Photodegradation of sertraline by solar radiation and influencing factors

Photodegradation is considered to be one of the most important processes of elimination of pharmaceutical drugs from natural water matrices. The high consumption and discharge of these substances, in particular antidepressants, to the aquatic environment supports the need to study degradation processes. This dissertation aimed at studying the direct and indirect photodegradation of sertraline, an antidepressant known for its persistence in the environment, and the evaluation of the influence of environmentally relevant factors in its photodegradation. The photodegradation experiments were developed under simulated solar light and the irradiation times converted to summer sunny days (SSD), an equivalent time in natural environmental conditions. The direct photodegradation was evaluated in solutions of sertraline prepared in ultrapure water and the indirect photodegradation was studied through the addition of photosensitizers (humic substances, Fe(III), nitrates and oxygen). Further irradiation studies were perfomed in aqueous samples collected from two wastewater treatment plants, Vouga river and Ria de Aveiro. The samples were chemically characterized (dissolved organic carbon, nitrates and nitrites and iron determination and UV/Vis spectroscopy). The quantification of sertraline was done by HPLC-UV and photoproducts from direct photodegradation were identified by electrospray mass spectrometry. An observed direct photodegradation rate of sertraline of 0.0062 h-1 was determined, corresponding to a half-life time of 111 h (equivalent to 29 SSD). A significant influence of photosensitizers was observed, the best results being achieved in irradiations of sertraline with humic acids, obtaining a half-life time of 12 h. This was attributed to the hydrophobicity of this substance and higher absortivity in the UV/Vis wavelength, which promote processes of indirect photodegradation. The degradation of sertraline in natural samples was also enhanced comparatively to the direct photodegradation, achieving half-life times between 10 and 25h; the best results were achieved in samples from the primary treatment of a wastewater treatment plant and Ria de Aveiro, with half-life times of 10 and 16 h, respectively. A total of six photoproducts formed during the direct photodegradation of sertraline were identified, three of which were not yet identified in the literature. The main factors contributing to the degradation of sertraline were analysed but this was not fully accomplished, requiring further studies of the composition of the natural matrices and the combined influence of distinct photosensitizers during the irradiation. Nevertheless, it was concluded that the photodegradation of sertraline is greatly influenced by indirect photodegradation processes, promoted by the presence of photosensitizers.

Exergetic, energetic, economic and environmental evaluation of concentrated solar power plants in Libya

The PhD project addresses the potential of using concentrating solar power (CSP) plants as a viable alternative energy producing system in Libya. Exergetic, energetic, economic and environmental analyses are carried out for a particular type of CSP plants. The study, although it aims a particular type of CSP plant – 50 MW parabolic trough-CSP plant, it is sufficiently general to be applied to other configurations. The novelty of the study, in addition to modeling and analyzing the selected configuration, lies in the use of a state-of-the-art exergetic analysis combined with the Life Cycle Assessment (LCA). The modeling and simulation of the plant is carried out in chapter three and they are conducted into two parts, namely: power cycle and solar field. The computer model developed for the analysis of the plant is based on algebraic equations describing the power cycle and the solar field. The model was solved using the Engineering Equation Solver (EES) software; and is designed to define the properties at each state point of the plant and then, sequentially, to determine energy, efficiency and irreversibility for each component. The developed model has the potential of using in the preliminary design of CSPs and, in particular, for the configuration of the solar field based on existing commercial plants. Moreover, it has the ability of analyzing the energetic, economic and environmental feasibility of using CSPs in different regions of the world, which is illustrated for the Libyan region in this study. The overall feasibility scenario is completed through an hourly analysis on an annual basis in chapter Four. This analysis allows the comparison of different systems and, eventually, a particular selection, and it includes both the economic and energetic components using the “greenius” software. The analysis also examined the impact of project financing and incentives on the cost of energy. The main technological finding of this analysis is higher performance and lower levelized cost of electricity (LCE) for Libya as compared to Southern Europe (Spain). Therefore, Libya has the potential of becoming attractive for the establishment of CSPs in its territory and, in this way, to facilitate the target of several European initiatives that aim to import electricity generated by renewable sources from North African and Middle East countries. The analysis is presented a brief review of the current cost of energy and the potential of reducing the cost from parabolic trough- CSP plant. Exergetic and environmental life cycle assessment analyses are conducted for the selected plant in chapter Five; the objectives are 1) to assess the environmental impact and cost, in terms of exergy of the life cycle of the plant; 2) to find out the points of weakness in terms of irreversibility of the process; and 3) to verify whether solar power plants can reduce environmental impact and the cost of electricity generation by comparing them with fossil fuel plants, in particular, Natural Gas Combined Cycle (NGCC) plant and oil thermal power plant. The analysis also targets a thermoeconomic analysis using the specific exergy costing (SPECO) method to evaluate the level of the cost caused by exergy destruction. The main technological findings are that the most important contribution impact lies with the solar field, which reports a value of 79%; and the materials with the vi highest impact are: steel (47%), molten salt (25%) and synthetic oil (21%). The “Human Health” damage category presents the highest impact (69%) followed by the “Resource” damage category (24%). In addition, the highest exergy demand is linked to the steel (47%); and there is a considerable exergetic demand related to the molten salt and synthetic oil with values of 25% and 19%, respectively. Finally, in the comparison with fossil fuel power plants (NGCC and Oil), the CSP plant presents the lowest environmental impact, while the worst environmental performance is reported to the oil power plant followed by NGCC plant. The solar field presents the largest value of cost rate, where the boiler is a component with the highest cost rate among the power cycle components. The thermal storage allows the CSP plants to overcome solar irradiation transients, to respond to electricity demand independent of weather conditions, and to extend electricity production beyond the availability of daylight. Numerical analysis of the thermal transient response of a thermocline storage tank is carried out for the charging phase. The system of equations describing the numerical model is solved by using time-implicit and space-backward finite differences and which encoded within the Matlab environment. The analysis presented the following findings: the predictions agree well with the experiments for the time evolution of the thermocline region, particularly for the regions away from the top-inlet. The deviations observed in the near-region of the inlet are most likely due to the high-level of turbulence in this region due to the localized level of mixing resulting; a simple analytical model to take into consideration this increased turbulence level was developed and it leads to some improvement of the predictions; this approach requires practically no additional computational effort and it relates the effective thermal diffusivity to the mean effective velocity of the fluid at each particular height of the system. Altogether the study indicates that the selected parabolic trough-CSP plant has the edge over alternative competing technologies for locations where DNI is high and where land usage is not an issue, such as the shoreline of Libya.

Chemical vapour deposition of vanadium oxide thermochromic thin films

Thermochromic materials change optical properties, such as transmittance or reflectance, with a variation in temperature. An ideal intelligent (smart) material will allow solar radiation in through a window in cold conditions, but reflect that radiation in warmer conditions. The variation in the properties is often associated with a phase change, which takes place at a definite temperature, and is normally reversible. Such materials are usually applied to window glass as thin films. This thesis presents the work on the development of thermochromic vanadium (IV) oxide (VO2) thin films – both undoped and doped with tungsten, niobium and gold nanoparticles – which could be employed as solar control coatings. The films were deposited using Chemical Vapour Deposition (CVD), using improved Atmospheric Pressure (APCVD), novel Aerosol Assisted (AACVD) and novel hybrid AP/AACVD techniques. The effects of dopants on the metalto- semiconductor transition temperature and transmittance/reflectance characteristics were also investigated. This work significantly increased the understanding of the mechanisms behind thermochromic behaviour, and resulted in thermochromic materials based on VO2 with greatly improved properties.

Phylogenetic and functional diversity of estuarine bacterioneuston

A micro-camada superficial da água (SML) é caracterizada pela ocorrência de grandes quantidades de compostos orgânicos, pela acumulação de contaminantes antropogênicos e é submetida a uma intensa radiação solar, extrema mudança de temperatura e, no caso dos estuários, flutuação de salinidade. Estas propriedades físico-químicas estão, provavelmente, a modular a comunidade bacteriana (bacterioneuston) com propriedades filogenéticas e funcionais específicas. Neste estudo, as abordagens dependentes e independentes do cultivo foram aplicadas para avaliar a estrutura e dinâmica das comunidades bacterioneuston e bacterioplâncton em três localizações geográficas ao longo do estuário da Ria de Aveiro. Além disso, comparámos a diversidade filogenética de grupos específicos (Aeromonas, Pseudomonas e Psychrobacter) presentes em bacterioneuston e bacterioplâncton. Finalmente, as duas comunidades foram comparadas em termos de prevalência e diversidade de bactérias resistentes aos antibióticos e respetivos genes de resistência. Bactérias heterotróficas cultiváveis foram enriquecidas em SML. Eletroforese em gel de gradiente desnaturante (DGGE) permitiu a identificação de filotipos específicos em SML. Além disso, a análise de agrupamento dos perfis de DGGE de ambas as comunidades revelou uma ligeira tendência de agrupamento de acordo com a camada amostrada. As diferenças entre as duas comunidades variaram de acordo com factores espaciais e temporais. Em termos de diversidade filogenética de grupos específicos, não foram identificadas diferenças consistentes entre SML e UW com relação às comunidades de Aeromonas. Com relação ao género Pseudomonas, uma unidade operacional taxonómica cultivável foi consistentemente hiper-representada nas amostras de SML. Metodologias dependentes e independentes do cultivo revelaram a presença de populações de Psychrobacter complexas e muito estáveis em todos os sítios e datas de amostragens, com diferenças significativas entre as comunidades de Psychrobacter presentes em SML e UW. Estirpes representativas de prováveis novas espécies também foram cultivadas. Em termos de resistência aos antibióticos, a prevalência de bactérias resistentes em SML foi alta sugerindo selecção pelas condições presentes em SML. É preciso enfatizar que a resistência aos antibióticos foi incomum entre as bactérias estuarinas e os mecanismos de resistência foram, predominantemente, intrínsecos. Pela combinação de abordagens inovadoras dependentes e independentes do cultivo, este estudo forneceu novas e consistentes informações com relação às diferenças em ambas as comunidades bacterianas e em relação a alguns dos fatores que contribuem para a sua formação.

Moringa oleifera plasticity to face climatic changes

Extreme abiotic factors, such drought combined with heat waves and/or high UVB radiation are predicted to become more frequent in the future. The impact on plant production of these challenges on multipurpose Moringa oleifera L. remains unclear. A susceptibility of this species may lead to increase poverty in endangered regions. M. oleifera is a woody species native from sub-Himalaya regions under high climate stress pressure. The interest on this species is emerging due to its several medicinal properties and its nutritional value. Agropharmaceutical industry is interest in this species too. To understand the impact of increased climate factors, young (2 months old) plants of this species were exposed to water deficit (WD) and UVB (alone or combined). WD and WD+UVB imposition consists of unwater for 4 days. After 1 day withholding water, UVB and WD+UVB were irradiated with 26.3 kJ m-2 distributed per 3 days. Immediately after treatment exposition (1 day) and after 10 days, plant water status, growth, carbon metabolism and oxidative stress were measured. Overall no significant differences were observed in WD, regarding the parameters analysed, except on gas exchanges, MDA and phenols. The plants exposed to UVB showed, in general, more severe effects, as higher pigment content, MDA and membrane permeability, while no changes were observed in the total antioxidant activity. Plants exposed to UVB+WD, despite changes observed, the impact was lower than the one observed in UVB exposed plants, meaning that a protective/adaptive mechanism was developed in the plants under combined stressors. On the other hand, in all treatments the net CO2 assimilation rate decreased. Results suggest that M. oleifera has some tolerance to WD and UVB, and that develops mechanism of adaptation to these two types of stress that often arise in combination under a climate change scenario.