Análise de compostos orgânicos voláteis (BTEX) no ar da Cidade de Évora

A poluição atmosférica é um dos principais factores de degradação da qualidade de vida da população. O conjunto BTEX (benzeno, tolueno, etilbenzeno e xilenos) constitui o grupo mais importante dos compostos orgânicos voláteis (VOCs) na atmosfera uma vez que participam na química da atmosfera e constituem um perigo para a saúde, nomeadamente o benzeno, por ser altamente cancerígeno. São maioritariamente libertados pelo tráfego automóvel. Neste trabalho foi determinada a concentração dos BTEX em nove pontos da cidade de Évora no período de 21 Março a 1 de Julho de 2009 tendo-se recorrido à técnica de amostragem passiva, com amostradores Radiello™, seguida de desadsorção líquida, usando CS2, e subsequente análise por GC-MS. A concentração de benzeno no ar da cidade de Évora não excedeu o valor legislado de 5 g/m3 neste período de amostragem, sendo as concentrações obtidas para os poluentes em geral muito baixas e na sua maioria inferiores ao LOQ do método analítico. ABSTRACT; Air pollution is the major factor in the degradation of the population quality of life. BTEX (benzene, toluene, ethylbenzene and xylenes) is the most important group of volatile organic compounds (VOCs) in the atmosphere because of their role in atmospheric chemistry and the risk they posed to human health, with benzene, being a highly carcinogenic compound. BTEX are released mainly by road traffic. Concentrations of BTEX were determined at nine sampling points in the city of Évora in the period from 21 March to 1 July 2009, using passive samplers Radiello™, followed by liquid desorption with CS2, and subsequent analysis by GC-MS. During the sampling period, the concentration of benzene in the outdoor air of Évora city did not exceed 5 g/m3, the maximum value admissible by legislation. The concentrations measured of the other pollutants were, in general, very low and mostly below the LOQ of the analytical method.

In vivo microvascular oximetry using multispectral imaging

This thesis describes the application of multispectral imaging to several novel oximetry applications. Chapter 1 motivates optical microvascular oximetry, outlines oxygen transport in the body, describes the theory of oximetry, and describes the challenges associated with in vivo oximetry, in particular imaging through tissue. Chapter 2 reviews various imaging techniques for quantitative in vivo oximetry of the microvasculature, including multispectral and hyperspectral imaging, photoacoustic imaging, optical coherence tomography, and laser speckle techniques. Chapter 3 describes a two-wavelength oximetry study of two microvascular beds in the anterior segment of the eye: the bulbar conjunctival and episcleral microvasculature. This study reveals previously unseen oxygen diffusion from ambient air into the bulbar conjunctival microvasculature, altering the oxygen saturation of the bulbar conjunctiva. The response of the bulbar conjunctival and episcleral microvascular beds to acute mild hypoxia is quantified and the rate at which oxygen diffuses into bulbar conjunctival vessels is measured. Chapter 4 describes the development and application of a highly novel non-invasive retinal angiography technique: Oximetric Ratio Contrast Angiography (ORCA). ORCA requires only multispectral imaging and a small perturbation of blood oxygen saturation to produce angiographic sequences. A pilot study of ORCA in human subjects was conducted. This study demonstrates that ORCA can produce angiographic sequences with features such as sequential vessel filling and laminar flow. The application and challenges of ORCA are discussed, with emphasis on comparison with other angiography techniques, such as fluorescein angiography. Chapter 5 describes the development of a multispectral microscope for oximetry in the spinal cord dorsal vein of rats. Measurements of blood oxygen saturation are made in the dorsal vein of both healthy rats, and in rats with the Experimental autoimmune encephalomyelitis (EAE) disease model of multiple sclerosis. The venous blood oxygen saturation of EAE disease model rats was found to be significantly lower than that of healthy controls, indicating increased oxygen uptake from blood in the EAE disease model of multiple sclerosis. Chapter 6 describes the development of video-rate red eye oximetry; a technique which could enable stand-off oximetry of the blood-supply of the eye with high temporal resolution. The various challenges associated with video-rate red eye oximetry are investigated and their influence quantified. The eventual aim of this research is to track circulating deoxygenation perturbations as they arrive in both eyes, which could provide a screening method for carotid artery stenosis, which is major risk-factor for stroke. However, due to time constraints, it was not possible to thoroughly investigate if video-rate red eye can detect such perturbations. Directions and recommendations for future research are outlined.

RELATIONSHIP BETWEEN COLUMN DENSITY AND SURFACE MIXING RATIO FOR O3 AND NO2: IMPLICATIONS FOR SATELLITE OBSERVATIONS AND THE IMPACTS OF VERTICAL MIXING

Satellites have great potential for diagnosis of surface air quality conditions, though reduced sensitivity of satellite instrumentation to the lower troposphere currently impedes their applicability. One objective of the NASA DISCOVER-AQ project is to provide information relevant to improving our ability to relate satellite-observed columns to surface conditions for key trace gases and aerosols. In support of DISCOVER-AQ, this dissertation investigates the degree of correlation between O3 and NO2 column abundance and surface mixing ratio during the four DISCOVER-AQ deployments; characterize the variability of the aircraft in situ and model-simulated O3 and NO2 profiles; and use the WRF-Chem model to further investigate the role of boundary layer mixing in the column-surface connection for the Maryland 2011 deployment, and determine which of the available boundary layer schemes best captures the observations. Simple linear regression analyses suggest that O3 partial column observations from future satellite instruments with sufficient sensitivity to the lower troposphere may be most meaningful for surface air quality under the conditions associated with the Maryland 2011 campaign, which included generally deep, convective boundary layers, the least wind shear of all four deployments, and few geographical influences on local meteorology, with exception of bay breezes. Hierarchical clustering analysis of the in situ O3 and NO2 profiles indicate that the degree of vertical mixing (defined by temperature lapse rate) associated with each cluster exerted an important influence on the shapes of the median cluster profiles for O3, as well as impacted the column vs. surface correlations for many clusters for both O3 and NO2. However, comparisons to the CMAQ model suggest that, among other errors, vertical mixing is overestimated, causing too great a column-surface connection within the model. Finally, the WRF-Chem model, a meteorology model with coupled chemistry, is used to further investigate the impact of vertical mixing on the O3 and NO2 column-surface connection, for an ozone pollution event that occurred on July 26-29, 2011. Five PBL schemes were tested, with no one scheme producing a clear, consistent “best” comparison with the observations for PBLH and pollutant profiles; however, despite improvements, the ACM2 scheme continues to overestimate vertical mixing.

Sensoriamento remoto a laser de aerossóis em uma refinaria de petróleo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Die mißverstandene Krise. Theoriedefizite in der umweltpädagogischen Kommunikation

Der Beitrag stellt den Versuch dar, unzureichende Annahmen über Mensch und Gesellschaft in der umweltpädagogischen Literatur zu identifizieren und zur Diskussion zu stellen. Dazu bietet der Verfasser zunächst einen Reflexionsrahmen an, der am Beispiel der Aufstellung einer Prioritätenliste für Maßnahmen gegen die Luftverschmutzung auf die Schwierigkeiten aufmerksam machen soll, die auftreten, wenn man sich in einer als Ganzes nicht überschaubaren Gesellschaft um Verständigung über die Umweltkrise bemüht. Danach analysiert der Verfasser einige in der umweltpädagogischen Literatur verbreitete Stellungnahmen zur Beschreibung, Erklärung und Eindämmung der Umweltkrise. Er kommt zu dem Ergebnis, daß Ignoranz gegenüber den Verständigungsschwierigkeiten über die Umweltkrise fundamentalistischen Behauptungen über Menschen und Gesellschaft in der umweltpädagogischen Literatur Vorschub leistet. (DIPF/Orig.)

THE INFLUENCE OF URBAN FORM AT DIFFERENT GEOGRAPHICAL SCALES ON TRAVEL BEHAVIOR; EVIDENCE FROM U.S. CITIES

Suburban lifestyle is popular among American families, although it has been criticized for encouraging automobile use through longer commutes, causing heavy traffic congestion, and destroying open spaces (Handy, 2005). It is a serious concern that people living in low-density suburban areas suffer from high automobile dependency and lower rates of daily physical activity, both of which result in social, environmental and health-related costs. In response to such concerns, researchers have investigated the inter-relationships between urban land-use pattern and travel behavior within the last few decades and suggested that land-use planning can play a significant role in changing travel behavior in the long-term. However, debates regarding the magnitude and efficiency of the effects of land-use on travel patterns have been contentious over the years. Changes in built-environment patterns is potentially considered a long-term panacea for automobile dependency and traffic congestion, despite some researchers arguing that the effects of land-use on travel behavior are minor, if any. It is still not clear why the estimated impact is different in urban areas and how effective a proposed land-use change/policy is in changing certain travel behavior. This knowledge gap has made it difficult for decision-makers to evaluate land-use plans and policies. In addition, little is known about the influence of the large-scale built environment. In the present dissertation, advanced spatial-statistical tools have been employed to better understand and analyze these impacts at different scales, along with analyzing transit-oriented development policy at both small and large scales. The objective of this research is to: (1) develop scalable and consistent measures of the overall physical form of metropolitan areas; (2) re-examine the effects of built-environment factors at different hierarchical scales on travel behavior, and, in particular, on vehicle miles traveled (VMT) and car ownership; and (3) investigate the effects of transit-oriented development on travel behavior. The findings show that changes in built-environment at both local and regional levels could be very influential in changing travel behavior. Specifically, the promotion of compact, mixed-use built environment with well-connected street networks reduces VMT and car ownership, resulting in less traffic congestion, air pollution, and energy consumption.

Determinação de mercúrio total no material particulado atmosférico do Distrito Federal, Brasil

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Tecnologia Química e Biológica, 2016.

Passivo ambiental: estudo de caso

Dissertação apresentada para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Contabilidade e Finanças

Mercury in Gas Operations - Occupational Health Risk Assessment

The project goal was to determine plant operations and maintenance worker’s level of exposure to mercury during routine and non-routine (i.e. turnarounds and inspections) maintenance events in eight gas processing plants. The project team prepared sampling and analysis plans designed to each plant’s process design and scheduled maintenance events. Occupational exposure sampling and monitoring efforts were focused on the measurement of mercury vapor concentration in worker breathing zone air during specific maintenance events including: pipe scrapping, process filter replacement, and process vessel inspection. Similar exposure groups were identified and worker breathing zone and ambient air samples were collected and analyzed for total mercury. Occupational exposure measurement techniques included portable field monitoring instruments, standard passive and active monitoring methods and an emerging passive absorption technology. Process sampling campaigns were focused on inlet gas streams, mercury removal unit outlets, treated gas, acid gas and sales gas. The results were used to identify process areas with increased potential for mercury exposure during maintenance events. Sampling methods used for the determination of total mercury in gas phase streams were based on the USEPA Methods 30B and EPA 1631 and EPA 1669. The results of four six-week long sampling campaigns have been evaluated and some conclusions and recommendations have been made. The author’s role in this project included the direction of all field phases of the project and the development and implementation of the sampling strategy. Additionally, the author participated in the development and implementation of the Quality Assurance Project Plan, Data Quality Objectives, and Similar Exposure Groups identification. All field generated data was reviewed by the author along with laboratory reports in order to generate conclusions and recommendations.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Evaluation of isoprene degradation in the detailed tropospheric chemical mechanism, MCM v3, using environmental chamber data

The isoprene degradation mechanism included in version 3 of the Master Chemical Mechanism (MCM v3) has been evaluated and refined, using the Statewide Air Pollution Research Center (SAPRC) environmental chamber datasets on the photo-oxidation of isoprene and its degradation products, methacrolein (MACR) and methylvinyl ketone (MVK). Prior to this, the MCM v3 butane degradation chemistry was also evaluated using chamber data on the photo-oxidation of butane, and its degradation products, methylethyl ketone (MEK), acetaldehyde (CH3CHO) and formaldehyde (HCHO), in conjunction with an initial evaluation of the chamber-dependent auxiliary mechanisms for the series of relevant chambers. The MCM v3 mechanisms for both isoprene and butane generally performed well and were found to provide an acceptable reaction framework for describing the NOx-photo-oxidation experiments on the above systems, although a number of parameter modifications and refinements were identified which resulted in an improved performance. All these relate to the magnitude of sources of free radicals from organic chemical process, such as carbonyl photolysis rates and the yields of radicals from the reactions of O3 with unsaturated oxygenates, and specific recommendations are made for refinements. In addition to this, it was necessary to include a representation of the reactions of O(3P) with isoprene, MACR and MVK (which were not previously treated in MCM v3), and conclusions are drawn concerning the required extent of free radical formation from these reactions. Throughout the study, the performance of MCM v3 was also compared with that of the SAPRC-99 mechanism, which was developed and optimized in conjunction with the chamber datasets.

Evaluation of alkene degradation in the detailed tropospheric chemistry mechanism, MCM v3, using environmental chamber data

The representation of alkene degradation in version 3 of the Master Chemical Mechanism (MCM v3) has been evaluated, using environmental chamber data on the photo-oxidation of ethene, propene, 1-butene and 1-hexene in the presence of NOx, from up to five chambers at the Statewide Air Pollution Research Center (SAPRC) at the University of California. As part of this evaluation, it was necessary to include a representation of the reactions of the alkenes with O(3P), which are significant under chamber conditions but generally insignificant under atmospheric conditions. The simulations for the ethene and propene systems, in particular, were found to be sensitive to the branching ratios assigned to molecular and free radical forming pathways of the O(3P) reactions, with the extent of radical formation required for proper fitting of the model to the chamber data being substantially lower than the reported consensus. With this constraint, the MCM v3 mechanisms for ethene and propene generally performed well. The sensitivity of the simulations to the parameters applied to a series of other radical sources and sink reactions (radical formation from the alkene ozonolysis reactions and product carbonyl photolysis; radical removal from the reaction of OH with NO2 and β-hydroxynitrate formation) were also considered, and the implications of these results are discussed. Evaluation of the MCM v3 1-butene and 1-hexene degradation mechanisms, using a more limited dataset from only one chamber, was found to be inconclusive. The results of sensitivity studies demonstrate that it is impossible to reconcile the simulated and observed formation of ozone in these systems for ranges of parameter values which can currently be justified on the basis of the literature. As a result of this work, gaps and uncertainties in the kinetic, mechanistic and chamber database are identified and discussed, in relation to both tropospheric chemistry and chemistry important under chamber conditions which may compromise the evaluation procedure, and recommendations are made for future experimental studies. Throughout the study, the performance of the MCM v3 chemistry was also simultaneously compared with that of the corresponding chemistry in the SAPRC-99 mechanism, which was developed and optimized in conjunction with the chamber datasets.

INDOOR MOLD After a Severe Weather Event

Many South Carolina residents are concerned about indoor mold after severe weather events. DHEC has compiled this informational handout with recommendations to guide decisions regarding mold in homes and workplaces.

Protecting yourself from wildfire smoke

The South Carolina Department of Health and Environmental Control has declared an air quality alert day for fine particulates, caused by smoke from widespread forest fires. This sheet gives seven tips for protecting yourself from wildfire smoke.