Zugl.: Karlsruhe, Univ., Diss., 2008 / Hergestellt on demand

Techn. Universiẗat, Diss., 2004--Darmstadt.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The frequent incorporation of radionuclides through ingestion of water and/or food is able to raise the levels of radiation within the body above the tolerable limit. Thus, foods grown on high radioactive background soils, such as in the vicinity of uranium mines, may be potential risk agents. The consumption of these products has the possibility to induce damages that, when accumulated, may evolve into carcinogenesis. In this work, we sought to evaluate the potential of low concentrations of radionuclides to promote radio-induced mutations. Emphasis was placed on the radionuclides 238U, 232Th and 40K, since these species contribute most to the increase of the levels of exposure to natural radioactivity. For the first time, plant bioindicators exposed to different concentrations of sterile uranium (0,25 g, 0,50 g, 0,75 g, and 1,00 g) were used. Seeds of lettuce (Lactuca sativa) and seeds of onion (Allium cepa) were used, cultivated in Petri dish for 3 and 7 days, respectively, in the presence of sterile uranium. This is the intrinsic time for germination for each of these plants and consequently, the period which its cells were exposed to the background radioactive while its tissues (roots) developed. Onion cells are considered as a universal bioindicator since they report a concordance of 71% to 91.5% with the tests performed with mammalian cells, besides maintaining a good agreement with the observed effects in human peripheral blood cells. The activities of the investigated radionuclides were obtained by means of high resolution gamma spectrometry, the 40K being the only one that was directly estimated. Since the 238U and 232Th are pure alpha emitters, their activities were indirectly obtained by emitting gamma radiation members of their series. Because it is a rock, it is possible to consider that these radionuclides are immobilized in the geological time scale of the sample. Thus, when establishing the condition of radioactive equilibrium, it was considered that the activities of the daughters were those of the respective progenitors of the series. Fourier Transform Infrared Spectroscopy analyzes were performed on the roots of both bioindicators to detect structural changes/degradations due to exposure to ionizing radiation or a possible incorporation of radionuclides. Cell damages were evaluated by means of the micronucleus test, a technique recommended by IAEA for the evaluation of radioinduced mutation. The results indicated activity values compatible with those from regions with low levels of background radioactivity. However, for both bioindicators, an incidence of damage greater than the limit recommended by the IAEA was observed. Infrared spectra do not indicate incorporation of uranium or some other element by plants. It has been demonstrated that it is possible to verify the effect of low concentrations of radionuclides in inducing damages to the cells of these species, making possible the use of these plants as bioindicators for the analysis of radiation effects. This study concludes that even at low concentrations, frequent exposure to investigated radionuclides may trigger local damage, whose carcinogenic potential may be associated mainly with the high LET of the alpha radiation emitters. / A incorporação frequente de radionuclídeos através de ingestão de água e/ou alimentos é capaz de elevar os níveis de radiação dentro do corpo acima do limite tolerável. Assim, alimentos cultivados em solos de alto background radioativo, como por exemplo, no entorno de minas de urânio, podem ser potenciais agentes de risco. O consumo desses produtos tem a possibilidade de induzir danos que, quando acumulados, podem evoluir para uma carcinogênese. Neste trabalho, buscou-se avaliar o potencial de baixas concentrações de radionuclídeos promoverem mutações radioinduzidas. Foi dado ênfase aos radionuclídeos 238U, 232Th e 40K, pois essas espécies são as que mais contribuem para o aumento dos níveis de exposição à radioatividade natural. Pela primeira vez foram utilizados bioindicadores vegetais expostos à diferentes concentrações de estéril de urânio (0,25 g, 0,50 g, 0,75 g e 1,00 g). Foram usadas sementes de alface (Lactuca sativa) e sementes de cebola (Allium cepa), cultivadas em placa de Petri por 3 e 7 dias, respectivamente, na presença de estéril de urânio. Esse é o tempo intrínseco para germinação de cada uma dessas plantas e consequentemente, o período em que as suas células ficaram expostas ao background radioativo, enquanto os seus tecidos (raízes) se desenvolviam. As células de cebola são consideradas como um bioindicador universal pois reportam uma concordância de 71% a 91,5% com os testes realizados com células de mamíferos, além de conservarem uma boa concordância com os efeitos observados em células de sangue periférico humano. As atividades dos radionuclídeos investigados foram obtidas por meio de espectrometria gama de alta resolução, sendo a do 40K a única que foi estimada diretamente. Como o 238U e o 232Th são emissores alfa puros, as suas atividades foram obtidas indiretamente por meio de membros emissores de radiação gama de suas séries. Por se tratar de uma rocha, é possível fazer a consideração de que esses radionuclídeos estão imobilizados na escala geológica de tempo da amostra. Assim, ao estabelecer a condição de equilíbrio radioativo, as atividades dos filhos foram consideradas como sendo a dos respectivos progenitores das séries. Análises por Espectroscopia no Infravermelho com Transformada de Fourier foram feitas nas raízes de ambos os bioindicadores para detectar alterações/ degradações estruturais decorrentes da exposição à radiação ionizante e/ou de uma possível incorporação de radionuclídeos. Os danos celulares foram investigados por meio do teste de micronúcleo, técnica recomendada pela IAEA para avaliar mutação radioinduzida. Os resultados indicaram valores de atividades compatíveis com àqueles de regiões de baixos níveis de radioatividade de fundo. No entanto, para ambos os bioindicadores observou-se uma incidência de danos superior ao limite recomendado pela IAEA. Os espectros de infravermelho não indicam incorporação de urânio ou de algum outro elemento pelas plantas. Demonstrou-se que é possível verificar o efeito de baixas concentrações de radionuclídeos em induzir danos às células dessas espécies, possibilitando o uso dessas plantas como bioindicadores para análise de efeitos da radiação. Este estudo conclui que mesmo para baixas concentrações, a exposição frequente aos radionuclídeos investigados pode desencadear danos locais, cujo potencial carcinogênico pode estar associado principalmente a alta LET dos emissores de radiação alfa. / São Cristóvão, SE

The work deals with the preparation and study of polyphosphate composites. Aluminum phosphates provide some unusual properties like high-heat resistance in terms of inorganic binders. The addition of chromium in the form of Cr2O3 or directly the bond with the aluminum-chromium-phosphate can improve the properties of this binder. Highly viscous Al2Cr(H2PO4)9 and Al3Cr(H2PO4)12 binders were prepared by dissolving Al(OH)3 and CrO3 in 85% phosphoric acid, and mixed with Al2O3 and Cr2O3 fillers. The composites were cured in the furnace at 150 °C for 24 h under pressure of 10 MPa. During the annealing at temperatures up to 1 500 °C changes in chemical structure of the cured composites were observed, leading to the understanding of the creation of crystalline phases and their eventual changes. The characterization of binders was mainly based on FT-IR, EDAX, TG-DTA and optical microscopy analyses.

No description available.

Microalga-based technologies are introduced to provide a new generation of biofuels. The cultivation of microalgae in wastewater as the growth medium may offer the dual benefit of wastewater treatment and sustainable biofuel production. The potential of microalgal biomass to be converted into biodiesel depends on the accumulation of lipids, mainly triacylglycerols. However, the presence of toxic contaminants in municipal or industrial wastewater could negatively affect the biomass growth and modify the pattern of lipid accumulation in algae cells. This research aims to evaluate the potential of cultivating microalgae in wastewater for the removal of selected contaminants and the production of biodiesel. The hypothesis underlying this work was that growing microalgae in the presence of contaminants, typically found in wastewater, may induce a stress response that potentially increases the lipid productivity and enhances the biofuel yield. This research explored the potential of microalgae to be used for the removal of wastewater pollutants while accumulating high concentrations of neutral lipid that can be converted into biodiesel. Physiological and transcriptional responses of two genera of green algae were observed in the presence of stresses induced by toxic metals in raw hydraulic fracturing flowback water and pharmaceuticals found in municipal wastewater. Two green algae, Dunaliella salina and Chlorella vulgaris, were selected based on the availability of genetic information, current trends in the alga industry, and specific growth requirement in hypersaline flowback water and municipal wastewater. The first part of this research focuses on the possibility of using the salt-tolerant green microalga, D. salina, for the removal of toxic metals from hydraulic fracturing flowback water. In the second part of this research, the freshwater green microalga, C. vulgaris, was exposed to a suite of pharmaceuticals, commonly found in municipal wastewater, and the effects on the biomass growth and lipid accumulation were evaluated. In Chapter 3, aqueous geochemical characteristics of hydraulic fracturing flowback water were determined. Metagenomic analysis was also used to characterize the microbial community structure of the water samples. This technique included DNA extraction, PCR amplification of genes for 16S and 18S ribosomal RNA, and pyrosequencing. Although the two flowback water samples were shown to have water property measures in the range of reported values in literature, they were significantly different from each other regarding water properties such as total dissolved solids and total organic carbon. They also had distinct microbial community structures. It was shown the flowback water samples contained mainly halophilic, anaerobic, and thermophilic species with a pattern that was expected to be seen in natural gas shale reservoirs. Chapter 4 covers the characterization of the effects of contaminants (toxic metals) in hydraulic fracturing flowback water on the biomass growth and cellular lipid accumulation in Dunaliella salina. Metals were analyzed using ICP-MS. Biomass accumulation was determined by spectrophotometry and gravimetric methods. Lipid accumulation and composition were determined by GC-MS after conversion into fatty acid methyl esters. D. salina was successfully cultivated in saline hydraulic fracturing flowback water, and algal biomass growth was associated with a significant reduction of several toxic metals in the samples. D. salina, grown in flowback water, accumulated high levels of cellular lipids. Also, the estimated biodiesel properties were comparable with other algal biodiesel and complied with the US and EU biodiesel standards. The last chapter of part one presents the effects of a collection of metals commonly found in hydraulic fracturing flowback water and other industrial wastewaters on growth and lipid accumulation of D. salina. The impacts of the nitrogen concentration in the growth medium were also observed. The Nile red assay (fluorescence measurement after Nile red staining) was used to assess lipid accumulation. A range of toxic effects on the algal growth was observed. However, the effects were lower at higher nitrogen level that may indicate to an improved toxicity resistance when nutrient stress is minimal. Even with a high dose-dependent toxicity on growth, some toxic metals increased lipid accumulation. Chapter 6 describes the microplate-based toxicity test conducted to characterize the effect of a range of emerging contaminants (pharmaceuticals) commonly found in municipal wastewater on the biomass growth and cellular lipid accumulation measured by Nile red staining assay. Similar to what was observed for metals in Chapter 5, some pharmaceuticals increased lipid accumulation, even with a high dose-dependent toxicity on algal growth. Most tested pharmaceuticals at municipal wastewater levels (low) did not have a significant effect on the algal growth and lipid accumulation. Toxicity data (EC50 of growth) were well in agreement with what was reported in literature and antibiotics were the most toxic compounds among the different pharmaceutical classes. Chapter 7 presents a further characterization of the effects of a few selected compound from the previous chapter. Changes in the algal lipid composition upon exposure to the selected compounds were determined by qualitative and quantitative analysis of the extracted lipids using GC-MS. FT-IR spectroscopy was used to detect changes in the cellular constituents. The transcriptional responses of the key genes involved in the lipid metabolism of C. vulgaris were also investigated upon exposure to tetracycline using reverse-transcription real-time PCR and the results were interpreted based on the measured levels of cellular lipids and other metabolites. Lipid accumulation was changed upon exposure of algae to pharmaceuticals; however, the FAMEs profile did not show a significant variation. FT-IR spectroscopy highlighted the subtle changes in the cellular basis, and FT-IR peak associated with lipids was strongly correlated with total FAMEs quantified by GC-MS (Pearson correlation coefficient = 0.89). Gene expression analysis showed a general down-regulation of genes involved in the lipid biosynthesis. Results from this research are expecting to help develop and optimize innovative algal-based technologies combining the benefits of wastewater treatment, sustainable biofuel production, and mitigation of carbon dioxide emissions. / Civil Engineering

Kalavasos-Ayios Dhimitrios (K-AD; Figure 1) is a Late Bronze Age (LBA) settlement on Cyprus. It is notable for having among the earliest examples of urbanism and monumental architecture on the island along side the sites of, for example, Kition, Alassa, Enkomi, and Maroni (Philokyprou 2011; Fisher et al. in press). The LBA on Cyprus marked the beginning of urban society, economy and architecture in Cyprus (Fisher et al. in press). This study explores the social processes associated with the transition to urbanism represented by the entangled relationship between the architectural creation of social spaces and the use of these spaces as platforms for the creation and negotiation of power and influence (Fisher 2009a, 2009b; Fisher et al. in press). Specifically this study will concentrate on the construction of plaster surfaces, the immobile architecture of these social spaces, as indexes of the social development at K-AD during the LBA. Analysis of pyrogenic lime and gypsum plasters was carried out using high-resolution microscopic methods based on the integration of petrography and soil micromorphology. These techniques are employed to optically examine in-situ and oriented plaster samples in laboratory thin section. Laboratory Fourier-transform infrared spectroscopy (FT-IR) analysis was applied to loose sediments to obtain spectroscopic data when necessary. Following the findings that lime plaster recipe variation is the result of human choice (Kingery et al. 1988; Love 2011, 2013a) the results of this analysis shows that the LBA architects at K-AD produced different recipes for different utilitarian uses and also that the construction of elite spaces demanded complex recipes that extend beyond utilitarian requirements, which can be classified as more “expensive,” resource-draining procedures (Kingery et al. 1988; Love 2011). Plaster is used at K-AD for both functional purposes and as an active component in societal creation and transformation. / Thesis / Master of Arts (MA) / Craft specialization is a core feature of urban life but the process of specialization is not perfectly understood. This thesis seeks to explore the use of lime plaster for constructing surfaces at the Late Bronze Age (LBA) site of Kalavasos-Ayios Dhimitrios (K-AD) on the island of Cyprus. Previous research has revealed a central, monumental complex, among the first of its kind on the island, surrounded by an early city. How did the LBA people create their living environment in this new setting? This thesis has shown, through the analysis of lime plaster features, floors and walls that the LBA inhabitants of K-AD were able to create diverse, specialized surfaces with a specialized lime plaster tradition in a scale and complexity that went beyond structural requirements, suggesting these surfaces were constructed with the explicit intent for creating space imbued with social meaning.

The effect of HZSM-5 catalyst and NaOH pretreatment on the product distribution and bio oil properties from pyrolysis of cellulose, hemicellulose and lignin model compounds was investigated at 450 °C. NaOH pretreated and untreated cellulose was pyrolyzed on sand and the HZSM-5 catalysts; VPISU001 HZSM-5, BASF HZSM-5, and Sud-Chemie HZSM-5. The pyrolysis of cellulose on BASF and Sud-Chemie HZSM-5 catalysts increased the yields of the organic liquid fraction, total liquid and char while decreasing the gas yields. However the catalyst decreased the organic and char yields while increasing the water yields but there was no change in gas yields. The NaOH treatment caused a decrease in the organic and total oil yields relative to the control but the char yield increased. The change in gas yields was not significant. The characterization of the oils using FTIR and ¹³C−nmr showed that, the VPISU001 HZSM-5 with and without NaOH pretreatment caused elimination of the levoglucosan fraction while increasing the aromatic fraction. The NaOH pretreated cellulose pyrolyzed on sand reduced the levoglucosan groups while increasing the aromatic fraction of the bio oil. In the hemicellulose studies, birchwood xylan and NaOH treated xylan samples were pyrolyzed on sand and VPISU001 HZSM-5 catalyst. The organic liquid yields were very low and ranged from 3.3 wt% to 7.2 wt%, the water yields ranged from 17.8-25.7 wt%, the char yield were 17.8-25 wt% and gas yield were 40.9-49.6 wt%. The HZSM-5 catalysts increased the water and gas yields and produced the lowest char yield. NaOH pretreatment produced the lowest water yield while the char yield was the highest. The combined effect of NaOH pretreatment and HZSM-5 produced the lowest organic yield and highest char yield. The FTIR and ¹³C-nmr analyses of the organic liquids showed that the HZSM-5 catalyst promoted the formation of aromatic products, while the NaOH pretreatment promoted the formation of aliphatic hydrocarbons. The combined effect of NaOH pretreatment and HZSM-5 catalyst seem to promote the formation of anhydrosugars. The main gases evolved were CO, CO₂ and low molecular weight hydrocarbons. The HZSM-5 catalyst promoted CO formation while NaOH pretreatment promoted CO₂. The HZSM-5 catalyst produced the highest yield of low molecular weight hydrocarbon gases. The lignin and model compounds studies involved using low molecular weight kraft lignin, guaiacol, and syringol which were pyrolyzed on sand and VPISU001 HZSM-5 catalyst at 450 °C. The kraft lignin pyrolysis produced low liquid and gas yields and high char yields. The HZSM-5 catalysts increased the water yield and decreased the organic liquid yield. NaOH pretreatment increased the char yield and decreased the liquid products. NaOH and the HZSM-5 catalyst together decreased the char and increased the gas yields. The ¹³C-nmr and FTIR analysis showed that NaOH pretreatment promoted the formation of mainly guaiacol while the HZSM-5 catalyst formed different aromatic components. NaOH pretreatment promoted the formation of more CO₂ than CO whilst HZSM-5 catalyst promoted the formation of more CO than CO₂. Methane formation was enhanced by NaOH pretreatment. Other hydrocarbon gases were however enhanced by the HZSM-5 catalysts. Pyrolysis of the model compounds on the HSZM-5 catalyst showed an increase in pyrolytic water. The HZSM-5 catalyst promoted demethylation in syringol pyrolysis as compared to guaiacol. / Master of Science

The effects of adding a biodegradable litter amendment (AmmoSoak), developed from steam exploded corncobs, to poultry litter prior to pyrolysis on the product yields and qualities were investigated. Mixtures of litter and AmmoSoak were pyrolyzed in a bench-scale fluidized bed reactor. The objective of the second phase was to start-up a pilot-scale fluidized bed reactor unit. The poultry litter had a lower higher heating value (HHV), higher moisture, ash, nitrogen, sulfur, and chlorine contents than AmmoSoak. Analysis of the poultry litter indicated a mixture of volatiles, hemicelluloses, cellulose, lignin, ash, and proteins. AmmoSoak had a simpler composition than the litter; mainly hemicelluloses, cellulose, and lignin. Bench-scale studies indicated that adding AmmoSoak affected the yields and characteristics of the products. Addition of Ammosoak increased the bio-oil and syngas yields and decreased char yields. Adding AmmoSoak to the feed decreased the pH, water contents, initial viscosity, and the rate at which the viscosity increased with time, while densities and HHVs increased. The addition of Ammosoak to poultry litter also increased the carbon and oxygen contents of the boi-oils while nitrogen, hydrogen, sulfur, chlorine and ash contents decreased. A pilot-scale fluidized bed reactor was designed, constructed, installed and investigated for the pyrolysis of poultry litter. Fluidization and thermal equilibrium of the reactor were successfully demonstrated. The reactor was heated by combustion of propane. To ensure complete combustion, the combustion water was collected and compared to the stoichiometric yield. Complete combustion was achieved. Bio-oil yields on the pilot scale were lower than those obtained on the bench-scale pyrolysis unit. The water soluble fractions of the bio-oils were rich in oxygen. Water insoluble fractions were rich in carbon and ash. / Master of Science

The thesis presents an experimental investigation of combustion performance and emissions of waste cooking oil (WCO) based biodiesel. To evaluate the comparative performance of biodiesel and diesel, combustions tests were conducted using Continuous Combustion rig (CCR) and Land Rover VM diesel engine. Firstly, physical properties of WCO biodiesel and diesel samples were measured in the laboratory. Elemental analysis of WCO biodiesel showed that there are differences between the functional groups in diesel and biodiesel which lead to major differences in the combustion characteristics of the two fuel types. It was found that biodiesel had 10% lower carbon content, almost no sulphur content for biodiesel and up to 12% more oxygen content compared with diesel. This explains the lower caloric value for WCO biodiesel (up to l8 %) compared with diesel. However, higher oxygen content and double bounds in WCO biodiesel increase its susceptibility to oxidation. The CCR test results showed an increase in combustion gas temperature with the increases in biodiesel blend ratio in diesel. This was due to a faster reaction rate for biodiesel than that of diesel leading to a faster brakeage of the hydrocarbon chain to release more heat. The engine tests were performed to measure the torque and emissions for different engine speeds and loads. In general a decrease in engine torque with up to 9% for biodiesel was observed, which was due to the lower calorific value of biodiesel compared with that of diesel. The brake specific fuel consumption (BSFC) increased as the biodiesel blend ratio in diesel increases due a greater mass of fuel being injected at a given injection pressure, compared with diesel. Using WCO blends ratio up to 75% in diesel showed a reduction in exhaust emission compared with diesel, however, at the cost of increased fuel consumption. A common conclusion can be drawn in favour of the WCO biodiesel as being a greener alternative to petro-diesel when used in blend with diesel. However, due to large variations in the biomass used for biodiesel production could lead to variations in physical and chemical properties between biodiesel produced from different biomass. Therefore more stringent standards need to be imposed for biodiesel quality in order to diminish the effect of variation in physicochemical properties on engine performance and emissions. The future work in developing standard test procedures for establishing fuel properties and limits/targets would be beneficial in using a large amount of waste cooking oil in the production of biodiesel, thus contributing to reduction in CO2 and waste minimisation.