On watching rather than reading Count Basil

Compte rendu de la présentation de la pièce « Count Basil » de Joanna Baillie montée par la compagnie Horizon Theatre lors du Congrès 2004 de la North American society for the study of romanticism (NASSR).

Indoor environment and the impact on the health of pre-exisiting asthmatics at work: the development of a risk management framework

This thesis examines the spatial and temporal variation in nitrogen dioxide (NO2) levels in Guernsey and the impacts on pre-existing asthmatics. Whilst air quality in Guernsey is generally good, the levels of NO2 exceed UK standards in several locations. The evidence indicates that people suffering from asthma have exacerbation of their symptoms if exposed to elevated levels of air pollutants including NO2, although this research has never been carried out in Guernsey before. In addition, exposure assessment of individuals is rarely carried out and research in this area is limited due to the complexity of undertaking such a study, which will include a combination of exposures in the home, the workplace and ambient exposures, which vary depending on the individual daily experience. For the first time in Guernsey, this research has examined NO2 levels in correlation with asthma patient admissions to hospital, assessment of NO2 exposures in typical homes and typical workplaces in Guernsey. The data showed a temporal correlation between NO2 levels and the number of hospital admissions and the trend from 2008-2012 was upwards. Statistical analysis of the data did not show a significant linear correlation due to the small size of the data sets. Exposure assessment of individuals showed a spatial variation in exposures in Guernsey and assessment in indoor environments showed that real-time analysis of NO2 levels needs to be undertaken if indoor micro environments for NO2 are the be assessed adequately. There was temporal and spatial variation in NO2 concentrations measured using diffusion tubes, which provide a monthly mean value, and analysers measuring NO2 concentrations in real time. The research shows that building layout and design are important factors for good air flow and ventilation and the dispersion of NO2 indoors. Environmental Health Officers have statutory responsibilities for ambient air quality, hygiene of buildings and workplace environments and this role needs to be co-ordinated with healthcare professionals to improve health outcomes for asthmatics. The outcome of the thesis was the development of a risk management framework for pre-existing asthmatics at work for use by regulators of workplaces and an information leaflet to assist in improving health outcomes for asthmatics in Guernsey.

Lifetime and distribution of ozone and related pollutants in the eastern United States

Most major cities in the eastern United States have air quality deemed unhealthy by the EPA under a set of regulations known as the National Ambient Air Quality Standards (NAAQS). The worst air quality in Maryland is measured in Edgewood, MD, a small community located along the Chesapeake Bay and generally downwind of Baltimore during hot, summertime days. Direct measurements and numerical simulations were used to investigate how meteorology and chemistry conspire to create adverse levels of photochemical smog especially at this coastal location. Ozone (O3) and oxidized reactive nitrogen (NOy), a family of ozone precursors, were measured over the Chesapeake Bay during a ten day experiment in July 2011 to better understand the formation of ozone over the Bay and its impact on coastal communities such as Edgewood. Ozone over the Bay during the afternoon was 10% to 20% higher than the closest upwind ground sites. A combination of complex boundary layer dynamics, deposition rates, and unaccounted marine emissions play an integral role in the regional maximum of ozone over the Bay. The CAMx regional air quality model was assessed and enhanced through comparison with data from NASA’s 2011 DISCOVER-AQ field campaign. Comparisons show a model overestimate of NOy by +86.2% and a model underestimate of formaldehyde (HCHO) by –28.3%. I present a revised model framework that better captures these observations and the response of ozone to reductions of precursor emissions. Incremental controls on electricity generating stations will produce greater benefits for surface ozone while additional controls on mobile sources may yield less benefit because cars emit less pollution than expected. Model results also indicate that as ozone concentrations improve with decreasing anthropogenic emissions, the photochemical lifetime of tropospheric ozone increases. The lifetime of ozone lengthens because the two primary gas-phase sinks for odd oxygen (Ox ≈ NO2 + O3) – attack by hydroperoxyl radicals (HO2) on ozone and formation of nitrate – weaken with decreasing pollutant emissions. This unintended consequence of air quality regulation causes pollutants to persist longer in the atmosphere, and indicates that pollutant transport between states and countries will likely play a greater role in the future.

Emisiones de gases de efecto invernadero en el humedal natural El Madrigal

En la presente investigaci?n se estudi? la din?mica de la generaci?n y captura de las emisiones de gases de efecto invernadero (GEI) en un humedal natural eutrofizado bajo condiciones tropicales denominado El Madrigal, ubicado en la vereda El Madrigal, del municipio de Riofr?o, Valle del Cauca. Con tal prop?sito se evalu? la variaci?n espacial de las emisiones de los GEI tales como metano (CH4), di?xido de carbono (CO2) y ?xido nitroso (N2O) y se estableci? su posible correlaci?n con par?metros de calidad de agua como pH, ox?geno disuelto, potencial de ?xido reducci?n, alcalinidad, fosfatos, nitratos entre otros y a su vez con el contenido de materia org?nica y nutrientes presente en los sedimentos. En este sentido, se determinaron y compararon las emisiones en cuatro puntos de muestreo establecidos en el humedal con caracter?sticas diferentes: P1 (Zona de intercambio de agua y sedimentos con R?o Cauca), P2 (Zona influenciada por actividades pisc?colas), P3 (Zona influenciada por vertimientos de aguas residuales y presencia de vegetaci?n) y P3A (Zona sin cobertura vegetal). En cada punto se realizaron mediciones de gases de efecto invernadero, par?metros in situ, calidad de agua y, sedimentos. Los valores de flux obtenidos evidenciaron que el humedal El Madrigal actu? como fuente y sumidero de gases de efecto invernadero durante todo el per?odo de muestreo. El punto P1 present? flux promedios de -1,96 ? 3,10 g.CH4.m-2 d-1; -0,12 ? 7,63 g.CO2.m-2 d-1 y 1,73 ? 5,75 mg.N2O.m-2 d-1. Para el caso del punto P2 se obtuvieron flux promedios de 0,898 ? 1,27 g.CH4.m-2 d-1; 1,03 ? 9,31 g.CO2.m-2 d-1 y -1,19 ? 5,08 mg.N2O.m-2 d-1. Por su parte el punto P3 evidenci? flux promedios de 3,08 ? 3,99 g.CH4.m-2 d-1; -2,74 ? 9,83 g.CO2.m-2 d-1 y 2,06 ? 5,20 mg.N2O.m-2 d-1. Por ?ltimo los flux promedios obtenidos para el punto P3A fueron 1,80 ? 6,89 g.CH4.m-2 d-1; 1,40 ? 8,40 g.CO2.m-2 d-1 y -1,24 ? 6,43 mg.N2O.m-2 d-1. Las pruebas estad?sticas indicaron que los flux de los gases de efecto invernadero estudiados presentaron una variaci?n espacial significativa entre los puntos muestreados. CH4 present? variaci?n entre los puntos P1, P2 y P3 (p<0.001 Mann-Whitney) y evidenci? similitudes entre los puntos P3A-P3 y P3A-P2 (p>0.05 Mann-Whitney). Para CO2 se evidenci? similitud para los flux obtenidos en los cuatro puntos (p>0.05 Mann-Whitney). Por su parte, para el ?xido nitroso tambi?n se present? un comportamiento similar en los cuatro puntos sin variaci?n significativa (p>0.05 Mann-Whitney). Con respecto a las relaciones entre los par?metros de calidad de agua, sedimentos y los flux de gases de efecto invernadero, se determin? que los par?metros con mayor influencia sobre la producci?n y consumo de CH4 CO2 y N2O fueron hierro f?rrico (Fe+3) Coeficiente Spearman = -73%), nitratos (NO3) (Coeficiente Spearman = -65%) y los nitritos (NO2) en sedimentos Coeficiente Spearman = 86%), respectivamente. Los resultados obtenidos en este estudio evidenciaron que la intervenci?n antr?pica contribuye al estado eutr?fico del ecosistema y este a su vez influencia la din?mica de producci?n y consumo de GEI favoreciendo el incremento en la generaci?n de estos, demandando medidas de manejo y control que permitan mitigar el impacto frente al cambio clim?tico

Reator de leito estruturado com recirculação submetido à aeração intermitente no tratamento de esgoto sanitário

The release of nitrogen compounds in water bodies can result in many environmental problems, so treat wastewater, such as sewage in order to remove not only organic matter but also nitrogen has been studied a few decades. From the above, the objective of this study was to evaluate the performance of a structured bed reactor, continuous flow, with recirculation, in removing organic matter and nitrogen present in wastewater under different cycles of intermittent aeration (AI) and to evaluate the influence of these cycles in the development of nitrifying bacteria (Oxidizing Bacteria Ammonia - BOA and Bacteria Oxidizing Nitrite - BON) and denitrifying (DESN) adhered (Support Material - MS) and suspension (Effluent - EF and sludge - LD). The reactor used has usable volume of 9.4 L. As support materials (MS) polyurethane foam was used, cut and fixed in PVC rods. 3 were worked aeration phases (AE) and non-aeration (AN) at different stage: Stage 1 (4 h EA / AN 2H); Stage 2 (2H EA / AN 1 h) and Phase 3 (2H EA / AN 2 h). During all hydraulic detention time phases was kept at 16 h and the effluent recirculated at a rate of 3 times the inflow. Were analyzed: pH, total alkalinity, temperature, chemical oxygen demand (COD), Biochemical Oxygen Demand (BOD), nitrogen Kjeldhl Total (NKT), ammonia-N-N-NH4+, nitrito-N-NO2+andnitrato-NO3-. The concentration of BOA, BON and DESN was determined using the number More Provável.gSSV-1 (NMP.gSSV-1). In phase 1 the percentage removal NTK N-NH4+ and NT was 76±10%, 70±21% and 67±10% respectively. In Phase 2 80±15% of removel NKT, 86±15% of N-NH4+ e 68±9% of removel NT e na Fase 3 de 58±20%, 72±28% and 41±6% of NKT, N-NH4+ of NT, respectively. The denitrification efficiency in stage 3 was over 70%, indicating that occurred in the reactor the process of simultaneous nitrification and denitrification (NDS). DQOT the removal percentages were 88 ± 4% in Phase 1, 94 ± 7 in Phase 2 and 90± 11% in Phase 3. The multivariate ANOVA applied to NMP.gSSV-1, it indicated that there was significant (F: 20,2, p <0,01) between the analyzed concentration of organisms AI in different cycles, but the differences between NMP.gSSV-1 depends not only isolated factors but of which means, and phase groups being analysis. From the results it is concluded that the working system is efficient in terms of nitrogen removal and organic matter, and that the stage with the highest availability of Dissolved Oxygen (DO) and C/N ratio (Step 2), was the one obtained the lower concentrations of organic matter effluents and N-NH4+. Hinted that there was a significant difference between the concentration (NMP.100mL-1) of the analyzed organizations (BOA, BON and DESN), but this difference does not depend on factors alone but of which means (MS, EF or LD), stages (1, 2 or 3) and groups (BOA, BON and DESN) is being considered.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Estudo comparativo de dois tipos de cultivo: monocultivo (camarões) versus cultivo integrado (algas/camarões)

The integrated culture of seaweed and aquatic animals is an ancient practice in Asian countries. The expansion of this practice to western countries is consequence of the recognition of this system as a sustainable alternative that allows economical diversification and mitigation of environmental impacts generated by effluents of aquaculture. This study evaluated the growth of the seaweed Gracilaria caudata and of the shrimp Litopenaeus vannamei in monoculture (shrimps) and integrated culture (shrimps and algae) systems, and accessed the effect of the seaweed in the water quality. There were two treatments in the experiment: monoculture (shrimps) and integrated culture (shrimps/ algae). The organisms were cultured in 6 aquaria (10L) filled with seawater (35.0±0.0 PSU and 28.1±0.4°C) for 28 days. The nutrients of water (PO43-, NH4+, NO2-, NO3- and DIN), the biomass and the relative growth rate (RGR, % day-1) of seaweed and shrimps were measured weekly. The parameters pH, temperature, salinity and dissolved oxygen were measured daily. The concentration of NH4+ in integrated culture (62.8±25.2µM) was lower (Mann-Whitney p<0.001) than in monoculture (85.6±24.3µM). The mean of PO4- in monoculture (10.4±4.6µM) was markedly higher (Mann-Whitney; p=0.024) than that in integrated culture (8.7±4.1µM). The level of dissolved oxygen in integrated culture (6.0±0.6mg/L) was higher (t-Student; P=0.014) than that in shrimp monoculture (5.8±0.6mg/L). The mean values of the parameters pH, NO2-, NO3- and DIN were 7.5±0.2, 10.1±12.2µM, 24.5±3.2µM and 120.17±30.76µM in monoculture, and 7.5±0.2, 10.5±13.2µM, 27.4±3.5µM and 100.76±49.59µM in integrated culture. There were not differences in these parameters between treatments. The biomass and RGR of seaweed reached 15.0±1.9g and 7.4±2.8% day-1 at the end of the experiment. The performance of shrimp was favorable in monoculture (1.5±0.8g; 5.7±1.6% dia-1) and in integrated culture (1.5±0.7g; 5.2±1.2% dia-1), and the rate of survival was 100% in both treatments. The tolerance and favorable performance of Gracilaria caudata suggest that this seaweed might be integrated into shrimp (Litopenaeus vannamei) culture systems

Photochemistry and transport of tropospheric ozone and its precursors in urban and remote environments

Tropospheric ozone (O3) adversely affects human health, reduces crop yields, and contributes to climate forcing. To limit these effects, the processes controlling O3 abundance as well as that of its precursor molecules must be fully characterized. Here, I examine three facets of O3 production, both in heavily polluted and remote environments. First, using in situ observations from the DISCOVER-AQ field campaign in the Baltimore/Washington region, I evaluate the emissions of the O3 precursors CO and NOx (NOx = NO + NO2) in the National Emissions Inventory (NEI). I find that CO/NOx emissions ratios derived from observations are 21% higher than those predicted by the NEI. Comparisons to output from the CMAQ model suggest that CO in the NEI is accurate within 15 ± 11%, while NOx emissions are overestimated by 51-70%, likely due to errors in mobile sources. These results imply that ambient ozone concentrations will respond more efficiently to NOx controls than current models suggest. I then investigate the source of high O3 and low H2O structures in the Tropical Western Pacific (TWP). A combination of in situ observations, satellite data, and models show that the high O3 results from photochemical production in biomass burning plumes from fires in tropical Southeast Asia and Central Africa; the low relative humidity results from large-scale descent in the tropics. Because these structures have frequently been attributed to mid-latitude pollution, biomass burning in the tropics likely contributes more to the radiative forcing of climate than previously believed. Finally, I evaluate the processes controlling formaldehyde (HCHO) in the TWP. Convective transport of near surface HCHO leads to a 33% increase in upper tropospheric HCHO mixing ratios; convection also likely increases upper tropospheric CH3OOH to ~230 pptv, enough to maintain background HCHO at ~75 pptv. The long-range transport of polluted air, with NO four times the convectively controlled background, intensifies the conversion of HO2 to OH, increasing OH by a factor of 1.4. Comparisons between the global chemistry model CAM-Chem and observations show that consistent underestimates of HCHO by CAM-Chem throughout the troposphere result from underestimates in both NO and acetaldehyde.

Glutathione Transferases as Detoxification Agents: Structural and Functional Studies

Glutathione transferases (GSTs) are a diverse family of enzymes that catalyze the glutathione-dependent detoxification of toxic compounds. GSTs are responsible for the conjugation of the tripeptide glutathione (GSH) to a wide range of electrophilic substrates. These include industrial pollutants, drugs, genotoxic carcinogen metabolites, antibiotics, insecticides and herbicides. In light of applications in biomedicine and biotechnology as cellular detoxification agents, detailed structural and functional studies of GSTs are required. Plant tau class GSTs play crucial catalytic and non-catalytic roles in cellular xenobiotic detoxification process in agronomically important crops. The abundant existence of GSTs in Glycine max and their ability to provide resistance to abiotic and biotic stresses such as herbicide tolerance is of great interest in agriculture because they provide effective and suitable tools for selective weed control. Structural and catalytic studies on tau class GST isoenzymes from Glycine max (GmGSTU10-10, GmGSTU chimeric clone 14 (Sh14), and GmGSTU2-2) were performed. Crystal structures of GmGSTU10-10 in complex with glutathione sulfenic acid (GSOH) and Sh14 in complex with S-(p-nitrobenzyl)-glutathione (Nb-GSH) were determined by molecular replacement at 1.6 Å and 1.75 Å, respectively. Major structural variations that affect substrate recognition and catalytic mechanism were revealed in the upper part of helix H4 and helix H9 of GmGSTU10-10. Structural analysis of Sh14 showed that the Trp114Cys point mutation is responsible for the enhanced catalytic activity of the enzyme. Furthermore, two salt bridges that trigger an allosteric effect between the H-sites were identified at the dimer interface between Glu66 and Lys104. The 3D structure of GmGSTU2-2 was predicted using homology modeling. Structural and phylogenetic analysis suggested GmGSTU2-2 shares residues that are crucial for the catalytic activity of other tau class GSTs–Phe10, Trp11, Ser13, Arg20, Tyr30, Leu37, Lys40, Lys53, Ile54, Glu66 and Ser67. This indicates that the catalytic and ligand binding site in GmGSTU2-2 are well-conserved. Nevertheless, at the ligandin binding site a significant variation was observed. Tyr32 is replaced by Ser32 in GmGSTU2-2 and thismay affect the ligand recognition and binding properties of GmGSTU2-2. Moreover, docking studies revealed important amino acid residues in the hydrophobic binding site that can affect the substrate specificity of the enzyme. Phe10, Pro12, Phe15, Leu37, Phe107, Trp114, Trp163, Phe208, Ile212, and Phe216 could form the hydrophobic ligand binding site and bind fluorodifen. Additionally, side chains of Arg111 and Lys215 could stabilize the binding through hydrogen bonds with the –NO2 groups of fluorodifen. GST gene family from the pathogenic soil bacterium Agrobacterium tumefaciens C58 was characterized and eight GST-like proteins in A. tumefaciens (AtuGSTs) were identified. Phylogenetic analysis revealed that four members of AtuGSTs belong to a previously recognized bacterial beta GST class and one member to theta class. Nevertheless, three AtuGSTs do not belong to any previously known GST classes. The 3D structures of AtuGSTs were predicted using homology modeling. Comparative structural and sequence analysis of the AtuGSTs showed local sequence and structural characteristics between different GST isoenzymes and classes. Interactions at the G-site are conserved, however, significant variations were seen at the active site and the H5b helix at the C-terminal domain. H5b contributes to the formation of the hydrophobic ligand binding site and is responsible for recognition of the electrophilic moiety of the xenobiotic. It is noted that the position of H5b varies among models, thus providing different specificities. Moreover, AtuGSTs appear to form functional dimers through diverse modes. AtuGST1, AtuGST3, AtuGST4 and AtuGST8 use hydrophobic ‘lock–and–key’-like motifs whereas the dimer interface of AtuGST2, AtuGST5, AtuGST6 and AtuGST7 is dominated by polar interactions. These results suggested that AtuGSTs could be involved in a broad range of biological functions including stress tolerance and detoxification of toxic compounds.

Quantification of air quality in space and time and its effects on health

The long-term adverse effects on health associated with air pollution exposure can be estimated using either cohort or spatio-temporal ecological designs. In a cohort study, the health status of a cohort of people are assessed periodically over a number of years, and then related to estimated ambient pollution concentrations in the cities in which they live. However, such cohort studies are expensive and time consuming to implement, due to the long-term follow up required for the cohort. Therefore, spatio-temporal ecological studies are also being used to estimate the long-term health effects of air pollution as they are easy to implement due to the routine availability of the required data. Spatio-temporal ecological studies estimate the health impact of air pollution by utilising geographical and temporal contrasts in air pollution and disease risk across $n$ contiguous small-areas, such as census tracts or electoral wards, for multiple time periods. The disease data are counts of the numbers of disease cases occurring in each areal unit and time period, and thus Poisson log-linear models are typically used for the analysis. The linear predictor includes pollutant concentrations and known confounders such as socio-economic deprivation. However, as the disease data typically contain residual spatial or spatio-temporal autocorrelation after the covariate effects have been accounted for, these known covariates are augmented by a set of random effects. One key problem in these studies is estimating spatially representative pollution concentrations in each areal which are typically estimated by applying Kriging to data from a sparse monitoring network, or by computing averages over modelled concentrations (grid level) from an atmospheric dispersion model. The aim of this thesis is to investigate the health effects of long-term exposure to Nitrogen Dioxide (NO2) and Particular matter (PM10) in mainland Scotland, UK. In order to have an initial impression about the air pollution health effects in mainland Scotland, chapter 3 presents a standard epidemiological study using a benchmark method. The remaining main chapters (4, 5, 6) cover the main methodological focus in this thesis which has been threefold: (i) how to better estimate pollution by developing a multivariate spatio-temporal fusion model that relates monitored and modelled pollution data over space, time and pollutant; (ii) how to simultaneously estimate the joint effects of multiple pollutants; and (iii) how to allow for the uncertainty in the estimated pollution concentrations when estimating their health effects. Specifically, chapters 4 and 5 are developed to achieve (i), while chapter 6 focuses on (ii) and (iii). In chapter 4, I propose an integrated model for estimating the long-term health effects of NO2, that fuses modelled and measured pollution data to provide improved predictions of areal level pollution concentrations and hence health effects. The air pollution fusion model proposed is a Bayesian space-time linear regression model for relating the measured concentrations to the modelled concentrations for a single pollutant, whilst allowing for additional covariate information such as site type (e.g. roadside, rural, etc) and temperature. However, it is known that some pollutants might be correlated because they may be generated by common processes or be driven by similar factors such as meteorology. The correlation between pollutants can help to predict one pollutant by borrowing strength from the others. Therefore, in chapter 5, I propose a multi-pollutant model which is a multivariate spatio-temporal fusion model that extends the single pollutant model in chapter 4, which relates monitored and modelled pollution data over space, time and pollutant to predict pollution across mainland Scotland. Considering that we are exposed to multiple pollutants simultaneously because the air we breathe contains a complex mixture of particle and gas phase pollutants, the health effects of exposure to multiple pollutants have been investigated in chapter 6. Therefore, this is a natural extension to the single pollutant health effects in chapter 4. Given NO2 and PM10 are highly correlated (multicollinearity issue) in my data, I first propose a temporally-varying linear model to regress one pollutant (e.g. NO2) against another (e.g. PM10) and then use the residuals in the disease model as well as PM10, thus investigating the health effects of exposure to both pollutants simultaneously. Another issue considered in chapter 6 is to allow for the uncertainty in the estimated pollution concentrations when estimating their health effects. There are in total four approaches being developed to adjust the exposure uncertainty. Finally, chapter 7 summarises the work contained within this thesis and discusses the implications for future research.

On watching rather than reading Count Basil

Compte rendu de la présentation de la pièce « Count Basil » de Joanna Baillie montée par la compagnie Horizon Theatre lors du Congrès 2004 de la North American society for the study of romanticism (NASSR).

Ambient Air Quality Monitoring in Metropolitan City of Lagos, Nigeria

Twenty one sampling locations were assessed for carbon monoxide (CO), carbondioxide (CO2), oxygen (O2), sulphur dioxide (SO2), nitrogen dioxide (NO2), nitrogen oxide (NO), suspended particulate matter (SPM) and noise level using air pollutants measurement methods approved by ASTM for each specific parameter. All equipments and meters were all properly pre-calibrated before each usage for quality assurance. Findings of the study showed that measured levels of noise (61.4 - 101.4 dBA), NO (0.0 - 3.0 ppm), NO2 (0.0 - 3.0 ppm), CO (1.0 – 42.0 ppm) and SPM (0.14 – 4.82 ppm) in all sampling areas were quite high and above regulatory limits however there was no significant difference except in SPM (at all the sampling points), and noise, NO2 and NO (only in major traffic intersection). Air quality index (AQI) indicates that the ambient air can be described as poor for SPM, varied from good to very poor for CO, while NO and NO2 are very good except at major traffic intersection where they were both poor and very poor (D-E). The results suggest that strict and appropriate vehicle emission management, industrial air pollution control coupled with close burning management of wastes should be considered in the study area to reduce the risks associated with these pollutants.

OBSERVATIONS AND EMISSIONS OF ENERGY-ASSOCIATED OZONE PRECURSORS IN THE MID-ATLANTIC UNITED STATES

Surface ozone is formed in the presence of NOx (NO + NO2) and volatile organic compounds (VOCs) and is hazardous to human health. A better understanding of these precursors is needed for developing effective policies to improve air quality. To evaluate the year-to-year changes in source contributions to total VOCs, Positive Matrix Factorization (PMF) was used to perform source apportionment using available hourly observations from June through August at a Photochemical Assessment Monitoring Station (PAMS) in Essex, MD for each year from 2007-2015. Results suggest that while gasoline and vehicle exhaust emissions have fallen, the contribution of natural gas sources to total VOCs has risen. To investigate this increasing natural gas influence, ethane measurements from PAMS sites in Essex, MD and Washington, D.C. were examined. Following a period of decline, daytime ethane concentrations have increased significantly after 2009. This trend appears to be linked with the rapid shale gas production in upwind, neighboring states, especially Pennsylvania and West Virginia. Back-trajectory analyses similarly show that ethane concentrations at these monitors were significantly greater if air parcels had passed through counties containing a high density of unconventional natural gas wells. In addition to VOC emissions, the compressors and engines involved with hydraulic fracturing operations also emit NOx and particulate matter (PM). The Community Multi-scale Air Quality (CMAQ) Model was used to simulate air quality for the Eastern U.S. in 2020, including emissions from shale gas operations in the Appalachian Basin. Predicted concentrations of ozone and PM show the largest decreases when these natural gas resources are hypothetically used to convert coal-fired power plants, despite the increased emissions from hydraulic fracturing operations expanded into all possible shale regions in the Appalachian Basin. While not as clean as burning natural gas, emissions of NOx from coal-fired power plants can be reduced by utilizing post-combustion controls. However, even though capital investment has already been made, these controls are not always operated at optimal rates. CMAQ simulations for the Eastern U.S. in 2018 show ozone concentrations decrease by ~5 ppb when controls on coal-fired power plants limit NOx emissions to historically best rates.

Lixiviação de nitrogênio em Latossolo incubado com lodo de esgoto.

Lodo de esgoto contém teores elevados de N orgânico. Se for aplicado em quantidade excessiva em solos, há risco de poluição de águas subsuperficiais com nitrato, produto da mineralização do N. Por essa razão, um dos critérios agronômicos para a determinação da taxa máxima de aplicação do lodo de esgoto é a quantidade de N mineral que será disponibilizada às culturas. Neste trabalho, são apresentados os resultados relativos à lixiviação de N mineralizado em um Latossolo Vermelho distroférrico incubado durante 224 dias com dois tipos de lodo de esgoto anaeróbios, um de origem urbana (Franca, SP) e outro com presença de despejos industriais (Barueri, SP). Cada lodo de esgoto foi aplicado em quatro doses, contendo 0,13, 0,3, 0,5 e 1,0 g kg-1 de N orgânico. Essa quantidade de substrato mineralizável foi equivalente a 5, 11, 22 e 43 t ha-1 de lodo de Franca, e a 8, 15, 31 e 61 t ha-1 de lodo de Barueri. O experimento foi conduzido em colunas de percolação, sob temperatura de 25 a 28 °C em laboratório, fazendo-se lixiviações com solução extratora de KCl 0,01 mol L-1. Foram determinadas as quantidades de N mineral (N-NH4 + e N-NO3 - + N-NO2 - ) extraídas nos percolados em doze épocas. Houve correlação significativa entre as quantidades aplicadas de N na forma orgânica e as quantidades de N mineralizadas durante a incubação nos dois tipos de lodo avaliados. O potencial de mineralização estimado pelo modelo exponencial simples foi de 73 mg kg-1 de N no solo sem aplicação de lodo, e aumentou de 107 para 224 mg kg-1 e de 132 para 364 mg kg-1 nos tratamentos com o lodo de esgoto de Franca e de Barueri, respectivamente. A fração de mineralização potencial do N orgânico dos dois tipos de lodo de esgoto decresceu com o aumento das doses aplicadas: 26, 25, 21 e 14 % para o de Franca, e 43, 39, 34 e 27 % para o de Barueri. Em consequência, o potencial de lixiviação de N no Latossolo aumentou de 46 para 207 % com as doses do lodo de Franca, e de 81 para 399 % com as doses do lodo de Barueri.

Opportunities for ceria-based mixed oxides versus commercial platinum-based catalysts in the soot combustion reaction. Mechanistic implications

The aim of this paper is to study the activities of ceria–zirconia and copper/ceria–zirconia catalysts, comparing with a commercial platinum/alumina catalyst, for soot combustion reaction under different gas atmospheres and loose contact mode (simulating diesel exhaust conditions), in order to analyse the kinetics and to deduce mechanistic implications. Activity tests were performed under isothermal and TPR conditions. The NO oxidation to NO2 was studied as well. It was checked that mass transfer limitations were not influencing the rate measurements. Global activation energies for the catalysed and non-catalysed soot combustion were calculated and properly discussed. The results reveal that ceria-based catalysts greatly enhance their activities under NOx/O2 between 425 °C and 450 °C, due to the “active oxygen”-assisted soot combustion. Remarkably, copper/ceria–zirconia shows a slightly higher soot combustion rate than the Pt-based catalyst (under NOx/O2, at 450 °C).