The constant growth in population worldwide over the past decades continues to put forward the need to provide access to safe, clean water to meet human needs. There is a need for cost-effective technologies for water and wastewater treatment that can meet the global demands and the rigorous water quality standards and at the same maximizing pollutant efficiency removal. Current remediation technologies have failed in keeping up with these factors without becoming cost-prohibitive. Nanotechnology has recently been sought as a promising option to achieve these goals. The use of iron oxide magnetic nanoparticles as nanoadsorbents has led to a new class of magnetic separation strategies for water treatment. We have developed magnetic nanocomposite systems able to capture polychlorinated biphenyls (PCBs), as model organic pollutants, in aqueous solution, providing a cost-effective water remediation technique. Two distinct methods were employed to develop these polyphenolic nanocomposite materials. The polyphenolic moieties were incorporated to create high affinity binding sites for organic pollutants within the nanocomposites. The first method utilized a surface initiated polymerization of polyphenolic-based crosslinkers and co-monomers on the surface of iron oxide magnetic nanoparticles to create a core-shell nanocomposite. The second method utilized a bulk polymerization method to create macroscale films composed of iron oxide nanoparticles incorporated into a polyphenolic-based polymer matrix, which were then processed into microparticles. Both methods produce nanocomposite materials that can bind chlorinated organics, can rapidly separate bound organics from contaminated water sources using magnetic decantation, and can use thermal destabilization of the polymer matrix for contaminant release and material regeneration. The polyphenol functionalities used to bind organic pollutants were quercetin multiacrylate (QMA) and curcumin multiacrylate (CMA), which are acrylated forms of the nutrient polyphenols quercetin (found in berries) and curcumin (found in turmeric), both with expected affinity for chlorinated organics. The affinity of these novel materials for PCB 126 was evaluated at equilibrium conditions using a gas chromatography coupled to electron capture detection (GC-ECD) for quantification purposes, and the data was fitted to the nonlinear Langmuir model to determine binding affinity (KD) and maximum biding capacity (Bmax). The KD values obtained demonstrated that the presence of the polyphenolic-based moieties, CMA and QMA, as crosslinkers enhanced the binding affinity for PCB 126, expected to be a result of their aromatic rich nature which provides sites for π – π stacking interactions between the nanoparticle surface and the PCBs in solution. These values are lower that the reported affinity coefficients for activated carbon, which is the gold standard for capture/binding of organic contaminants in water and waste water treatment. Furthermore, upon exposure to an alternating magnetic field (AMF) for a period of 5 minutes, over 90% of the bound PCB on these materials was released, offering a low-cost regeneration method for the nanocomposites. Additionally, this novel regeneration strategy does not require the use of large volumes of harsh organic solvents that oftentimes become harmful byproducts. Overall, we have provided strong evidence that these novel nanocomposites have a promising application as nanoadsorbents for specific organic contaminants in contaminated water sources providing high binding affinities, a low-cost regeneration technique and are capable of withstanding use under environmental conditions offering a cost effective alternative to current remediation approaches.

A emissão de resíduos tem contribuído imensamente para que os seres humanos se tornem vulneráveis e expostos a elementos químicos tóxicos, dentre eles, o arsênio. Este elemento ocupa o primeiro lugar na lista de substâncias de elevada prioridade, com alto risco toxicológico e de exposição segundo a Agency for Toxic Substances and Disease Registry (ATSDR) do Centers for Disease Control and Prevention (CDC). A exposição ao arsênio está associada ao surgimento de vários tipos de câncer, diabetes, aterosclerose, doenças cardiovasculares, pulmonares, imunológicas, hematológicas, gastrintestinais, hepáticas, renais, neurológicas, dentre outras. Uma das mais importantes fontes antropogênicas de arsênio é a mineração, que pode contribuir para contaminação de solos, água, ar e alimentos. Um exemplo de contaminação ambiental por arsênio, no Brasil, ocorre na cidade de Paracatu-MG, devido à exploração de uma mina de ouro. Entretanto, pouco se sabe em relação às condições ambientais na região e aos níveis de exposição da população local. Neste sentido, este trabalho teve como objetivos: (i)-avaliar a concentração de arsênio em amostras de material particulado, amostras de água doce superficial (sub-bacia do rio Paracatu), solos e de água tratada disponível para o consumo humano em bairros próximos e distantes da região de mineração; (ii)- avaliar a concentração de arsênio em amostras de urina e unha de moradores dos bairros monitorados no item (i); e (iii) propor um método de remedição ambiental de amostras de águas contaminadas da região utilizando nanomaterial magnético. Os valores da concentração de material particulado apresentaram grandes variações entre as regiões em estudo, mas ficaram dentro do limite estabelecido pela ATSDR de 20 a 100ng/m3 para regiões urbanas. Já as amostras de águas superficiais apresentaram valores alterados em relação ao estabelecido de 10?g L-1 segundo o CONAMA 357 de 2005. As concentrações de As em água de beber em geral estiveram dentro dos limites estabelecidos. Os valores de As em urina e unha apresentaram valores mínimos menores que o limite de detecção (< LOD) e valores máximos de 9.210 ?g g-1 de creatinina em urina e 31.502 ng g-1 em unha. Finalmente, o método proposto para remediação química apresentou grande eficiência para adsorção de As, com capacidade máxima de adsorção de 37,3 mg g- 1. Além disso, sua aplicação na remediação das águas superficiais contaminadas ou em áreas de rejeitos da região de mineração é de extrema simplicidade / The emission of waste has contributed immensely to humans become vulnerable and exposed to toxic chemicals, among them, the arsenic. This element occupies the first place in the list of substances of high priority, with high toxicological risk and exposure according Agency for Toxic Substances and Disease Registry (ATSDR) of Centers for Disease Control and Prevention (CDC). Exposure to arsenic is associated with the appearance of various types of cancer, diabetes, atherosclerosis, cardiovascular disease, pulmonary, immunological, hematological, gastrointestinal, hepatic, renal, neurological, among others. One of the major anthropogenic sources of arsenic in the world is mining, which can contribute to contamination of soil, water, air and food. An example of environmental contamination by arsenic in Brazil occurs in the Paracatu city of -MG, due to the operation of a gold mine. However, little is known about the risks of the local population to arsenic exposure, although several effects typically associated with high exposure to this toxic chemical. Then, the aims of this study were: (i) assess the concentration of arsenic in particulate matter samples, surface freshwater samples (sub-basin of the Paracatu river), soil and of treated water available for human consumption in neighborhoods with nearby mining region; (ii) Evaluate the concentration of arsenic in urine and nail samples of residents from region of item (i); and (iii) propose a method for environmental remediation of contaminated water samples from the region using magnetic nanomaterial. The values of particulate matter concentration showed large variations between regions under study, but were within the limit established by ATSDR from 20 to 100 ng /m3 in urban areas. As for the surface water samples showed alterations values in relation with the 10?g L-1 established according to CONAMA 357 of 2005. The concentrations in drinking water generally were within the established limits. Soil samples showed high As concentrations. The values in urine and nail showed since lower values than the minimum limit of detection ( < LOD) until maximum values of 9,210?g g -1 creatinine in urine and 31,502ng g -1 in nail. Finally, the proposed chemical remediation method showed high efficiency for adsorption of As, with maximum adsorption capacity of 37.3 mg g-1. It is easily possible its application in the remediation of contaminated surface water or in areas of mining wastes.

This work shows that toughness (resistance) to fracture propagation is an inherent characteristic of cohesionless particulate materials, which is significant for understanding hydraulic fracturing in geotechnical, geological, and petroleum applications. We have developed experimental techniques to quantify the initiation and propagation of fluid-driven fractures in saturated particulate materials. The fracturing liquid is injected into particulate materials, where the fluid flow is localized in thin crack-like conduits. By analogy, we call them 'cracks' or 'hydraulic fractures'. Based on the laboratory observations and scale analysis, this work offers physical concepts to explain the observed phenomena. When a fracture propagates in a solid, new surfaces are created by breaking material bonds. Consequently, the material is in tension at the fracture tip. In contrast, all parts of the cohesionless particulate material (including the tip zone of hydraulic fracture) are likely to be in compression. In solid materials, the fluid front lags behind the front of the propagating fracture, while the lag zone is absent for fluid-driven fractures in cohesionless materials. The compressive stress state and the absence of the fluid lag are important characteristics of hydraulic fracturing in particulate materials with low, or no, cohesion. Our experimental results show that the primary factor affecting peak (initiation) pressure is the magnitude of the remote stresses. The morphology of fracture and fluid leak-off zone, however, changes significantly not only with stresses, but also with other parameters such as flow rate, fluid rheology, and permeability. Typical features of the observed fractures are multiple off-shots and the bluntness of the fracture tip. This suggests the importance of inelastic deformation in the process of fracture propagation in cohesionless materials. Similar to solid materials, fractures propagated perpendicular to the least compressive stress. However, peak injection pressures are significantly greater than the maximum principle stresses in the experiments. Further, by incorporating the dominate experimental parameters into dimensionless form; a reasonable power-law fit is achieved between a dimensionless peak injection pressure and dimensionless stress. Scaling indicates that there is a high pressure gradient in the leak-off zone in the direction normal to the fracture. Fluid pressure does not decrease considerably along the fracture, however, due to the relatively wide fracture aperture. This suggests that hydraulic fractures in unconsolidated materials propagate within the toughness-dominated regime. Furthermore, the theoretical model of toughness-dominated hydraulic fracturing can be matched to the experimental pressure-time dependences with only one fitting parameter. Scale analysis shows that large apertures at the fracture tip correspond to relatively large 'effective' fracture (surface) energy, which can be orders of magnitude greater than typical for hard rocks.

Data de aprova??o ausente. / ?rea de concentra??o: Qu?mica Anal?tica. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2016-12-21T17:35:27Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) rodrigo_carvalho_hott.pdf: 1415995 bytes, checksum: f0a923f5addbb9b380763851a41b99e6 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-01-31T13:51:38Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) rodrigo_carvalho_hott.pdf: 1415995 bytes, checksum: f0a923f5addbb9b380763851a41b99e6 (MD5) / Made available in DSpace on 2017-01-31T13:51:38Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) rodrigo_carvalho_hott.pdf: 1415995 bytes, checksum: f0a923f5addbb9b380763851a41b99e6 (MD5) Previous issue date: 2016 / A elevada toxicidade e potencial de acumula??o de ars?nio em diversos ambientes t?m incentivado pesquisas de novos m?todos de remo??o desse ?on em ?guas contaminadas. Dentre os diversos processos utilizados, a adsor??o contendo ?xidos de ferro tem apresentado bons resultados na remedia??o de ambientes aqu?ticos contaminados por ars?nio. Entretanto, muito do ars?nio liberado no ambiente aqu?tico ? proveniente de efluentes de minera??o, que apresenta meio extremamente ?cido, o que impossibilita a a??o da maioria dos adsorventes utilizados. Neste contexto, a K-jarosita surge como alternativa na remo??o de ars?nio em ambientes contaminados devido sua estabilidade neste ?mbito de baixo pH. Os estudos deste trabalho foram realizados no campus do Mucuri da UFVJM e tiveram como objetivo sintetizar, caracterizar e avaliar atrav?s de ensaios de adsor??o a efetividade de nanopart?culas de k-jarosita na remo??o de ars?nio inorg?nico (III e V) e ars?nio org?nico (?cido monometilars?nico-MMA) em ?gua contaminada, bem como a dessor??o destes elementos promovendo a libera??o dos s?tios de adsor??o dos nanomateriais. A K-jarosita foi caracterizada atrav?s da difratometria de raios-X, com seus pontos de reflex?o estando de acordo com o arquivo padr?o JCPDS 36-427. Seus dados difratom?tricos foram refinados pelo m?todo de Rietveld, caracterizando sua estrutura como rombo?drica de densidade 3,045g cm-3. Apresenta uma ?rea superficial de 9 m2 determinada atrav?s do m?todo BET, sendo uma estrutura mesoporosa, com poros apresentando volume de 0,034 cm3 g-1 e tamanho m?dio de 90?, determinados pelo m?todo BJH. Nos testes de adsor??o, os estudos cin?ticos demonstraram que a K-jarosita apresenta uma r?pida adsor??o, tendo o As(V) sido mais adsorvido que os demais. Com rela??o ao efeito de competi??o de ?nions, foram realizados ensaios com NO3-, PO43- e SO42-, sendo observada pouca interfer?ncia dos ?ons nitrato e fosfato, e um efeito de aumento de adsor??o do ?on sulfato com rela??o ao As (V). No caso do pH, foram avaliadas as faixas de pH do meio ?cido ao meio alcalino, sendo que nestas foi verificada maior estabilidade da K-jarosita em pH pr?ximo de 3, fora do qual ocorre sua desestabiliza??o com forma??o de outros ?xidos de ferro. A dessor??o ocorre em pH acima de 12, sendo o As-i (V) e o As-o MMA os mais facilmente liberados. Foram avaliadas isotermas de Langmuir, Freundlich, Langmuir-Freundlich e Redlich-Peterson, sendo todas adequadas ? adsor??o de ars?nio pela K-jarosita, tendo o modelo de Langmuir-Freundlich apresentado um melhor ajuste. A capacidade m?xima de adsor??o pelas nanopart?culas de K-jarosita foi de 11,12 mg g-1 para As (III), de 18,26 mg g-1 para As (V) e de 13,35 mg g-1 para MMA. Em an?lise de amostras de ?guas superficiais de rios contaminados por ars?nio, provenientes do munic?pio de Paracatu/MG, todas ficaram ap?s a adsor??o por K-jarosita abaixo dos limites estabelecidos pela legisla??o vigente. Foi realizada tamb?m a recupera??o do ars?nio ap?s dessor??o na forma de Ag3AsO4, o qual apresentou grande efici?ncia em ensaios de fotocat?lise, que tamb?m foram realizados. E como forma de funcionalizar o uso das nanopart?culas de K-jarosita, foram desenvolvidos prot?tipos de filtros que apresentaram grande efici?ncia na remo??o do ars?nio em amostras de ?gua. Atrav?s deste estudo, foi poss?vel verificar que a K-jarosita apresenta grande potencial de ser utilizada como forma de remedia??o ambiental em ambientes aquosos contaminados por ars?nio. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, [2016]. / The high toxicity and potential of arsenic accumulation in different environments have encouraged works of new ion removal methods in contaminated water. Among the various processes used, the adsorption containing iron oxides has shown good results in the remediation of aquatic environments contaminated by arsenic. However, much of the arsenic is released into the aquatic environment from mining waste, which presents extremely acid medium, which prevents the action of most adsorbents used. In this context, the K-jarosite is an alternative in the removal of arsenic in contaminated environments due to its stability in the context of low pH. Studies of this work were carried out in the Mucuri campus from UFVJM and aimed to synthesize, characterize and evaluate through adsorption tests the effectiveness of K-jarosite nanoparticles in inorganic arsenic removal (III and V) and organic arsenic (monometilars?nic acid -MMA) in contaminated water and desorption of these elements promoting the release of nanomaterials adsorption sites. The K-jarosite was characterized by diffraction of X-rays, with their reflection points are in accordance with the standard file JCPDS 36-427. Its difratom?trics data were refined by the Rietveld method, characterizing its structure and density of rhombohedral 3,045g cm-3. Having a surface area of 9 m2 determined by the BET method, being a mesoporous structure with pores having volume of 0.034 cm3 g-1 and 90 ? average size determined by the BJH method. In adsorption tests, kinetic studies have shown that K-jarosite has a rapid adsorption, and the As (V) was adsorbed more than the others. With respect to anions competition effect, tests were performed with NO3-, PO43- and SO42-, and observed little interference of nitrate and phosphate ions, and sulfate ion adsorption increased effect with respect to As (V). In the case of pH, the pH ranges from acid to alkaline medium were evaluated, and these were verified increased stability of K-jarosite at pH around 3, out of which a destabilization occurs with formation of other iron oxides. The desorption occurs at pH above 12 and the As-i (V) and o-MMA to more easily released. Langmuir isotherms were evaluated, Freundlich, Langmuir-Freundlich and Redlich-Peterson, all being suitable for the adsorption of arsenic by K-jarosite having the model of Langmuir-Freundlich presented a better fit. The maximum adsorption capacity for K-jarosite nanoparticles was 11.12 mg g-1 for As (III) 18.26 mg g-1 to As (V) and 13.35 mg g-1 for MMA . In analysis of surface water samples from contaminated rivers by arsenic, from the Paracatu city / MG, all they were after adsorption by K-jarosite below the limits established by law. It also performed the recovery of arsenic desorbed in the form of Ag3AsO4, which showed great efficiency in photocatalysis tests were also performed. And as a way to functionalize the use of K-jarosite nanoparticles filter prototypes were developed that showed high efficiency in the removal of arsenic in water samples. Through this study, we found that K-jarosite has potential to be used as a form of environmental remediation in aqueous environments contaminated by arsenic.

A emissão de resíduos tem contribuído imensamente para que os seres humanos se tornem vulneráveis e expostos a elementos químicos tóxicos, dentre eles, o arsênio. Este elemento ocupa o primeiro lugar na lista de substâncias de elevada prioridade, com alto risco toxicológico e de exposição segundo a Agency for Toxic Substances and Disease Registry (ATSDR) do Centers for Disease Control and Prevention (CDC). A exposição ao arsênio está associada ao surgimento de vários tipos de câncer, diabetes, aterosclerose, doenças cardiovasculares, pulmonares, imunológicas, hematológicas, gastrintestinais, hepáticas, renais, neurológicas, dentre outras. Uma das mais importantes fontes antropogênicas de arsênio é a mineração, que pode contribuir para contaminação de solos, água, ar e alimentos. Um exemplo de contaminação ambiental por arsênio, no Brasil, ocorre na cidade de Paracatu-MG, devido à exploração de uma mina de ouro. Entretanto, pouco se sabe em relação às condições ambientais na região e aos níveis de exposição da população local. Neste sentido, este trabalho teve como objetivos: (i)-avaliar a concentração de arsênio em amostras de material particulado, amostras de água doce superficial (sub-bacia do rio Paracatu), solos e de água tratada disponível para o consumo humano em bairros próximos e distantes da região de mineração; (ii)- avaliar a concentração de arsênio em amostras de urina e unha de moradores dos bairros monitorados no item (i); e (iii) propor um método de remedição ambiental de amostras de águas contaminadas da região utilizando nanomaterial magnético. Os valores da concentração de material particulado apresentaram grandes variações entre as regiões em estudo, mas ficaram dentro do limite estabelecido pela ATSDR de 20 a 100ng/m3 para regiões urbanas. Já as amostras de águas superficiais apresentaram valores alterados em relação ao estabelecido de 10?g L-1 segundo o CONAMA 357 de 2005. As concentrações de As em água de beber em geral estiveram dentro dos limites estabelecidos. Os valores de As em urina e unha apresentaram valores mínimos menores que o limite de detecção (< LOD) e valores máximos de 9.210 ?g g-1 de creatinina em urina e 31.502 ng g-1 em unha. Finalmente, o método proposto para remediação química apresentou grande eficiência para adsorção de As, com capacidade máxima de adsorção de 37,3 mg g- 1. Além disso, sua aplicação na remediação das águas superficiais contaminadas ou em áreas de rejeitos da região de mineração é de extrema simplicidade / The emission of waste has contributed immensely to humans become vulnerable and exposed to toxic chemicals, among them, the arsenic. This element occupies the first place in the list of substances of high priority, with high toxicological risk and exposure according Agency for Toxic Substances and Disease Registry (ATSDR) of Centers for Disease Control and Prevention (CDC). Exposure to arsenic is associated with the appearance of various types of cancer, diabetes, atherosclerosis, cardiovascular disease, pulmonary, immunological, hematological, gastrointestinal, hepatic, renal, neurological, among others. One of the major anthropogenic sources of arsenic in the world is mining, which can contribute to contamination of soil, water, air and food. An example of environmental contamination by arsenic in Brazil occurs in the Paracatu city of -MG, due to the operation of a gold mine. However, little is known about the risks of the local population to arsenic exposure, although several effects typically associated with high exposure to this toxic chemical. Then, the aims of this study were: (i) assess the concentration of arsenic in particulate matter samples, surface freshwater samples (sub-basin of the Paracatu river), soil and of treated water available for human consumption in neighborhoods with nearby mining region; (ii) Evaluate the concentration of arsenic in urine and nail samples of residents from region of item (i); and (iii) propose a method for environmental remediation of contaminated water samples from the region using magnetic nanomaterial. The values of particulate matter concentration showed large variations between regions under study, but were within the limit established by ATSDR from 20 to 100 ng /m3 in urban areas. As for the surface water samples showed alterations values in relation with the 10?g L-1 established according to CONAMA 357 of 2005. The concentrations in drinking water generally were within the established limits. Soil samples showed high As concentrations. The values in urine and nail showed since lower values than the minimum limit of detection ( < LOD) until maximum values of 9,210?g g -1 creatinine in urine and 31,502ng g -1 in nail. Finally, the proposed chemical remediation method showed high efficiency for adsorption of As, with maximum adsorption capacity of 37.3 mg g-1. It is easily possible its application in the remediation of contaminated surface water or in areas of mining wastes.

This thesis focuses on the synthesis and applications of nanoscale zero valent iron (nZVI) in the environmental remediation of contaminants. The polyvalent characteristics of this nanomaterial are evaluated in this work with the study of its application in a wide range of contaminants: heavy metals and pesticides in water medium, and malodorous sulfur compounds present in air streams. Moreover, a novel method of synthesis of encapsulated nZVI from a waste material is presented, which meets the principles of green chemistry and at the same time represents a low-cost method of obtaining nZVI with improved characteristics. Chapter 1 describes the current state of the topics that will be discussed in the rest of the thesis. Specifically, the different mechanisms of contaminant remediation by nZVI are discussed, a summary of the current synthesis methods is presented and the principal modifications of nZVI to improve its characteristics are described. Finally, the limitations of the current techniques are assessed, which will be the starting point of the thesis. In Chapter 2, the application of nZVI to heavy metal removal during long time periods is explored. The contaminants studied are Zn, Cd, Ni, Cu and Cr, which are the most common heavy metals found in ground and wastewater. A delivery-effect of the heavy metal ions that had already been attached to nZVI surface is observed after long reaction times, which is a consequence of the nZVI aging and oxidation. The conditions that influence the delivery-effect are assessed and possible solutions to this detected problem are presented. In Chapter 3, nZVI is applied to the removal of sulfur-based odorous compounds in air streams. The compounds studied are hydrogen sulfide and dimethyl disulfide (DMDS), which are commonly found in wastewater treatment plants. Both nZVI loading and pH are varied to assess their influence on the process. Bimetallic nanoscale particles of Cu/Fe, Ni/Fe and Pd/Fe are synthesized in order to improve the DMDS abatement by the nZVI. The advantages of this new method for odor removal are discussed at the look of the experimental results. Lastly, a pilot scale test was performed in a wastewater treatment plant in order to test the effectiveness of the nZVI in a real application. The nZVI were applied in a scrubber to eliminate the sulfurous compounds from the pre-treatment area of the wastewater treatment plant. Chapter 4 deals with the application of nZVI to the oxidation of non-biodegradable pollutants by the Fenton reaction. Specifically, the effect of pH on the degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) is studied. The advantages of using nZVI as a Fenton reagent compared to homogeneous Fenton are described. Furthermore, the addition of UV-light to the process is investigated. Finally, the main degradation intermediates of the reaction are identified and a degradation mechanism is accordingly proposed. In Chapter 5, the presence of polychlorinated dioxins and furans (PCDD/Fs) in the nZVI surface is addressed. Studies have shown that nZVI enhances the formation of such chlorinated compounds during thermal processes, but it is unclear which the origin of the compounds is. It has been suggested that nZVI could possess impurities such as PCDD/Fs in its surface. Therefore, the concentration of PCDD/Fs in both commercial and laboratory-synthesized nanoparticles is analyzed. PCDD/Fs pattern and WHO-TEQ concentrations are also obtained. As an outcome of the results obtained in this chapter, a recommendation for preventing the PCDD/Fs presence in nZVI is given. Chapter 6 is dedicated to the synthesis of carbon-encapsulated nanoparticles using hydrothermal carbonization (HTC) of an agricultural waste, particularly, olive mill wastewater (OMW). This novel method, in addition to meet the green chemistry principles, makes profit of the high polyphenol content of OMW to maximize the fraction of incorporated iron into the nZVI. Moreover, the carbon layer surrounding the nZVI protects it against oxidation and avoids its aggregation. Several HTC conditions are explored to study their implications in the characteristics of the material obtained. A deep characterization of the encapsulated nZVI is also presented in this chapter. In Chapter 7, the applications of the encapsulated nZVI synthesized in Chapter 6 are explored and compared for the same contaminants that have been studied in the previous chapters. Then, the advantages of encapsulated nZVI in comparison with common nZVI are discussed at the end of the chapter, and an estimation of the synthesis costs with this method is addressed. Lastly, in Chapter 8, the main conclusions of the thesis are summarized and suggestions for future work are presented.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23290号 / エネ博第415号 / 新制||エネ||80(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 石原 慶一, 教授 手塚 哲央, 教授 大垣 英明 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Polychlorinated biphenyls (PCBs) are a class of environmentally persistent halogenated organic compounds that were once used as stabilizers to improve the properties of a variety of materials such as lubricants, heat transfer fluids, paints, and caulking materials. PCBs are also capable of migration through processes such as spillage into soils, leaching into groundwater, and volatilization into the atmosphere. Although banned in 1979 over health concerns, PCBs persist in these materials to this day because they are resistant to biotic degradation and natural weathering processes. The wide variety of contaminated materials means that many existing treatment options cannot be used across all media. This research focuses on the adaptation of a reductive dehalogenation system for dechlorination of PCBs from machine oils, paints, sludges, and soils. The system utilizes magnesium, glacial acetic acid, and ethanol in order to remove the chlorine atoms from the biphenyl backbone, which is less toxic and can be broken down biotically. A treatment plan was devised for machine oil contaminated with PCBs, involving sorption of PCBs onto a column of super activated alumina followed by desorption into hexane and treatment of the hexane with magnesium and acidified ethanol to dechlorinate the PCBs. In a small-scale study, 98.5% of PCBs from an oil sample were sorbed to the column, and the PCBs that were subsequently desorbed were dechlorinated to below detectable levels within one day of magnesium and acidified ethanol treatment. Information from small-scale studies was used to design larger sorption columns intended for use at a field site. iv A field study was conducted to compare the effectiveness of two different treatment system pastes at removing PCBs from painted surfaces. These pastes were formulated with bulking and viscosity control agents in order to cling to vertical surfaces, and contained either acidified ethanol and magnesium (Activated Metal Treatment System, AMTS) or acidified ethanol only (Non-Metal Treatment System, NMTS). AMTS was capable of 64.8% average removal of PCBs from paint, while NMTS demonstrated 89.5% average removal but required a second step to dechlorinate the extracted PCBs. This system allows for treatment of surfaces without demolishing the structure. AMTS was also studied for in situ dechlorination of PCBs in soils, and NMTS enclosed in a polyethylene barrier was studied for extraction of PCBs from sludges. A two-step system was devised for the ex situ treatment of PCB-contaminated soils. Solvent extraction with ethanol or an ethanol/ethyl lactate cosolvent is followed by dechlorination using magnesium and glacial acetic acid. Studies included the optimization of extraction solvent, cosolvent ratio, cost, and reuse of magnesium or extraction solvent. Surface analysis of magnesium particles used in dechlorination showed a precipitate occluding part of the surface, which was thought to be a combination of magnesium ethoxide and magnesium hydroxide. This precipitate is thought to come from the reaction of magnesium ethoxide formed during the PCB dechlorination process with pore water extracted from the soil.

This thesis reports the investigation of Bismuth oxybromide (BiOBr) semiconductor material as an efficient photocatalyst for the sunlight harvesting as well as environmental cleanup. I have utilised different synthetic methodologies to obtain BiOBr and its derivatives, such as co-precipitation, ultrasonification, and photo-deposition; and have studied their structural and optical properties by X-ray diffraction and surface analysis techniques. I report the synthesis and characterisation of two new p-n heterojunction systems, AgBr-BiOBr and BiOBr-ZnFe₂O₄, and have performed initial studies on photocatalytic reaction and their catalytic decomposition mechanisms. I have also reported the surface modification method including the deposition of noble metal on BiOBr to investigate the role played by the noble metal and the interactions between semiconductor and metal using various characterisation measurements. Furthermore, a continuous series of BiOBr-BiOI solid solutions were synthesised, characterised and the photocatalytic degradation was performed on the as-obtained semiconductors, to study the band structure properties of the solid solutions.

PCBs are recalcitrant compounds of no known natural origin that persist in the environment despite their ban by the United States Environmental Protection Agency in 1979 due to negative health effects. Transport of PCBs from elastic sealants into concrete, brick, and granite structures has resulted in the need for a technology capable of removing these PCBs from the materials. This research investigated the use of a nonmetal treatment system (NMTS) and an activated metal treatment system (AMTS) for the remediation and degradation of PCBs from concrete, brick, and granite affixed with PCB-laden caulking. The adsorption of PCBs onto the components of concrete and the feasibility of ethanol washing were also investigated. NMTS is a sorbent paste containing ethanol, acetic acid, and fillers that was developed at the University of Central Florida Environmental Chemistry Laboratory for the in situ remediation of PCBs. Combining NMTS with magnesium results in an activated treatment system used for reductive dechlorination of PCBs. NMTS was applied to laboratory-prepared concrete as well as field samples by direct contact as well as by a novel sock-type delivery. The remediation of PCBs from field samples using NMTS and AMTS resulted in a 33-98% reduction for concrete, a 65-70% reduction for brick, and an 89% reduction in PCB concentration for granite. The limit of NMTS for absorption of Aroclor 1254 was found to be roughly 22,000 mg Aroclor 1254 per kg of treatment system or greater. The activated treatment system resulted in a 94% or greater degradation of PCBs after seven days with the majority of degradation occurring in the first 24 hours. The adsorption of PCBs to individual concrete components (hydrated cement, sand, crushed limestone, and crushed granite) was found to follow the Freundlich isotherm model with greater adsorption to crushed limestone and crushed granite compared to hydrated cement and iv sand. Ethanol washing was shown to decrease the concentration of laboratory-prepared concrete by 68% and the concentration of PCBs in the ethanol wash were reduced by 77% via degradation with an activated magnesium system.