Loading...
6 results
Search Results
Now showing 1 - 6 of 6
- Road tunnel, roadside, and urban background measurements of aliphatic compounds in size-segregated particulate matterPublication . Oliveira, Cesar; Martins, Natercia; Mirante, Fátima; Caseiro, Alexandre; Pio, Casimiro; Matos, Manuel; Silva, Hugo; Oliveira, Cristina; Camões, FilomenaParticulate matter samples were collected in a road tunnel in Lisbon (PM0.5, PM0.5-1, PM1-2.5, and PM2.5-10) and at two urban locations representing roadside and background stations (PM2.5 and PM2.5-10). Samples were analysed for organic and elemental carbon (OC and EC), n-alkanes, n-alkenes, hopanes, some isoprenoid compounds, and steranes. Particulate matter concentrations in the tunnel were 17-31 times higher than at roadside in the vicinity, evidencing an aerosol origin almost exclusively in fresh vehicle emissions. PM0.5 in the tunnel comprised more than 60% and 80% of the total OC and EC mass in PM10, respectively. Concentrations of the different aliphatic groups of compounds in the tunnel were up to 89 times higher than at roadside and 143 times higher than at urban background. Based on the application of hopane-to-OC or hopanes-to-EC ratios obtained in the tunnel, it was found that vehicle emissions are the dominant contributor to carbonaceous particles in the city but do not represent the only source of these triterpenic compounds. Contrary to what has been observed in other studies, the Sigma hopane-to-EC ratios were higher in summer than in winter, suggesting that other factors (e.g. biomass burning, dust resuspension, and different fuels/engine technologies) prevail in relation to the photochemical decay of triterpenoid hydrocarbons from vehicle exhaust
- OC/EC ratio observations in Europe: Re-thinking the approach for apportionment between primary and secondary organic carbonPublication . Casimiro Pio; Cerqueira, Mario; Harrison, Roy M.; Nunes, Teresa; Mirante, Fátima; Alves, Célia; Oliveira, Cesar; Sanchez de la Campa, Ana; Artinano, Begona; Matos, ManuelThis study explores a large set of OC and EC measurements in PM(10) and PM(2.5) aerosol samples, undertaken with a long term constant analytical methodology, to evaluate the capability of the OC/EC minimum ratio to represent the ratio between the OC and EC aerosol components resulting from fossil fuel combustion (OC(ff)/EC(ff)). The data set covers a wide geographical area in Europe, but with a particular focus upon Portugal, Spain and the United Kingdom, and includes a great variety of sites: urban (background, kerbside and tunnel), industrial, rural and remote. The highest minimum ratios were found in samples from remote and rural sites. Urban background sites have shown spatially and temporally consistent minimum ratios, of around 1.0 for PM(10) and 0.7 for PM(2.5).The consistency of results has suggested that the method could be used as a tool to derive the ratio between OC and EC from fossil fuel combustion and consequently to differentiate OC from primary and secondary sources. To explore this capability, OC and EC measurements were performed in a busy roadway tunnel in central Lisbon. The OC/EC ratio, which reflected the composition of vehicle combustion emissions, was in the range of 03-0.4. Ratios of OC/EC in roadside increment air (roadside minus urban background) in Birmingham, UK also lie within the range 03-0.4. Additional measurements were performed under heavy traffic conditions at two double kerbside sites located in the centre of Lisbon and Madrid. The OC/EC minimum ratios observed at both sites were found to be between those of the tunnel and those of urban background air, suggesting that minimum values commonly obtained for this parameter in open urban atmospheres over-predict the direct emissions of OC(ff) from road transport. Possible reasons for this discrepancy are explored. (C) 2011 Elsevier Ltd. All rights reserved.
- Mesoporous nanosilica-supported polyoxomolybdate as catalysts for sustainable desulfurizationPublication . Mirante, Fátima; Gomes, Neide; Branco, Luis; Cunha-Silva, Luís; Almeida, Pedro L.; Pillinger, Martyn; Gago, S.; Granadeiro, Carlos; Balula, SaleteMesoporous silica nanoparticles (MSNs) strategically functionalized were used to immobilize a homogeneous polyoxomolybdate catalyst [PMo12O40](3-) (PMo12), active but unstable. The PMo12@TBA-MSN composite (where TBA refers to surface-tethered tributylammonium groups) conferred high stability to the polyoxomolybdate catalytic center and displayed an increase in efficiency for the oxidative desulfurization (ECODS) of a diesel simulant under sustainable conditions (using H2O2 as oxidant and an ionic liquid, [BMIM]PF6, as solvent). Continuous reuse of the catalyst and ionic liquid solvent in consecutive ECODS cycles was successfully performed, avoiding the production of residual wastes. The performance of the PMo12@TBA-MSN catalyst improved upon its reuse, leading to complete desulfurization of a multicomponent model diesel containing benzothiophene derivatives after just 1 h of the catalytic stage of the process. The robust nature of the supported catalyst was indicated by characterization of the recovered solid which showed retention of the structural and chemical integrities.
- Efficient heterogeneous polyoxometalate-hybrid catalysts for the oxidative desulfurization of fuelsPublication . Mirante, Fátima; Dias, Luís; Silva, Mariana; Ribeiro, Susana; Corvo, Marta C.; De Castro, Baltazar; Granadeiro, Carlos; Balula, SaleteThe heterogenization of the highly active monovacant polyoxotungstate ([PW11O39](7-), abbreviated as PW11) was achieved by preparing the corresponding long chain quaternary ammonium salt (ODA(7)PW(11), ODA = CH3(CH2)(17)(CH3)(3)N). The complete cation exchange confers total heterogeneity to the monovacant catalyst while keeping its oxidative catalytic activity. In fact, the heterogeneous catalyst allowed for the complete desulfurization of a multicomponent model diesel (2000 ppm S) after 40 min of reaction, conciliating extraction (using BMIMPF6 solvent) and oxidation (ECODS process using H2O2 oxidant). The heterogeneous catalyst has shown a superior desulfurization performance when compared with the homogeneous quaternary ammonium TBAPW(11) catalyst (TBA = (C4H9)(4) N). Both hybrid catalysts have been successfully reused in consecutive ECODS cycles. Additionally, the long carbon chain cations provide a protective environment around the polyoxometalate allowing for ODA(7)PW(11) to retain its heterogeneity and structure after the ECODS process.
- Size-segregated chemical composition of aerosol emissions in an urban road tunnel in PortugalPublication . Pio, Casimiro; Mirante, Fátima; Oliveira, Cesar; Matos, Manuel; Caseiro, Alexandre; Oliveira, Cristina; Querol, Xavier; Alves, Célia; Martins, Natércia; Cerqueira, Mário; Camões, Filomena; Silva, Hugo; Plana, FelicianoAn atmospheric aerosol study was performed in 2008 inside an urban road tunnel, in Lisbon, Portugal. Using a high volume impactor, the aerosol was collected into four size fractions (PM0.5, PM0.5-1, PM1-2.5 and PM2.5-10) and analysed for particle mass (PM), organic and elemental carbon (OC and EC), polycyclic aromatic hydrocarbons (PAH), soluble inorganic ions and elemental composition. Three main groups of compounds were discriminated in the tunnel aerosol: carbonaceous, soil component and vehicle mechanical wear. Measurements indicate that Cu can be a good tracer for wear emissions of road traffic. Cu levels correlate strongly with Fe, Mn, Sn and Cr, showing a highly linear constant ratio in all size ranges, suggesting a unique origin through sizes. Ratios of Cu with other elements can be used to source apportion the trace elements present in urban atmospheres, mainly on what concerns coarse aerosol particles. (C) 2013 Elsevier Ltd. All rights reserved.
- Large-pore silica spheres as support for samarium-coordinated undecamolybdophosphate: Oxidative desulfurization of dieselsPublication . Mirante, Fátima; Alves, Ana C.; Julião, Diana; Almeida, Pedro L.; Gago, S.; Valença, Rita; Ribeiro, Jorge; De Castro, Baltazar; Granadeiro, Carlos; Balula, SaleteA novel composite has been prepared through the immobilization of the Keggin sandwich-type [Sm (PMo11O39)(2)](11-) anion (SmPOM) on large-pore silica spheres previously functionalized with trimethylammonium groups (TMA). The resulting SmPOM@TMA-LPMS material has been evaluated as heterogeneous catalyst in a biphasic desulfurization 1:1 diesel/extraction solvent system using H2O2 as oxidant. Preliminary experiments were conducted with different extraction solvents, acetonitrile and [BMIM]PF6 ionic liquid. The optimized extractive and catalytic oxidative desulfurization system (ECODS) with [BMIM]PF6 was able to reach complete sulfur removal from a model diesel containing 2100 ppm S in just 60 min (10 min of initial extraction + 50 min of catalytic step). The reutilization of catalyst and extraction phase has been successfully performed without loss of desulfurization efficiency in consecutive cycles, turning the process more sustainable and cog-effective. The remarkable results with simulated diesel have motivated the application of the catalyst in the desulfurization of untreated real diesel and 74% of efficiency was achieved after only 2 h for three consecutive cycles.