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The Back to Nature project was developed as a collaborative doctoral award between the British Museum and the School of Geography and the Environment, University of Oxford. The British Museum has a large collection of limestone artefacts, some of which have deteriorated to an extent that a consolidation treatment, to improve internal cohesion, has been deemed necessary to ensure the value of the artefacts is maintained. Previous consolidation practices within the museum had centred on the use of organic consolidants. In the past, inorganic consolidants had been considered ineffective chiefly due to poor penetration depth and inconsistent deposition within the stone. Recent scientific developments within conservation, particularly the development of nano-limes, coupled with a trend towards treatments offering physical and chemical compatibility, led to the British Museum reconsidering the use of inorganic consolidants. Three inorganic consolidants: ammonium oxalate treatment, Calcite In-situ Precipitation System (CIPS), and CaLoSil have been investigated by the Back to Nature project to assess their potential for use on the British Museum’s deteriorated limestone artefacts. The investigation involved a developmental sequence of four experimental phases to assess the effectiveness of each consolidant upon freshly cut, artificially pre-weathered, and naturally weathered stone samples. In all experiments an organic silane Wacker SILRES BS OH 100 was used as a comparison. A variety of analytical methods were used including: Equotip, GrindoSonic, Scanning Electron Microscopy, Karsten Tubes, Drilling Resistance Measurement System, spectrophotometry, X-ray Diffraction and Ion Chromatography. Experiments show that the CIPS treatment could hold promise for use as a consolidant. Ammonium oxalate only appears to provide consolidation at the surface level, and CaLoSil would need modifying and more investigation before using in the museum environment. The differences noted between experiments on artificially weathered and naturally weathered stone indicate that a two-step process, involving testing on both types of samples, would give the best indication of consolidant effectiveness. High variability between samples shows a large number are needed to give an accurate interpretation of change due to consolidation.

This dissertation examines the microbial and functional diversity in Kartchner Caverns, a limestone cave in Arizona, USA. Kartchner is highly oligotrophic due to the lack of photosynthesis and the limited inputs of organic material from the surface. This characteristic poses a challenge for microbial life in the cave. The first objective of this work was to evaluate the bacterial richness, diversity and taxonomic composition of speleothems surfaces within Kartchner Caverns in order to gain insight into the distribution patterns associated with these communities. Secondly, the metabolic strategies used by cave communities to survive harsh cave conditions were investigated based on phylogenetic associations and metagenomics. Both objectives were directed toward answering the questions "who are there?" and "what are they doing?". The 454-pyrotag analysis of the V6 region of the 16S rRNA gene revealed an unexpectedly high bacterial diversity with each speleothem supporting a unique bacterial community profile. A focused study on one room of the cave revealed three community types: Type 1 was dominated by the phylum Proteobacteria; Type 2 by Actinobacteria; and Type 3 by Acidobacteria. Phylogenetic associations of the sequences generated by the 454 sequencing and by a Sanger clone library suggested cave microbial communities are supported by chemoautotrophic activities such as nitrite and iron oxidation. Results from the phylogenetic associations guided the metagenomic analysis which supports the presence of chemoautotrophic activities in the cave. Genes for two complete CO2 fixation mechanisms, the Calvin-Benson-Bashan and the rTCA cycles were identified in the cave metagenome, as well as genes for ammonia and nitrite oxidation. These genes are associated with both Bacteria and Archaea suggesting members of both domains are acting as primary producers in the cave ecosystem. Comparative analysis of cave samples to other environments suggests an overabundance of DNA repair mechanisms which could be potentially used by cave communities to overcome the toxicity due to high concentrations of calcium on the speleothem surfaces. This work provides the first comprehensive analysis of the microbial diversity and potential strategies used by microbial communities to survive under the extreme conditions found in a semi-arid limestone cave environment.

Alvars are globally rare rock barren ecosystems on limestone pavement. This thesis focused on the quantitative classification of vegetation of Manitoba alvars, the relationships between vegetation patterns and environmental factors and the effects of grazing on vegetation. Vegetation plots were completed across twenty sites. Cluster analysis, indicator species analysis and PCA were used to describe eight vegetation types. A RDA revealed moisture regime, soil depth, bare rock cover and disturbance (grazing and browsing) are the most important factors affecting floristic composition. Grazing effects were studied at two sites using paired plots on either side of a fenceline dividing grazed and ungrazed areas. PCA and RDA showed significant difference between vegetation compositions based on grazing. A partitioning of species richness and diversity by introduced and native species revealed that both sites experienced significant replacement by introduced species. Current grazing levels on Manitoba alvars are severely impacting the vegetation of this ecosystem. / October 2016

Master of Science / Department of Geology / Abdelmoneam Raef / Advancements, applications, and success of time-lapse (4D) seismic monitoring of carbonate reservoirs is limited by these systems’ inherent heterogeneity and low compressibility relative to siliciclastic systems. To contribute to the advancement of 4D seismic monitoring in carbonates, an investigation of amplitude envelope across frequency sub-bands was conducted on a high-resolution 4D seismic data set acquired in fine temporal intervals between a baseline and eight monitor surveys to track CO₂-EOR from 2003-2005 in the Hall-Gurney Field, Kansas. The shallow (approximately 900 m) Plattsburg ‘C Zone’ target reservoir is an oomoldic limestone within the Lansing-Kansas City (LKC) supergroup – deposited as a sequence of high-frequency, stacked cyclothems. The LKC reservoir fluctuates around thin-bed thickness within the well pattern region and is susceptible to amplitude tuning effects, in which CO₂ replacement of initial reservoir fluid generates a complex tuning phenomena with reduction and brightening of amplitude at reservoir thickness above and below thin-bed thickness, respectively. A thorough analysis of horizon snapping criteria and parameters was conducted to understand the sensitivity of these autonomous operations and produce a robust horizon tracking workflow to extend the Baseline Survey horizon data to subsequent Monitor Surveys. This 4D seismic horizon tracking workflow expedited the horizon tracking process across monitor surveys, while following a quantitative, repeatable approach in tracking the LKC and maintaining geologic integrity despite low signal-to-noise ratio (SNR) data and misties between surveys. Analysis of amplitude envelope data across frequency sub-bands (30-80 Hz) following spectral decomposition identified geometric features of multiple LKC shoal bodies at the reservoir interval. In corroboration with prior geologic interpretation, shoal boundaries, zones of overlap between stacked shoals, thickness variation, and lateral changes in lithofacies were delineated in the Baseline Survey, which enhanced detail of these features’ extent beyond capacity offered from well log data. Lineaments dominated by low-frequency anomalies within regions of adjacent shoals’ boundaries suggest thicker zones of potential shoal overlap. Analysis of frequency band-to-band analysis reveals relative thickness variation. Spectral decomposition of the amplitude envelope was analyzed between the Baseline and Monitor Surveys to identify spectral and tuning changes to monitor CO₂ migration. Ambiguity of CO₂ effects on tuning phenomena was observed in zones of known CO₂ fluid replacement. A series of lineaments highlighted by amplitude brightening from the Baseline to Monitor Surveys is observed, which compete with a more spatially extensive effect of subtle amplitude dimming. These lineaments are suggestive of features below tuning thickness, such as stratigraphic structures of shoals, fractures, and/or thin shoal edges, which are highlighted by an increased apparent thickness and onset of tuning from CO₂. Detailed analysis of these 4D seismic data across frequency sub-bands provide enhanced interpretation of shoal geometry, position, and overlap; identification of lateral changes in lithofacies suggestive of barriers and conduits; insight into relative thickness variation; and the ability of CO₂ tuning ambiguity to highlight zones below tuning thickness and improve reservoir characterization. These results suggest improved efficiency of CO₂ -EOR reservoir surveillance in carbonates, with implications to ensure optimal field planning and flood performance for analogous targets.

Molluscan succession was studied in 18 abandoned limestone quarries of different age in Bohemian Karst. The number of species in studied quarries increases in the time. The less species were found in the oldest quarries. This trend was probably caused by habitat diversity decline although it is not conclusive. The best predictors of mollusk species composition are type of surrounding vegetation, light and the cover of tree layer. It is important to take into account correlations of the other environmental variables with light and the cover of tree layer. Compositions of mollusk assemblages of north and south-facing slopes differ, but these differences diminish with ongoing succession. Quarries represent suitable model sites for the study of succession.

O projeto de lavra em minerações de calcário para fabricação de Cimento tem se mostrado de extrema importância em um mercado cada vez mais competitivo, como o de fabricação de cimento. No Brasil, dentro das minerações de grande porte, as minerações de calcário representam cerca de 20% de todo minério explotado. Metodologias que permitam um melhorar aproveitamento da jazida mineral ganham relevância para orientar projetos de longo prazo e exigem ferramentas para a tomada de decisão sobre o investimento ou não em projetos fabris e, consequentemente, sobre a viabilidade de projetos de lavra. A metodologia proposta foi aplicada em um exemplo e apresenta uma visão global dos problemas enfrentados em minerações de calcário e que facilitará a tomada de decisão sobre investimentos com premissas reais utilizadas por companhias cimenteiras. Além das premissas, serão apresentados problemas recorrentes encontrados quando se avalia a abertura de minerações de calcário para fabricação de cimento, com diversas variáveis exógenas ao projeto, como comunidades no entorno, sítios arqueológicos, cavernas protegidas, vegetação, entre outros, além dos fatores internos ao mesmo, como os teores, o \"blend\" de camadas, a relação estéril/minério, avaliações geotécnicas, entre outros. / The cement mining project for cement manufacturing has proved to be extremely important in an increasingly competitive market, such as cement manufacturing. In Brazil, within large-scale mining, limestone mining accounts for about 20% of all ore mined. Methodologies that allow a better use of the mineral deposit become of extreme importance to guide long-term projects and require tools for decision making on investment or not in manufacturing projects, and consequently on the feasibility of mining projects. The methodology proposed and applied in an application example will present an overview of the problems faced in limestone mining and will facilitate the decision making on investments with real premises used by cement companies. In addition to the premises, we will present current problems encountered when assessing the opening of limestone quarries for cement manufacturing, with innumerable variables exogenous to the project, such as surrounding communities, archaeological sites, protected caves, and vegetation, among others, besides the internal factors, such as ore grade, the blend of layers, the strip ratio, geotechnical evaluations, and others.

O carvão mineral apresenta-se como uma importante alternativa para geração termoelétrica no Brasil. Os carvões brasileiros, porém, são caracterizados por elevados teores de enxofre, e na sua combustão libera-se consideráveis de quantidades dióxido de enxofre. O processo de combustão em leito fluidizado apresenta-se particularmente adequado para a queima destes carvões, notadamente devido à possibilidade da utilização de absorventes calcários para remoção in loco do dióxido de enxofre produzido na combustão. Neste trabalho estudou-se a combustão em leito fluidizado atmosférico borbulhante de um carvão mineral beneficiado para uso termoelétrico denominado CE4500, procedente de Criciúma-SC. Para absorção de enxofre utilizou-se um calcário dolomítico procedente de Ipeúna-SP. Utilizou-se a planta piloto para combustão em leito fluidizado do Laboratório de Engenharia Térmica e Fluidos da EESC-USP, com câmara de combustão de 0,5 x 0,5 m de seção transversal e 3 m de altura. Ensaios foram realizados para diferentes velocidades de fluidização e relações (Ca+Mg)/S de alimentação. Concentrações de gases foram medidas ao longo da altura e da seção transversal do reator, permitindo verificar a homogeneidade do processo, além do efeito dos pontos de alimentação de carvão e calcário sobre esta homogeneidade. Determinou-se conversões e coeficientes globais de taxa de reação para a combustão do carvão e para a sulfatação do calcário. Avalia-se que os resultados obtidos representam uma significativa contribuição para auxílio ao projeto de reatores, e para a validação de modelos matemáticos de simulação. / Mineral coal stands as an important alternative for thermoelectric power generation in Brazil. Brazilian coals, however, are characterized by high sulfur contents, and significant amounts of sulfur dioxide are produced in its combustion. The fluidized bed combustion process is particularly suitable for burning those coals, notably due to the possibility of using limestone absorbents to in loco remove the sulfur dioxide produced in the combustion. In this work the atmospheric bubbling fluidized bed combustion of a mineral coal was studied, which is a benefited coal for thermoelectric use named CE4500, from Criciúma-SC. A dolomitic limestone from Ipeúna-SP was used for sulfur absorption. The pilot scale fludized bed combustion plant of the Laboratory of Thermal and Fluids Engineering of EESC-USP was used, which has a combustion chamber of 0.5 x 0.5 m of cross section and is 3 m high. Tests were performed for different fluidization velocities and (Ca+Mg)/S feed ratios. Gas concentrations were measured along the height and the cross section of the reactor, allowing to verify the process homogeneity, besides the effect of the coal and limestone feeding points over this homogeneity. Conversions and global reaction rates were determined for both coal combustion and absorption by limestone. It is evaluated that the results that were obtained represent a significant contribution regarding reactor design as well as modeling validation.

A gestão do processo de recuperação de uma área degradada pela mineração consiste em três etapas principais: planejamento; implementação das medidas de correção ou prevenção e implementação de gestão. Neste trabalho, foi desenvolvido um instrumento de avaliação que pode ser usado por órgãos públicos ou por empresas de mineração para auxiliar no controle e melhoria das práticas de recuperação ambiental. A avaliação é feita por meio da aplicação de um roteiro, fundamentado nas boas práticas internacionais e nacionais relacionadas à recuperação ambiental de minas. Para fins de teste e calibração, os roteiros foram aplicados em três minas de calcário, nas quais se verificou que as evidências - visuais, documentais e verbais (obtidas por meio de entrevistas) - coletadas devem ser interpretadas dentro de um contexto que envolva o entendimento das características ambientais e operacionais particulares de cada mina. As categorias de classificação da avaliação da eficácia de medidas de recuperação ambiental foram definidas em: eficaz, parcialmente eficaz, não eficaz e não se aplica. Ante aos resultados, foi possível identificar um \"cenário atual\" das práticas de recuperação ambiental empregadas em cada mina inspecionada e consequentemente recomendar ações visando a melhoria das práticas atuais e a redução de um futuro passivo ambiental. Diante destes resultados, conclui-se que o procedimento de avaliação da eficácia de medidas de recuperação ambiental desenvolvido nesta pesquisa é adequado, mas sua aplicação somente pode ser feita por um profissional que detenha alguma experiência no assunto, fator primordial para o julgamento e contextualização das evidências coletadas. O roteiro proposto nesta pesquisa ainda pode ser aplicado em outras minas de diferentes minerais e pedreiras. / The reclamation process management of an area degraded by mining activity consists of three main steps: planning. application of correction or prevention measures and monitoring. In this work, an assessment tool to be used by public bodies or by mining companies in order to support the control and improvement of environmental reclamation practices was developed. The assessment has been carried out with a script based on the national and international good practices regarding environmental reclamation in mines. For testing and calibration purposes, the scripts were applied in three limestone mines. The conclusion is that the evidences - visual, documental and verbal (interview) - must be analyzed in a context which involves the understanding of the environmental and operational characteristics in each mine. The categories for classification of the efficacy assessment of environmental reclamation measures have been defined as: efficacious, partially efficacious, non-efficacious and not applicable. Considering the results, it was possible to identify a \"current scenario\" of the environmental reclamation practices used in each inspected mine and consequently recommend actions to improve the current practices and reduce a future environmental liability. It was concluded that the procedure of the efficacy assessment of the environmental reclamation practices developed in this research is appropriate, but its application can only be made by a professional that presents some experience in the subject. It is a decisive factor for the evaluation and contextualization of the collected evidences. The proposed script for this research can still be applied in other mines with different minerals and quarries.

A geração de energia em larga escala a partir da combustão de carvões minerais impõe pesados ônus ao meio ambiente devido às emissões de poluentes. O processo de combustão em leito fluidizado destaca-se neste contexto, permitindo reduções de emissões de gases \'SO IND.X\' e \'NO IND.X\' acima de de 90%. O projeto, otimização e escalonamento de reatores de leito fluidizado são realizados de forma quase completamente empírica, através de desenvolvimentos em plantas de demonstração de escalas reduzidas. Os custos e tempos de implementação envolvidos são elevadíssimos, tornando ferramentas teóricas de apoio altamente desejáveis. Neste trabalho, desenvolve-se a modelagem e simulação da combustão em leito fluidizado atmosférico borbulhante de carvão mineral com altos teores de cinzas e enxofre com dessulfuração por calcário, através de uma abordagem fenomenológica. Comparações das predições do modelo são realizadas com dados experimentais gerados na planta piloto do NETeF, e estudos paramétricos são realizados para avaliação das performances do reator. As comparações mostram concordâncias e discrepâncias qualitativas e quantitativas entre perfis simulados e medidos das concentrações de gases e distribuições granulométricas do particulado. Isso indica a necessidade de aperfeiçoamentos na modelagem fenomenológica, notadamente com relação às correlações e dados empíricos utilizados. Apesar das discrepâncias, o modelo apresenta bons resultados quantitativos de eficiência de absorção de enxofre em comparação com os dados experimentais. / Energy generation through coal combustion imposes heavy environmental impacts due to pollutant emissions. The process of fluidized bed combustion distinguishes in this context allowing for emission reductions of \'SO IND.X\' and \'NO IND.X\' above 90%. The design, scaling-up, and optimization of fluidized bed reactors are mostly empirical, through small-scale demonstration plant developments. The costs and times of implementation involved in those developments are huge, making theoretical tools of analysis highly desirable. In this work modeling and simulation are performed for atmospheric bubbling fluidized bed combustion of high ash high sulfur coals, including desulfurization by limestone. A phenomenological approach to modeling is applied. Comparison of predictions are made against empirical measurements performed in the NETF pilot plant, and parametric studies are developed to evaluate reactor performances. The comparisons show both agreements and disagreements, qualitative as well as quantitative, between predictions and measured gas concentrations and particulate size distributions. This points to the necessity for improvements on the phenomenological modeling procedure that was applied, notably regarding the empirical correlations and data that were considered. Despite the discrepancies, the model produces good quantitative results of sulfur absorption efficiency in comparison to the empirical data.