CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A utilizaÃÃo de resÃduos como materiais alternativos tem se mostrado uma soluÃÃo satisfatÃria de acordo com vÃrias pesquisas realizadas. Os produtos da combustÃo do carvÃo mineral (PCCs) sÃo resÃduos que causam impacto ambiental, mas apresentam grande potencial de utilizaÃÃo no setor da construÃÃo civil na produÃÃo de argamassas e concretos. Apresentam elevado teor de sÃlica (SiO2), podendo ser utilizados como pozolanas. Esta pesquisa objetivou verificar a viabilidade da utilizaÃÃo dos produtos da combustÃo do carvÃo mineral em argamassas de assentamento e revestimento. As matÃrias-primas foram caracterizadas quanto aos aspectos fÃsicos, quÃmicos e para os PCCs tambÃm foi avaliada sua pozolanicidade. Foram confeccionadas argamassas de referÃncia e com adiÃÃo de PCCs nos teores de 10, 20, 30, 40 e 50% como substituto parcial do cimento. ApÃs tempos de cura de 7 e 28 dias, foram feitos teste de resistÃncia à traÃÃo na flexÃo e resistÃncia à compressÃo. AlÃm disso, as argamassas foram sujeitas a anÃlises de difraÃÃo de Raios â X, Microscopia EletrÃnica de Varredura, absorÃÃo de Ãgua, determinaÃÃo de Ãndice de vazios e massa especÃfica aparente. Os resultados obtidos mostraram-se compatÃveis quando comparados com os dados da literatura, demonstrando ser viÃvel a aplicaÃÃo dos produtos da combustÃo do carvÃo mineral na indÃstria da construÃÃo civil. / The use of residues as alternative materials has proven successful according to several investigations. Coal combustion products (CCPs) is a residue that causes environmental impact, but it has a great potential for use in civil engineering construction in the production of mortars and concrete. It posesses a high content of silica (SiO2) and so it can be used as pozzolan. This research aimed to verify the viability of adding coal combustion products to mortars for bricklaying and covering. The raw materials were submitted to physical, and chemical characterization. CCPs were also rated according to their pozzolanicity. Reference mortars were prepared, as well as mortars containing 10, 20, 30, 40 and 50% amounts of CCPs as a partial replacement for cement. After curing time of 7 and 28 days, prismatic samples were tested to determine their tensile strength in bending and their compression strength. Moreover, the mortars were subjected to X-ray diffraction, scanning electron microscopy and determination of water absorption, voids and apparent density. The results obtained were consistent with literature data, showing that application of coal combustion products in the construction industry is a viable alternative.

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Durante a queima do carvÃo mineral sÃo gerados vÃrios tipos de resÃduos ou subprodutos (produtos da combustÃo do carvÃo, ou PCCs). Esses produtos incluem as cinzas volantes, as cinzas pesadas ou de fundo, a escÃria da caldeira, e o gesso do FGD - Flue Gas Desulfurization.Embora alguns PCCs sejam reutilizados como matÃria-prima para a construÃÃo civil, a maioria deles à depositada em aterros ou represas de contenÃÃo. AlÃm de ocupar vastas extensÃes de terra, existe uma grande preocupaÃÃo com o fato de que produtos quÃmicos tÃxicos dos PCCs podem dissolver na Ãgua e essa Ãgua poluÃda pode lixiviar, contaminando tanto Ãguas subterrÃneas quanto superficiais. Este trabalho teve como objetivo fabricar e caracterizar peÃas cerÃmicas a partir de resÃduos da extraÃÃo do granito Asa Branca, com adiÃÃo de produtos gerados pela combustÃo do carvÃo de uma usina termoelÃtrica. Foram avaliadas a microestrutura e algumas propriedades fÃsicas e mecÃnicas dessas peÃas. Os materiais utilizados foram granito Asa Branca e o subproduto da combustÃo do carvÃo mineral ( fornecido pela Energia de Portugal â EDP), nas concentraÃÃes de 10%p, 20%p e 30%p. Para a caracterizaÃÃo das amostras foram utilizadas as tÃcnicas de: DifraÃÃo de Raios-X, FluorescÃncia de Raios-X, Microscopia EletrÃnica de Varredura (MEV), AnÃlise TermogravimÃtrica (ATG). Para a determinaÃÃo das propriedades fÃsicas foram realizados os ensaios de ContraÃÃo Superficial e MÃssica; AbsorÃÃo de Ãgua e Microdureza Vickers. Os resultados obtidos permitem concluir que o uso de produto da combustÃo do carvÃo mineral como reforÃo em peÃas feitas com pà de Granito Asa Branca à tecnicamente viÃvel. / During the burning of mineral coal a series of different residues or byproducts (coal combustion products, or CCPs) are generated. These byproducts include fly ash, bottom ash, boiler slag, and flue gas desulfurization gypsum. Although some types of CCPs can be used as alternative raw materials for construction products, the majority of them are deposited in landfills or surface impoundments. Besides the occupation of large areas there is a major concern with the fact that toxic chemicals from the CCPs can dissolve in water, and this polluted water can spread underground, contaminating both groundwater and surface waters. The present work investigated the fabrication and characterization of ceramic products made from Asa Branca granite powder with the addition of products generated by the combustion of mineral coal in a power plant. The microstructure and some physical and mechanical properties of these parts were evaluated. The materials used were Asa Branca Granite and a mixture of CCPs supplied by EDP (Energia de Portugal) which were added in the concentrations of 10, 20 and 30% wt. to the granite matrix. The following techniques were used for the characterization of the materials: X-ray diffraction, X-ray fluorescence, Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA). Determination of physical properties was performed by means of Surface Contraction and Weight Loss tests; Water Absorption and Vickers Microhardness. The results showed that the use of products generated by the combustion of coal as reinforcements for the parts made from Asa Branca Granite powder is technically viable.

<p>Mercury contamination in aquatic ecosystems is a concern as anaerobic aquatic sediments are the primary regions of methylmercury production in freshwater and coastal regions. Methlymercury is a bioaccumulative neurotoxin, and human exposure to methylmercury can result in impaired functioning of the central nervous system and developmental disabilities in children. To minimize the risk of human exposure to methylmercury, it is important to be knowledgeable of the various sources which can supply mercury to aquatic ecosystems as well as have a complete understanding of the biogeochemical processes which are involved in methylmercury production in aquatic systems. In this dissertation work, both mercury biogeochemical speciation in anaerobic aquatic sediments and sources of mercury to aquatic systems were addressed. </p><p>The biogeochemical speciation of mercury is a critical factor which influences the fate and transformation of mercury in aquatic environments. In anaerobic sediments, mercury chemical speciation is controlled by reduced sulfur groups, such as inorganic sulfide and reduced sulfur moieties in dissolved organic matter (DOM). The formation of mercury sulfide nanoparticles through stabilization by dissolved organic matter (DOM) was investigated in precipitation studies using dynamic light scattering. Mercury sulfide nanoparticles (particle diameter < 100 nm) were stabilized through precipitation reactions that were kinetically hindered by DOM. To further investigate the interaction between DOM and metal sulfides, similar precipitation studies were performed using zinc sulfide and a number of DOM isolates (humic and fulvic acids) representing a range of DOM properties. The results of these experiments suggest that the mechanism of metal sulfide particle stabilization may be electrostatic or electrosteric, depending on the nature of the DOM molecule.</p><p>The mercury that is methylated in aquatic systems enters these environments via a number of sources, including atmospheric deposition, landscape runoff and other industrial and municipal activities. In two separate field studies, two potential sources of mercury to aquatic systems were investigated: landscape runoff and coal combustion products. The mercury loading to aquatic environments from these sources and their potential for transformation to methylmercury were investigated.</p><p>Landscape runoff from a Duke University campus catchment (Durham, NC) was identified as a source of mercury to a stream-wetland. The source of mercury to the runoff was likely from a `legacy' source of mercury; the historic application of mercury fungicide compounds to turf grass during the 20th century. Downstream of the point where the runoff was discharged to the stream-wetland, methylmercury concentrations were detected in stream sediments (up to 11% of total mercury), suggesting that this legacy mercury could be transformed to methylmercury. </p><p>The environmental impact of coal combustion products (CCPs) with respect to mercury and methylmercury was also investigated in a river system (Roane County, TN) that was inundated with fly ash and bottom ash from the Tennessee Valley Authority Kingston coal ash spill in 2008. Elevated total mercury and methylmercury sediment concentrations (relative to upstream sediments) were detected in regions impacted by the ash spill, and our biogeochemical data suggested that the ash may have stimulated methylmercury production in river sediments.</p><p>The results of this dissertation work address the formation of mercury sulfide (along with zinc sulfide) nanoparticles in anaerobic aquatic sediments. In the current mercury methylation paradigm, dissolved mercury species such as Hg(SH)02(aq) and HgS0(aq) are assumed to be the only mercury species that are available for methylation. The results of this dissertation work suggests that in previous studies, HgS0(aq) may have been mistaken as mercury sulfide nanoparticles which may be formed in under supersaturated conditions (with respect to HgS(s)) where DOM is present. Mercury sulfide nanoparticles are a mercury biogeochemical species that has been largely ignored in the research literature and whose role in the mercury biogeochemical cycle and in mercury methylation remains to be investigated.</p><p> This dissertation work also identifies potential sources of mercury to aquatic systems, namely, landscape runoff and CCPs. Atmospheric deposition is currently considered to be the major source of mercury to inland aquatic water bodies compared to sources such as landscape runoff and CCPs. However, in the watershed studied in this dissertation, landscape runoff was identified as a larger source of mercury than atmospheric deposition, suggesting that these so-called `minor' sources may actually be major sources of mercury to watersheds depending on land usage, and should be considered in watershed models. Furthermore, the environmental hazards of mercury-associated with CCPs has typically been determined through leaching experiments, such as the Toxicity Characteristic Leaching Procedure (TCLP), which are not representative of environmental conditions and do not predict that CCPs may influence mercury methylation in aquatic sediments. Thus, in this dissertation work, we suggest that leaching protocols such as the TCLP should be re-evaluated. </p><p>Overall, this dissertation work will be useful in future studies examining mercury speciation and bioavailability to methylating bacteria in aquatic sediments, and the formation of metal sulfide nanoparticles in aquatic systems. Additionally, data on sources of mercury will be useful in developing policies for the regulation of these sources and in assessing the risk to human health from mercury methylation.</p> / Dissertation

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O aumento da produÃÃo de resÃduos gera a necessidade de tratÃ-los e/ou armazenÃ-los de forma adequada, minimizando ou eliminando os prejuÃzos ambientais. Nesta pesquisa, foram estudados os Produtos da CombustÃo do CarvÃo Mineral (PCCs) e borra branca de alumÃnio. Os PCCs foram obtidos durante a queima do carvÃo mineral em uma usina termoelÃtrica e a borra branca foi obtida durante o processo de recuperaÃÃo de alumÃnio. Com o objetivo principal de produzir um cimento a partir da moagem de alta energia, os resÃduos foram caracterizados quimicamente por DifraÃÃo de Raios X (DRX), FluorescÃncia de Raios X (FRX), Espectroscopia de Infravermelho (INFRA) e fisicamente por Tempo de Pega e ResistÃncia à CompressÃo. As anÃlises quÃmicas mostraram a presenÃa de uma das fases que constitui o cimento Portland, e outras duas fases semelhantes. No entanto, ao realizar as caracterizaÃÃes fÃsicas, os resultados mostraram a nÃo formaÃÃo de cimento. Por outro, foi observado que à possÃvel formar mulita a temperaturas mais baixas que a apresentada na literatura, utilizando moagem de alta energia e sinterizaÃÃo a 1200ÂC. A formaÃÃo de mulita a temperaturas mais baixas a partir de resÃduos apresenta grande potencial de utilizaÃÃo dos materiais estudados, na indÃstria cerÃmica. / The increased production of waste generates the need to treat them and / or store them appropriately, minimizing or eliminating environmental damage. In this research, we studied the Coal Combustion Products (CCPs) and white aluminum dross. The CCPs were obtained during the burning of coal in a power plant and the white dross was obtained during the recovery process of aluminum. With the main objective of producing cement using high-energy milling, the residues were chemically characterized by X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), Infrared Spectroscopy (INFRA) and physically by determination of Setting Time and Compressive Strength. Chemical analysis showed the presence of a phase which is observed in Portland cement, and two other similar phases. However, when performing physical characterizations, the results showed no formation of cement. On the other hand, it was observed that it is possible to form mullite at lower temperatures than the one presented in the literature using high energy milling and sintering at 1200ÂC. The formation of mullite from waste at lower temperatures presents great potential for use of CCPs and white aluminum dross in the ceramic industry.

This thesis describes improvements on newly-discovered high-strength pozzolan-based materials fabricated via a low-cost chemical reaction that takes place between 90 and 115 ℃ for 3 to 24 hours. The reported results focus on pozzolan constituents acquired from Coal Combustion Products (CCPs) such as cenospheres, fly ash C and F, as well as bottom ash. The thesis reports on various types of these materials with specific gravity ranging from 0.5 to 1.6; compressive strength ranging from 300 to 3600 psi, and compressive modulus ranging from 50 to 240 ksi. In addition to their good mechanical properties under compression that are attractive for the building and construction industries, the materials further exhibit great potential for applications as energy absorption cores in sandwich construction that could extend their value in other industries including the automotive and aerospace industries. For example, the load-displacement curve exhibits a short elastic zone followed by a long load-plateau; while the materials crush through a controlled vertical cracking process. Additionally, an attempt was made to further decrease the manufacturing cost of the material by investigating incorporation of chemicals that accelerates dehydration of the mixture. One such successful chemical reported in this thesis is aluminum phosphate; while it is not conclusive how the chemical improves any major property.

Although products of coal combustion (PCCs) such as coal ash are currently exempted from classification as a hazardous waste in the United States under the 1976 Resource Conservation and Recovery Act (RCRA), the U.S. Environmental Protection Agency (EPA) is now revising a proposed rule to modify disposal practices for these materials in order to prevent contamination of ground- and surface water sources by leached trace elements. This paper analyzes several aspects of EPA’s scientific reasoning for instating the rule, with the intent of answering the following questions: 1) Are EPA’s cited values for PCC production and disposal accurate estimates of annual totals?; 2) In what ways can EPA’s leaching risk modeling assessment be improved?; 3) What is the total quantity of trace elements contained within all PCCs disposed annually?; and 4) What would be the potential costs and feasibility of reclassifying PCCs not under RCRA, but under existing NRC regulations as low-level radioactive waste (LLRW)? Among the results of my calculations, I found that although EPA estimates for annual PCC disposal are 20% larger than industry statistics, these latter values appear to be closer to reality. Second, EPA appears to have significantly underestimated historical PCC disposal: my projections indicate that EPA’s maximum estimate for the quantity of fly ash landfilled within the past 90 years was likely met by production in the last 30 years alone, if not less. Finally, my analysis indicates that while PCCs may potentially meet the criteria for reclassification as low-level radioactive waste by NRC, the cost of such regulation would be many times that of the EPA June proposed disposal rule ($220-302 billion for PCCs disposed in 2008 alone, versus $1.47 billion per year for the Subtitle C option and $236-587 million for Subtitle D regulatory options). / text