Characterization of water-soluble organic matter from urban aerosols

Water-soluble organic matter (WSOM) from atmospheric particles comprises a complex array of molecular structures that play an important role on the physic-chemical properties of atmospheric particles and, therefore, are linked to several global-relevant atmospheric processes which impact the climate and public health. Due to the large variety of sources and formation processes, adequate knowledge on WSOM composition and its effects on the properties of atmospheric aerosol are still limited. Therefore, this thesis aims at providing new insights on the molecular composition of WSOM from fine atmospheric aerosols typical of an urban area (Aveiro, Portugal). In a first step, adsorption phenomena of semivolatile organic compounds on quartz fibre filters employed in the collection of atmospheric aerosols were assessed. Afterwards, atmospheric aerosol samples were collected during fifteen months, on a weekly basis. A mass balance of aerosol samples was performed in order to set the relative contribution of elemental carbon, WSOM and water-insoluble organic matter to the aerosol mass collected at the urban area of Aveiro, with a special focus on the assessment of the influence of different meteorological conditions. In order to assess the chemical complexity of the WSOM from urban aerosols, their structural characteristics were studied by means of Fourier transform infrared infrared - Attenuated Total Reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopies, as well as their elemental composition. The structural characterization of aerosol WSOM samples collected in the urban area highlighted a highly complex mixture of functional groups. It was concluded that aliphatic and aromatic structures, hydroxyl groups and carboxyl groups are characteristic to all samples. The semi-quantitative assessment of the CPMAS 13C NMR data showed different distributions of the various functional groups between the aerosol samples collected at different seasons. Moreover, the presence of signals typical of lignin-derived structures in both CPMAS 13C NMR and FTIR-ATR spectra of the WSOM samples from the colder seasons, highlights the major contribution of biomass burning processes in domestic fireplaces, during low temperature conditions, into the bulk chemical properties of WSOM from urban aerosols. A comprehensive two-dimensional liquid chromatography (LC x LC) method, on-line coupled to a diode array, fluorescence, and evaporative light scattering detectors, was employed for resolving the chemical heterogeneity of the aerosol WSOM samples and, simultaneously, to map the hydrophobicity versus the molecular weight distribution of the samples. The LC x LC method employed a mixed-mode hydrophilic interaction column operating under aqueous reversed phase mode in the first dimension, and a size-exclusion column in the second dimension, which was found to be useful for separating the aerosol WSOM samples into various fractions with distinct molecular weight and hydrophobic features. The estimative of the average molecular weight (Mw) distribution of the urban aerosol WSOM samples ranged from 48 to 942 Da and from 45 to 1241 Da in terms of UV absorption and fluorescence detection, respectively. Findings suggest that smaller Mw group fractions seem to be related to a more hydrophobic nature.

Caracterização geológica e geofísica da área do porto da Figueira da Foz

No âmbito de um projeto realizado para a Administração Portuária do Porto da Figueira da Foz, foram recolhidos dados geofísicos no offshore da costa da Figueira da Foz, utilizando um sistema combinado de sonar de varrimento lateral e de sísmica de alta resolução com o objetivo de compreender a distribuição de sedimentos ao longo do fundo marinho e assim entender melhor a sua origem. Os dados de varrimento lateral foram processados, analisados e representados em mosaicos recorrendo ao software integrado TRINTON Prespective. Foram colhidas 10 amostras de sedimentos de fundo que foram analisadas do ponto de vista granulométrico e que foram usadas para a calibração dos mosaicos do sonar de varrimento lateral de modo a produzir um mapa semi-quantitativo de classificação dos sedimentos de fundo. Os dados de reflexão sísmica foram processados e analisados através dos softwares SPW e RadExPro. Os mapas de sonar de varrimento lateral produzidos (mosaicos) mostram uma relação entre o tamanho de grão e composição dos depósitos de plataforma interna e os processos geológicos que ocorrem na zona costeira adjacente. Também se verifica uma relação entre a orientação da costa e a sua consequente exposição às ondas incidentes, e como isso afeta e altera a distribuição do tamanho grão. Neste contexto, a interpretação combinada dos mosaicos do sonar de varrimento lateral com os dados de granulometria e a batimetria dos sedimentos permitiram uma cartografia interpretativa detalhada da morfologia do mar, uma melhor compreensão do controlo da linha costeira na propagação das ondas e correntes e, por conseguinte, na transferência de sedimento no litoral. Os dados de sísmica permitem ainda verificar a espessura das várias camadas geológicas em profundidade.