Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5

Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM10 and PM2.5 characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650% for PM10, and 720% for PM2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600–21 000% and 5100–20 800% higher than at the reference site for PM10 and PM2.5, respectively, accounting for 49% of total PAH (SPAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300–1300% and 140–1700% higher for PM10 and PM2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780% and 760% in PM10 and PM2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84% and 86% of SPAH in PM10 and PM2.5, respectively, and at the smoking site 56% and 55% of SPAH in PM10 and PM2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health.

Influence of traffic emissions on the carcinogenic polycyclic aromatic hydrocarbons in outdoor breathable particles

Because polycyclic aromatic hydrocarbons (PAHs) have been proven to be toxic, mutagenic, and/or carcinogenic, there is widespread interest in analyzing and evaluating exposure to PAHs in atmospheric environments influenced by different emission sources. Because traffic emissions are one of the biggest sources of fine particles, more information on carcinogenic PAHs associated with fine particles needs to be provided. Aiming to further understand the impact of traffic particulate matter (PM) on human health, this study evaluated the influence of traffic on PM10 (PM with aerodynamic diameter <10 µm) and PM2.5 (PM with aerodynamic diameter <2.5 µm), considering their concentrations and compositions in carcinogenic PAHs. Samples were collected at one site influenced by traffic emissions and at one reference site using lowvolume samplers. Analysis of PAHs was performed by microwave-assisted extraction combined with liquid chromatography (MAE-LC); 17 PAHs, including 9 carcinogenic ones, were quantified. At the site influenced by traffic emissions, PM10 and PM2.5 concentrations were, respectively, 380 and 390% higher than at the background site. When influenced by traffic emissions, the total concentration of nine carcinogenic compounds (naphthalene, chrysene, benzo(a)anthracene, benzo(b) fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and dibenzo(a,l)pyrene) was increased by 2400 and 3000% in PM10 and PM2.5, respectively; these nine carcinogenic compounds represented 68 and 74% of total PAHs (ƩPAHs) for PM10 and PM2.5, respectively. All PAHs, including the carcinogenic compounds, were mainly present in fine particles. Considering the strong influence of these fine particles on human health, these conclusions are relevant for the development of strategies to protect public health.

Impact of vehicular traffic emissions on particulate-bound PAHs: levels and associated health risks

Considering vehicular transport as one of the most health‐relevant emission sources of urban air, and with aim to further understand its negative impact on human health, the objective of this work was to study its influence on levels of particulate‐bound PAHs and to evaluate associated health risks. The 16 PAHs considered by USEPA as priority pollutants, and dibenzo[a, l]pyrene associated with fine (PM2.5) and coarse (PM2.5–10) particles were determined. The samples were collected at one urban site, as well as at a reference place for comparison. The results showed that the air of the urban site was more seriously polluted than at the reference one, with total concentrations of 17 PAHs being 2240% and 640% higher for PM2.5 and PM2.5–10, respectively; vehicular traffic was the major emission source at the urban site. PAHs were predominantly associated with PM2.5 (83% to 94% of ΣPAHs at urban and reference site, respectively) with 5 rings PAHs being the most abundant groups of compounds at both sites. The risks associated with exposure to particulate PAHs were evaluated using the TEF approach. The estimated value of lifetime lung cancer risks exceeded the health‐based guideline levels, thus demonstrating that exposure to PM2.5‐bound PAHs at levels found at urban site might cause potential health risks. Furthermore, the results showed that evaluation of benzo[a] pyrene (regarded as a marker of the genotoxic and carcinogenic PAHs) alone would probably underestimate the carcinogenic potential of the studied PAH mixtures.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Impact of urban atmospheric environment on hospital admissions in the elderly

OBJECTIVE: To analyze the impact of intra-urban atmospheric conditions on circulatory and respiratory diseases in elder adults. METHODS: Cross-sectional study based on data from 33,212 hospital admissions in adults over 60 years in the city of São Paulo, southeastern Brazil, from 2003 to 2007. The association between atmospheric variables from Congonhas airport and bioclimatic index, Physiological Equivalent Temperature, was analyzed according to the district's socioenvironmental profile. Descriptive statistical analysis and regression models were used. RESULTS: There was an increase in hospital admissions due to circulatory diseases as average and lowest temperatures decreased. The likelihood of being admitted to the hospital increased by 12% with 1ºC decrease in the bioclimatic index and with 1ºC increase in the highest temperatures in the group with lower socioenvironmental conditions. The risk of admission due to respiratory diseases increased with inadequate air quality in districts with higher socioenvironmental conditions. CONCLUSIONS: The associations between morbidity and climate variables and the comfort index varied in different groups and diseases. Lower and higher temperatures increased the risk of hospital admission in the elderly. Districts with lower socioenvironmental conditions showed greater adverse health impacts.

Análise do sistema de tratamento de efluentes gasosos de uma central de valorização energética de resíduos sólidos urbanos

Trabalho Final de Mestrado para obtenção do grau de Mestre Em Engenharia Química e Biológica Ramo de processos Químicos

Spinning reserve and emission unit commitment through stochastic optimization

This paper proposes a stochastic mixed-integer linear approach to deal with a short-term unit commitment problem with uncertainty on a deregulated electricity market that includes day-ahead bidding and bilateral contracts. The proposed approach considers the typically operation constraints on the thermal units and a spinning reserve. The uncertainty is due to the electricity prices, which are modeled by a scenario set, allowing an acceptable computation. Moreover, emission allowances are considered in a manner to allow for the consideration of environmental constraints. A case study to illustrate the usefulness of the proposed approach is presented and an assessment of the cost for the spinning reserve is obtained by a comparison between the situation with and without spinning reserve.

Matching CO2 large point sources and potential geological storage sites in mainland Portugal

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, Perfil Gestão e Sistemas Ambientais

Spinning reserve and emission unit commitment through stochastic optimization

This paper proposes a stochastic mixed-integer linear approach to deal with a short-term unit commitment problem with uncertainty on a deregulated electricity market that includes day-ahead bidding and bilateral contracts. The proposed approach considers the typically operation constraints on the thermal units and a spinning reserve. The uncertainty is due to the electricity prices, which are modeled by a scenario set, allowing an acceptable computation. Moreover, emission allowances are considered in a manner to allow for the consideration of environmental constraints. A case study to illustrate the usefulness of the proposed approach is presented and an assessment of the cost for the spinning reserve is obtained by a comparison between the situation with and without spinning reserve.

The effect of metal transfer modes and shielding gas composition on the emission of ultraafine particles in MAG steel welding

The present study aims to characterize ultrafine particles emitted during gas metal arc welding of mild steel and stainless steel, using different shielding gas mixtures, and to evaluate the effect of metal transfer modes, controlled by both processing parameters and shielding gas composition, on the quantity and morphology of the ultrafine particles. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the main welding parameters, namely the current intensity and the heat input of the Welding process. The emission of airborne ultrafine particles increases with the current intensity as fume formation rate does. When comparing the shielding gas mixtures, higher emissions were observed for more oxidizing mixtures, that is, with higher CO2 content, which means that these mixtures originate higher concentrations of ultrafine particles (as measured by number of particles. by cubic centimeter of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding welders exposure.

Emission of airborne ultrafine particles during welding of steel plates

The present study is focused on the characterization of ultrafine particles emitted in welding of steel using mixtures of Ar+CO2, and intends to analyze which are the main process parameters which may have influence on the emission itself. It was found that the amount of emitted ultrafine particles (measured by particle number and alveolar deposited surface area) are clearly dependent from the distance to the welding front and also from the main welding parameters, namely the current intensity and heat input in the welding process. The emission of airborne ultrafine particles seem to increase with the current intensity as fume formation rate does. When comparing the tested gas mixtures, higher emissions are observed for more oxidant mixtures, that is, mixtures with higher CO2 content, which result in higher arc stability. The later mixtures originate higher concentrations of ultrafine particles (as measured by number of particles by cm3 of air) and higher values of alveolar deposited surface area of particles, thus resulting in a more hazardous condition regarding worker's exposure. © 2014 Sociedade Portuguesa de Materiais (SPM). Published by Elsevier España, S.L. All rights reserved.

Budget impact from the incorporation of positron emission tomography – computed tomography for staging lung cancers

OBJECTIVE To estimate the budget impact from the incorporation of positron emission tomography (PET) in mediastinal and distant staging of non-small cell lung cancer.METHODS The estimates were calculated by the epidemiological method for years 2014 to 2018. Nation-wide data were used about the incidence; data on distribution of the disease´s prevalence and on the technologies’ accuracy were from the literature; data regarding involved costs were taken from a micro-costing study and from Brazilian Unified Health System (SUS) database. Two strategies for using PET were analyzed: the offer to all newly-diagnosed patients, and the restricted offer to the ones who had negative results in previous computed tomography (CT) exams. Univariate and extreme scenarios sensitivity analyses were conducted to evaluate the influence from sources of uncertainties in the parameters used.RESULTS The incorporation of PET-CT in SUS would imply the need for additional resources of 158.1 BRL (98.2 USD) million for the restricted offer and 202.7 BRL (125.9 USD) million for the inclusive offer in five years, with a difference of 44.6 BRL (27.7 USD) million between the two offer strategies within that period. In absolute terms, the total budget impact from its incorporation in SUS, in five years, would be 555 BRL (345 USD) and 600 BRL (372.8 USD) million, respectively. The costs from the PET-CT procedure were the most influential parameter in the results. In the most optimistic scenario, the additional budget impact would be reduced to 86.9 BRL (54 USD) and 103.8 BRL (64.5 USD) million, considering PET-CT for negative CT and PET-CT for all, respectively.CONCLUSIONS The incorporation of PET in the clinical staging of non-small cell lung cancer seems to be financially feasible considering the high budget of the Brazilian Ministry of Health. The potential reduction in the number of unnecessary surgeries may cause the available resources to be more efficiently allocated.

Implementation of a new reference values database for semiquantification in123I-FP-CIT brain single emission tomography

Brain dopamine transporters imaging by Single Emission Tomography (SPECT) with 123I-FP-CIT (DaTScanTM) has become an important tool in the diagnosis and evaluation of Parkinson syndromes.This diagnostic method allows the visualization of a portion of the striatum – where healthy pattern resemble two symmetric commas - allowing the evaluation of dopamine presynaptic system, in which dopamine transporters are responsible for dopamine release into the synaptic cleft, and their reabsorption into the nigrostriatal nerve terminals, in order to be stored or degraded. In daily practice for assessment of DaTScan TM, it is common to rely only on visual assessment for diagnosis. However, this process is complex and subjective as it depends on the observer’s experience and it is associated with high variability intra and inter observer. Studies have shown that semiquantification can improve the diagnosis of Parkinson syndromes. For semiquantification, analysis methods of image segmentation using regions of interest (ROI) are necessary. ROIs are drawn, in specific - striatum - and in nonspecific – background – uptake areas. Subsequently, specific binding ratios are calculated. Low adherence of semiquantification for diagnosis of Parkinson syndromes is related, not only with the associated time spent, but also with the need of an adapted database of reference values for the population concerned, as well as, the examination of each service protocol. Studies have concluded, that this process increases the reproducibility of semiquantification. The aim of this investigation was to create and validate a database of healthy controls for Dopamine transporters with DaTScanTM named DBRV. The created database has been adapted to the Nuclear Medicine Department’s protocol, and the population of Infanta Cristina’s Hospital located in Badajoz, Spain.

Development of procedures for the simulation of atmospheric flows over complex terrain, using OpenFOAM

The main purpose of this work was the development of procedures for the simulation of atmospheric ows over complex terrain, using OpenFOAM. For this aim, tools and procedures were developed apart from this code for the preprocessing and data extraction, which were thereafter applied in the simulation of a real case. For the generation of the computational domain, a systematic method able to translate the terrain elevation model to a native OpenFOAM format (blockMeshDict) was developed. The outcome was a structured mesh, in which the user has the ability to de ne the number of control volumes and its dimensions. With this procedure, the di culties of case set up and the high computation computational e ort reported in literature associated to the use of snappyHexMesh, the OpenFOAM resource explored until then for the accomplishment of this task, were considered to be overwhelmed. Developed procedures for the generation of boundary conditions allowed for the automatic creation of idealized inlet vertical pro les, de nition of wall functions boundary conditions and the calculation of internal eld rst guesses for the iterative solution process, having as input experimental data supplied by the user. The applicability of the generated boundary conditions was limited to the simulation of turbulent, steady-state, incompressible and neutrally strati ed atmospheric ows, always recurring to RaNS (Reynolds-averaged Navier-Stokes) models. For the modelling of terrain roughness, the developed procedure allowed to the user the de nition of idealized conditions, like an uniform aerodynamic roughness length or making its value variable as a function of topography characteristic values, or the using of real site data, and it was complemented by the development of techniques for the visual inspection of generated roughness maps. The absence and the non inclusion of a forest canopy model limited the applicability of this procedure to low aerodynamic roughness lengths. The developed tools and procedures were then applied in the simulation of a neutrally strati ed atmospheric ow over the Askervein hill. In the performed simulations was evaluated the solution sensibility to di erent convection schemes, mesh dimensions, ground roughness and formulations of the k - ε and k - ω models. When compared to experimental data, calculated values showed a good agreement of speed-up in hill top and lee side, with a relative error of less than 10% at a height of 10 m above ground level. Turbulent kinetic energy was considered to be well simulated in the hill windward and hill top, and grossly predicted in the lee side, where a zone of ow separation was also identi ed. Despite the need of more work to evaluate the importance of the downstream recirculation zone in the quality of gathered results, the agreement between the calculated and experimental values and the OpenFOAM sensibility to the tested parameters were considered to be generally in line with the simulations presented in the reviewed bibliographic sources.