultrassônicas e a resistência superficial por martelo de rebote permitiram inferir que as alterações ocorridas foram predominantemente superficiais, uma vez que ocorreu maior perda de resistência superficial do que redução de velocidade. A rocha que apresenta maior perda de resistência superficial é o Monzonito Preto Piracaia, que em contrapartida apresenta baixa alteração de velocidade ultrassônica. A alteração de cor foi expressiva em todas as rochas, sendo o procedimento de imersão parcial em soluções ácidas o mais agressivo. / The purpose of this research was to evaluate the susceptibility to accelerated weathering tests of five rocks used in the historical and cultural patrimony of the cities of Rio de Janeiro and São Paulo in order to determine their resistance to: chemically aggressive environments through exposure to SO2 and NaCl in saturated chambers; partial immersion in acidic and alkaline solutions (H2SO4, HCl, HNO3 and NaOH); and thermal shock cycling. The rocks covered in the study were: Itaquera Granite, Gray Mauá Granite and Black Piracaia Monzonite, from São Paulo; Augen Gneiss from Rio de Janeiro and a white marble from Espirito Santo. All the rocks have been widely used in the construction of buildings and monuments of the two cities, except for the marble, which was included in the study due to its use in various historical monuments. To the rocks subjected to the artificial weathering, determinations of their physical characteristics were made, before and after the tests: density, porosity, water absorption, water absorption by capillarity, water absorption by Karsten tube, point load strength index, ultrasound pulse velocity, surface resistance by rebound hammer (Schmidt\'s hammer) and color by spectrophotometry. Also, petrographic analyses of the rocks and X - ray diffraction in salts generated in the bodies partially immersed in solutions were carried out. The characterization of unaltered rocks was cataloged with the intention of contributing to future studies of conservation and restoration, considering that the access to quarries and their availability tend to decrease due to the urbanization and exhaustion of quarries. Among the alterations imposed, thermal shock was the one that most affected the rocks. While chemical alterations were more aggressive on the marble, more subtle alterations were observed in the other lithotypes, as expected. The ultrasonic wave propagation velocity methods and the surface resistance by rebound hammer allowed to infer that the alterations occurred were predominantly superficial, since there was a greater loss of surface resistance than reduction of velocity. The rock that presented the greatest loss of surface resistance is the Black Piracaia Monzonite, which in turn has a low ultrasonic velocity change. The color change was significant in all rocks, with the partial immersions in acidic solutions being the most forceful procedure for this characteristic.

Le Sud du Brésil est une région où l'agriculture est très intensive et la pression sur les sols est beaucoup plus importante que dans la région amazonienne. Ainsi, il est important d'étudier les processus d'altération des roches qui constituent des étapes clés du développement des sols et de leurs fonctions environnementales.Dans ce contexte, ce travail vise à : (i) caractériser la morphologie, les propriétés physiques et chimiques de profils d'altération développés en l'absence ou avec une intervention humaine minimale : (ii) établir les évolutions géochimiques et minéralogiques des sols dans un environnement subtropical ; et (iii) évaluer l'impact des actions anthropiques sur la minéralogie des horizons de surface. Cette étude concerne des sols du Rio Grande do Sul dont le climat subtropical (T ~17°C et P ~1800 mm/an) favorise l'accumulation de matière organique ainsi que la formation de minéraux argileux 2:1 en faible proportion. Les indices d'altération (Weathering Intensity Scale – WIS, Chemical Index of Alteration - CIA) permettent de classer les profils selon leur degré d'altération et de leur composition minéralogique différente (smectite, smectite + kaolinite, kaolinite). Dans la dernière partie les résultats montrent qu'après 12 ans de culture des sols avec un système intégré culture-élevage les surfaces non pâturées présentent une proportion moins importante de minéraux 2:1. Les surfaces sous pâturage intensif et modéré présentent une aluminisation plus élevée de la couche interfoliaire des minéraux 2:1. La fixation d'une partie de l'aluminium dans la phase solide du sol, ce qui pourrait le rendre moins disponible pour les plantes et diminuer sa phytotoxicité. / Southern Brazil is a region with a very intensive agriculture and the pressure on soil is considerably more intense than in the Amazonian region. Thus, it is necessary to study weathering processes as they control soil development and their environmental functions.In this context, this work aims to: (i) characterize the morphological, physical and chemical properties of weathering profiles developed in the absence, or with minimal human action; (ii) establish the geochemical and mineralogical evolution of soils in a subtropical environment; and (iii) assess the impact of anthropogenic actions on on the mineralogy of surface horizons. This study concerns soils of Rio Grande do Sul where the subtropical climate (T ~17°C and P ~1800mm/yr) favored the accumulation of organic matter and occurrence of 2:1 clay minerals in low proportion. The weathering indices (Weathering Intensity Scale - WIS and Chemical Index of Alteration - CIA) make it possible to classify the profiles according to their weathering intensity and their different mineralogical compositions (smectite, smectite + kaolinite, kaolinite).In the last chapter, the results show that after 12 years of cultivation under an integrated soybean–beef cattle production system, the ungrazed areas presented lower proportion of 2:1 minerals. The areas under intensive grazing and moderate grazing presented higher aluminization of the interlayer of 2:1 minerals. The higher aluminization under intensive and moderate grazing managements may be a drain of aluminum in the soil solid phase and possibly making it less available to plants and decreasing its phytotoxicity. / O sul do Brasil é uma região com uma agricultura muito intensa e com grande pressão de uso do solo, consideravelmente mais intenso do que na região da Amazônia. Assim, é necessário desenvolver estudos que relacionem o desenvolvimento do solo com seu respectivo material de origem, detalhando as transformações na zona de transição solo-rocha e suas implicações para as atividades ambientais e humanas. Neste contexto, este trabalho tem como objetivo: (i) caracterizar os aspectos mineralógicos, pedoquimicos e geoquimicos dos perfis de alteração desenvolvidos na ausência ou mínima ação humana; (ii) caracterizar qualitativa e semi-quantitativamente os minerais primários e os minerais pedogênicos em solos inseridos em regiões ecossistêmicas importantes do Rio Grande do Sul; e (iii) avaliar o impacto de diferentes intensidades de pastejo na mineralogia de um Latossolo, sob sistema de produção integrada soja-bovinos de corte no sul do Brasil. Este estudo foi realizado em solos do Rio Grande do Sul, onde o clima subtropical (temperatura média anual ~ 17°C, precipitação anual média de 1800mm/ano) favorece o acúmulo de matéria orgânica ea ocorrência de argilominerais 2:1.Os índices de intemperismo (Weathering Intensity Scale - WIS e Chemical Index of Alteration - CIA), considerando a composição mineralógica dos perfis de alteração, indicaram a seguinte sequência crescente do grau de intemperismo: esmectita < caulinita - esmectita < caulinita. O estudo mostrou diferenças importantes nos solos, mesmo entre aqueles formados a partir do mesmo material de origem, devido às diferenças climáticas e de relevo. Por fim, após 12 anos sob um sistema integrado de produção de soja-bovinos de corte, as áreas não pastejadas apresentaram menor intensidade para os argilominerais 2:1. Por outro lado, as áreas sob pastejo intensivo e pastejo moderado apresentaram comportamento semelhante, devido à maior aluminização da entrecamada dos argilominerais 2:1. A maior aluminização sob pastejo intensivo e moderado pode ser um dreno de alumínio na fase sólida do solo, tornando-o menos disponível para as plantas e diminuindo sua fitotoxicidade.

Chemical weathering of silicate rock consumes atmospheric CO2 and supplies the oceans with cations, thereby controlling both seawater chemistry and climate. The rate of CO2 consumption is closely linked to the rate of CO2 outgassing from the planetary interior, providing a negative feedback loop essential to maintaining an equable climate on Earth. Reconstruction of past global temperatures indicates that a pronounced episode of global cooling began ~50 million years ago, coincident with the collision of India and Asia, and the subsequent exhumation of the Himalayas and Tibet. This has drawn attention to the possible links between exhumation, erosion, changes in silicate weathering rates, and climate. However, many of the present-day weathering processes operating on the continents remain debated and poorly constrained, hampering our interpretations of marine geochemical archives and past climatic shifts. To constrain the controls on silicate weathering, this thesis investigates the lithium (Li) isotopic composition of river waters, suspended sediments and bed load sediments in the Alaknanda river basin, forming the headwaters of the Ganges. Due to the large fractionation of Li isotopes in the Earth’s surface environment, Li is sensitive to small changes in silicate weathering processes. As a consequence of the pronounced gradients in climate (rainfall and temperature) and erosion across the basin, the river waters show large variations in their Li isotopic composition (δ7Li), ranging from +7.4 to +35.4‰, covering much of the observed global variation. This allows a detailed investigation of the controls on Li isotope fractionation, and by extension silicate weathering. The Li isotopic composition is modelled using a one-dimensional reactive transport model. The model incorporates the continuous input of Li from rock dissolution, removal due to secondary mineral formation, and hydrology along subsurface flow paths. Modelling shows that the Li isotopic variations can be described by two dimensionless variables; (1) the Damköhler number, ND, which relates the silicate dissolution rate to the fluid transit time, and (2) the net partition coefficient of Li during weathering, kp, describing the partitioning of Li between secondary clay minerals and water, which is primarily controlled by the stoichiometry of the weathering reactions. The derived values of the controlling parameters ND and kp, are investigated over a range of climatic conditions and on a seasonal basis, shedding light onto variations in the silicate weathering cycle. In a kinetically limited weathering regime such as the Himalayan Mountains, both climate and erosion exert critical controls the weathering intensity (the fraction of eroded rock which is dissolved) and the weathering progression (which minerals that are being weathered), and consequently the fractionation of Li isotopes and silicate weathering in general. Modelling of the Li isotopic composition provides an independent estimate of the parameters which control silicate weathering. These estimates are then used to constrain variables such as subsurface fluid flux, silicate dissolution rates, fluid transit times and the fraction of rock which is weathered to form secondary clay minerals. The simple one-dimensional reactive transport model therefore provides a powerful tool to investigate the minimum controls on silicate weathering on the continents.

Esta pesquisa teve por objetivo avaliar a suscetibilidade a ensaios de intemperismo acelerado de cinco rochas usadas no patrimônio histórico e cultural das cidades do Rio de Janeiro e São Paulo, para determinar suas resistências frente a: ambientes quimicamente agressivos por meio de exposições em câmaras saturadas de SO2 e NaCl; imersão parcial em soluções ácidas e alcalina (H2SO4, HCl, HNO3 e NaOH); e ciclagens de choque térmico. As rochas abordadas no estudo foram: Granito Itaquera, Granito Cinza Mauá e Monzonito Preto Piracaia, de São Paulo; Gnaisse Facoidal do Rio de Janeiro e um mármore branco do Espírito Santo. Com exceção do mármore, incluído no estudo devido aos diversos monumentos históricos feitos em mármores dos mais variados, todas as rochas tiveram larga utilização na construção de edifícios e monumentos das duas cidades. Nas rochas submetidas às alterações foram feitas determinações, previamente e posteriormente aos ensaios, de suas características físicas: densidade, porosidade, absorção de água, absorção de água por capilaridade, absorção de água por tubo de Karsten, índice de resistência ao carregamento pontual, velocidade de propagação de ondas ultrassônicas, resistência superficial por martelo de rebote (martelo de Schmidt) e cor por espectrofotometria. Foram efetuadas também análises petrográficas das rochas e difratometria de raios X em sais gerados nos corpos parcialmente imersos em soluções. A caracterização das rochas sãs foi catalogada com o intuito de contribuir com estudos de conservação-restauração futuros, considerando que o acesso a pedreiras e disponibilidade das mesmas tendem a diminuir, devido à urbanização e exaustão de pedreiras. Dentre as alterações impostas, a que mais impactou as rochas foi a do choque térmico. As alterações de caráter químico foram mais agressivas sobre o mármore, gerando alterações mais sutis nos outros litotipos, conforme era esperado. Os métodos de velocidade de propagação de ondas ultrassônicas e a resistência superficial por martelo de rebote permitiram inferir que as alterações ocorridas foram predominantemente superficiais, uma vez que ocorreu maior perda de resistência superficial do que redução de velocidade. A rocha que apresenta maior perda de resistência superficial é o Monzonito Preto Piracaia, que em contrapartida apresenta baixa alteração de velocidade ultrassônica. A alteração de cor foi expressiva em todas as rochas, sendo o procedimento de imersão parcial em soluções ácidas o mais agressivo. / The purpose of this research was to evaluate the susceptibility to accelerated weathering tests of five rocks used in the historical and cultural patrimony of the cities of Rio de Janeiro and São Paulo in order to determine their resistance to: chemically aggressive environments through exposure to SO2 and NaCl in saturated chambers; partial immersion in acidic and alkaline solutions (H2SO4, HCl, HNO3 and NaOH); and thermal shock cycling. The rocks covered in the study were: Itaquera Granite, Gray Mauá Granite and Black Piracaia Monzonite, from São Paulo; Augen Gneiss from Rio de Janeiro and a white marble from Espirito Santo. All the rocks have been widely used in the construction of buildings and monuments of the two cities, except for the marble, which was included in the study due to its use in various historical monuments. To the rocks subjected to the artificial weathering, determinations of their physical characteristics were made, before and after the tests: density, porosity, water absorption, water absorption by capillarity, water absorption by Karsten tube, point load strength index, ultrasound pulse velocity, surface resistance by rebound hammer (Schmidt\'s hammer) and color by spectrophotometry. Also, petrographic analyses of the rocks and X - ray diffraction in salts generated in the bodies partially immersed in solutions were carried out. The characterization of unaltered rocks was cataloged with the intention of contributing to future studies of conservation and restoration, considering that the access to quarries and their availability tend to decrease due to the urbanization and exhaustion of quarries. Among the alterations imposed, thermal shock was the one that most affected the rocks. While chemical alterations were more aggressive on the marble, more subtle alterations were observed in the other lithotypes, as expected. The ultrasonic wave propagation velocity methods and the surface resistance by rebound hammer allowed to infer that the alterations occurred were predominantly superficial, since there was a greater loss of surface resistance than reduction of velocity. The rock that presented the greatest loss of surface resistance is the Black Piracaia Monzonite, which in turn has a low ultrasonic velocity change. The color change was significant in all rocks, with the partial immersions in acidic solutions being the most forceful procedure for this characteristic.

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No. of bitstreams: 1 DISSERTAÇÃO-ÉRITON GONÇALO RUBEM.pdf: 2575591 bytes, checksum: d7e93a9078f655ec22ccea74a604b55e (MD5) Previous issue date: 2014-07-14 / FAPEAM - Fundação de Amparo à Pesquisa do Estado do Amazonas / Wood when exposed to sunlight undergoes chemical degradation surface which causes a change of color and weakening its mechanical strength. This process of surface degradation is commonly called weathering process. Although providing satisfactory results, the conventional methods of analysis expose the operator to hazardous environments and / or toxic materials necessary in the analyzes. An alternative to traditional destructive evaluation would be to use non-destructive methods for evaluating properties of wood. As an option to perform the analysis nondestructively technology emerges near infrared Fourier transform (FT-NIR), which gives information about the chemical properties of a sample. The study aimed to evaluate the effects of weathering on the main macroconstituintes wood (cellulose and lignin) through FR-NIR technology. To achieve the proposed objective we chose to use timber waste from three Amazonian forest species: Maçaranduba (Manilkara huberi), Tauari (Couratari stellata) and Marupá (Simarouba amara) chosen for having high, medium and low density respectively and relative insertion timber market in the Amazon region. The samples were subjected to methods of natural and artificial weathering, where the natural weathering test lasted a year and the artificial weathering test lasted 27 weeks. The samples were analyzed weekly with the FT-NIR spectrophotometer over the period of natural and artificial weathering tests. The test results showed changes in spectra during the processes of natural and artificial weathering and UV light prove that the chemical structure of modified wood by decomposition of the chemical constituents and the formation of lignin-related cellulose compounds. In the natural and artificial weathering test maçaranduba takes longer to break down cellulose and lignin, but with the increase in period of weathering, the peaks related to pulp and lignin change and decrease and tend. The rate of decomposition of the wood surface is characteristic of each species. / A madeira quando exposta à radiação solar sofre degradação química superficial que provoca uma mudança de cor e um enfraquecimento da sua resistência mecânica. Esse processo de degradação superficial é comumente chamado de processo de intemperização. Apesar de apresentarem resultados satisfatórios, os métodos de análise convencionais expõem o operador aos ambientes de risco e/ou materiais tóxicos indispensáveis nas análises. Uma alternativa à tradicional avaliação destrutiva seria o uso de métodos não destrutivos para avaliar as propriedades da madeira. Como opção para realização das análises de forma não destrutiva surge a tecnologia de infravermelho próximo com transformada de Fourier (FT-NIR), que permite obter informações sobre as propriedades químicas de uma amostra. O trabalho teve por objetivo avaliar os efeitos do intemperismo nos principais macroconstituintes da madeira (celulose e lignina) através da tecnologia FR-NIR. Para alcançar o objetivo proposto optou-se pela utilização de resíduos madeireiros de três espécies florestais amazônicas: Maçaranduba (Manilkara huberi), Tauari (Couratari stellata) e Marupá (Simarouba amara) escolhidas por apresentarem alta, média e baixa densidade respectivamente e relativa inserção no mercado madeireiro da região Amazônica. As amostras foram submetidas aos métodos de intemperização natural e artificial, onde o teste de intemperização natural teve duração de um ano e o teste de intemperização artificial teve a duração de 27 semanas. As amostras foram analisadas semanalmente com o espectrofotômetro FT-NIR durante o período dos testes de intemperização natural e artificial. Os resultados dos testes mostraram alteração nos espectros durante os processos de intemperização natural e artificial e provam que a luz UV modificou a estrutura química da madeira por meio da decomposição de constituintes químicos da lignina e da formação de compostos relacionados à celulose. No teste de intemperismo natural e artificial a maçaranduba demora mais para decompor a celulose e a lignina, porém com o aumento do período de intemperização, todas as bandas referentes à celulose e à lignina se alteram e tendem e diminuir. A velocidade de decomposição da superfície da madeira é característica de cada uma das espécies estudadas.

The Cretaceous Mowry Shale is an organic-rich, siliceous marine shale, and as such is a known source rock in the Western United States. Studies have documented that total organic carbon (TOC) in the Wind River Basin, Wyoming increases to the southeast. These studies cover large areas with limited sample sets. In this study, over 250 samples were collected near Lander, Wyoming to address spatial heterogeneity of TOC within the Mowry Shale at a much finer scale than previously examined. Samples were collected along five vertical sections at three localities, and following correlation of the vertical sections, which was strongly aided by the presence of regional bentonite horizons, samples were collected laterally from the same unit at regular 25-foot intervals. These samples were analyzed using pyrolysis and x-ray diffraction techniques. Average TOC values are fairly consistent within the study area (1.65%, with a range of 2.10% to 1.15%). Average Tmax values for vertical and lateral samples is 433 °C with a standard deviation of 7.25 °C suggesting immature to very early oil window thermal maturity. Kerogen types are determined to be dominantly type III, suggesting a dominance of terrestrial input, becoming slightly more mixed type II/III to the southeast. Redox-sensitive trace metals such as uranium, thorium, vanadium, chromium, cobalt, and molybdenum values all suggest a slightly oxygenated sediment water interface during time of deposition. These pyrolysis and trace metal data suggest that the study area was in a prograding proximal marine/prodeltaic depositional environment during Upper Mowry time with influences from higher energy bottom flows. Lateral homogeneity of strata and the low variability in geochemical character across the study area suggest that the local basin in the study area was not segmented by structural or oceanographic conditions. While efforts were made to collect unaltered outcrop samples (digging back into what appeared to be unfractured, unaltered rock), alteration or weathering of organic material is a concern for source rock evaluation of near-surface outcrops. In order to address this concern, a 5-foot-deep trench was dug back into the outcrop at the target horizon in one locality. Samples were taken at regular three-inch intervals from this trench as it was excavated to determine the effect of weathering on TOC in the study area. Based on pyrolysis results, TOC was affected by weathering only along fracture sets (several samples intersected fractures in the shallow subsurface) and did not appreciably increase from the surface to a depth of five feet. Due to the impermeable nature of shale rock, decreases of TOC due to weathering appear to be limited to the immediate surface of samples and along fracture sets.

Exploration companies commonly rely on geochemistry to identify alteration of distinctive geochemical and mineralogical character, surrounding metal sulphide deposits that were precipitated from hydrothermal fluids. However, examination of raw analytical data is prone to error due to closure effects and the difficulty in removing the effects of background variation in unaltered rocks from the variations imposed by later hydrothermal alteration. Closure can be avoided by using ratios, or by utilising mass balance approaches based on fixing volume, mass or concentration changes between samples of parent and daughter lithologies. Using a parent-daughter approach is limiting, because only pairs of samples can be compared at any one time and because an unaltered equivalent must be produced for each sample examined in this way. Pearce Element Ratio analysis and General Element Ratio analysis (PER and GER) are not restricted in this fashion, and are more amenable to interrogation of large data sets. PER and GER are also capable of decoupling background variation from that variation due to hydrothermal alteration. Furthermore, these ratio methods are readily applied to commercially derived lithogeochemical assays. In this study, various analytical methods and interpretive techniques (including PER and GER) have been applied to identify alteration in rocks around the Century and Elura Zn-Pb-Ag deposits, and to assess whether primary ore-related alteration effects can still be identified once altered rocks have been subjected to weathering. Ratios of trace elements over a conserved element have been used to generate a suite of pathfinder elements for each deposit. Elements enriched in host rocks around both deposits include the economic metals Zn, Pb and Ag, along with Rb and Tl. Sodium is ubiquitously depleted in altered rocks. Other elements in the pathfinder suites are distinctive to each deposit type, and include a number of major and trace elements that are added or removed from the rocks around the mineralised zones. For example, Sb and As are enriched in rocks around Elura mineralisation while Ge and Cd are enriched in samples around Century deposit. Iron carbonate development accompanied by potassic alteration, the destruction of albite and the absence of chlorite are the dominant mineral alteration effects at both deposits. PER and GER diagrams have been used to quantify the intensity of this alteration and allow lithogeochemistry to be used to vector towards high intensity alteration, which is adjacent to Century and Elura mineralisation. These ratio methods are applied to both visibly and cryptically altered rocks at both deposits, and have a very high degree of success in classifying alteration in unweathered rocks. The following simple PER ratios indicate proximity to Elura mineralisation: Ca/C, K/Al for shales, K/(Al-Na) for siltstones/sandstones. The following simple PER ratios indicate proximity to Century mineralisation: Mn/Ti, Mg/Ti and Fe/Ti vs C/Ti, K/Ti vs Al/Ti, K/Ti vs (Al-Na)/Ti. Pathfinder elements can be overlain onto PER and GER diagrams to aid in ranking the prospectivity of samples, and to assess mineral hosts for individual pathfinder elements. Weathering destroys most indicators of alteration in the Elura area, while alteration signatures are better preserved in host rocks around the Century deposit.