Air pollution from traffic emissions in Oporto, Portugal: health and environmental implications

Air pollution represents a serious risk not only to environment and human health, but also to historical heritage. In this study, air pollution of the Oporto Metropolitan Area and its main impacts were characterized. The results showed that levels of CO, PM10 and SO2 have been continuously decreasing in the respective metropolitan area while levels of NOx and NO2 have not changed significantly. Traffic emissions were the main source of the determined polycyclic aromatic hydrocarbons (PAHs; 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in air of the respective metropolitan area. The mean concentration of 18 PAHs in air was 69.9��39.7 ng m���3 with 3���4 rings PAHs accounting for 75% of the total ��PAHs. The health risk analysis of PAHs in air showed that the estimated values of lifetime lung cancer risks considerably exceeded the health-based guideline level. Analytical results also confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. FTIR and EDX analyses showed that gypsum was the most important constituent of black crusts of the characterized historical monument Monastery of Serra do Pilar classified as ���UNESCO World Cultural Heritage���. In black crusts, 4���6 rings compounds accounted approximately for 85% of ��PAHs. The diagnostic ratios confirmed that traffic emissions were the major source of PAHs in black crusts; PAH composition profiles were very similar for crusts and PM10 and PM2.5.

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM10 and PM2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO2, PM10, NO2, CO, and O3; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ngm���3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10���6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98��10���7 in PM10 and 1.06��10���6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO2, NO2, PM10, CO, and solar radiation had positive correlation with PAHs concentrations, while O3, temperature, relative humidity, and wind speed were negatively correlated.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in fa��ades 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 fa��ades 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 fa��ades of two historical monuments: Hospital Santo Ant��nio 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 ��m 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 Ant��nio, 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 ��PAHs. 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 fa��ades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Exposure to polycyclic aromatic hydrocarbons and assessment of potential risks in preschool children

As children represent one of the most vulnerable groups in society, more information concerning their exposure to health hazardous air pollutants in school environments is necessary. Polycyclic aromatic hydrocarbons (PAHs) have been identified as priority air pollutants due to their mutagenic and carcinogenic properties that strongly affect human health. Thus, this work aims to characterize levels of 18 selected PAHs in preschool environment, and to estimate exposure and assess the respective risks for 3���5-year-old children (in comparison with adults). Gaseous PAHs (mean of 44.5��������12.3 ng m���3) accounted for 87 % of the total concentration (��PAHs) with 3���ringed compounds being the most abundant (66 % of gaseous ��PAHs). PAHs with 5 rings were the most abundant ones in the particulate phase (PM; mean of 6.89��������2.85 ng m���3) being predominantly found in PM1 (78 % particulate ��PAHs). Overall child exposures to PAHs were not significantly different between older children (4���5 years old) and younger ones (3 years old). Total carcinogenic risks due to particulate-bound PAHs indoors were higher than outdoor ones. The estimated cancer risks of both preschool children and the staff were lower than the United States Environmental Protection Agency (USEPA) threshold of 10���6 but slightly higher than WHO-based guideline.

Numerical solution of a PDE system with non-linear steady state conditions that translates the air stripping pollutants removal

This work deals with the numerical simulation of air stripping process for the pre-treatment of groundwater used in human consumption. The model established in steady state presents an exponential solution that is used, together with the Tau Method, to get a spectral approach of the solution of the system of partial differential equations associated to the model in transient state.

Spectral solution for the air stripping pollutants removal dynamic model with non linear steady state conditions

This work deals with the numerical simulation of air stripping process for the pre-treatment of groundwater used in human consumption. The model established in steady state presents an exponential solution that is used, together with the Tau Method, to get a spectral approach of the solution of the system of partial differential equations associated to the model in transient state.

Biofiltration of Air/Styrene and Air/Styrene/Acetone mixtures in a bubble column reactor

The goal of this work was the treatment of polluted waste gases in a bubble column reactor (BCR), in order to determinate the maximum value of reactor���s efficiency (RE), varying the inlet concentration (C in) of the pollutants. The gaseous mixtures studied were: (i) air with styrene and (ii) air with styrene and acetone. The liquid phase used to contain the biomass in the reactor was a basal salt medium (BSM), fundamental for the microorganisms��� development. The reactor used in this project consists of a glass column of 620mm height and inside diameter 75mm. In all essays there were continually measured: pH, dissolved oxygen and liquid���s temperature. Temperature and pH were controlled (T=24��C, 7.0 ��� pH ��� 7.7). In all experiments the liquid volume (including the biomass) used in the reactor was kept constant (1.5L) as well as the total gas flowrate (1 L/min). Concerning the goal of the work, some parameters were calculated: the organic load (OL), removal efficiency (RE), elimination capacity (EC), biomass concentration (xf) and dry biomass concentration (Xdw). In a first series of experiments, the gas mixture used was air with styrene, varying its concentration from 191 mg.m-3 to 6500 mg.m-3.It was concluded that the RE maximum value (97%) was obtained for C in Sty = 4200 mg.m-3. For the maximum tested value of C in Sty, RE obtained was 20%. In a second step, the gaseous mixture included acetone, varying C in Sty between 225 mg.m-3 and 2659 mg.m-3 and C in Ac between 153mg.m-3 and 1389 mg.m-3. The aim of these tests was the determination of C in Ac for which RE was maximum, obtaining C in Ac = 750 mg.m-3. A third series of experiments was performed, in which C in Ac was maintained equal to that value and C in Sty was varied until higher values (5422 mg.m-3). RE maximum values obtained in this last series were 100% for styrene and 40% for acetone. One important conclusion is the fact that the microorganisms available degrade better styrene than acetone. On the ambit of this study, it was possible to identify the species available in biomass: Xanthobacter antotrophicus py2, Enterobacter aerogenes, Nocardia, Corynebacterium Spp., Rhodococcus rhodochrous e Pseudomonas Sp.

Ultrafine Particles in Ambient Air of an Urban Area: Dose Implications for Elderly

Due to their detrimental effects on human health, the scientific interest in ultrafine particles (UFP) has been increasing, but available information is far from comprehensive. Compared to the remaining population, the elderly are potentially highly susceptible to the effects of outdoor air pollution. Thus, this study aimed to (1) determine the levels of outdoor pollutants in an urban area with emphasis on UFP concentrations and (2) estimate the respective dose rates of exposure for elderly populations. UFP were continuously measured over 3 weeks at 3 sites in north Portugal: 2 urban (U1 and U2) and 1 rural used as reference (R1). Meteorological parameters and outdoor pollutants including particulate matter (PM10), ozone (O3), nitric oxide (NO), and nitrogen dioxide (NO2) were also measured. The dose rates of inhalation exposure to UFP were estimated for three different elderly age categories: 64���70, 71���80, and >81 years. Over the sampling period levels of PM10, O3 and NO2 were in compliance with European legislation. Mean UFP were 1.7 �� 104 and 1.2 �� 104 particles/cm3 at U1 and U2, respectively, whereas at rural site levels were 20���70% lower (mean of 1 ��104 particles/cm3). Vehicular traffic and local emissions were the predominant identified sources of UFP at urban sites. In addition, results of correlation analysis showed that UFP were meteorologically dependent. Exposure dose rates were 1.2- to 1.4-fold higher at urban than reference sites with the highest levels noted for adults at 71���80 yr, attributed mainly to higher inhalation rates.

Modela����o do transporte e dispers��o atmosf��rica de poluentes produzidos por uma refinaria: estudo de caso

Mestrado em Engenharia Qu��mica.Ramo Tecnologias de Protec����o Ambiental

Avalia����o da qualidade do ar interior e estudos CFD em espa��os do ISEP

Mestrado em Engenharia Qu��mica. Ramo Tecnologias de Protec����o Ambiental.

Remedia����o de solos contaminados com produtos farmac��uticos ��� oxida����o / redu����o qu��mica

Actualmente, a polui����o do ar, ��gua e solo s��o problem��ticas nas quais se t��m centrado diversos estudos. Reduzir ou eliminar a concentra����o dos diversos poluentes presentes nestes meios �� uma meta que se pretende atingir. Neste ��mbito, t��m sido desenvolvidos diversos estudos e trabalhos, utilizando diversas tecnologias, como qu��micas e biol��gicas, de forma a conseguir-se atingir este fim. Esta tese teve como principal objectivo estudar a remedia����o de solos contaminados com produtos farmac��uticos recorrendo �� oxida����o/redu����o qu��mica. Assim, come��ou por se estudar a remedia����o de ��gua contaminada com ibuprofeno, uma vez, que a matriz l��quida �� mais f��cil de estudar que o solo. Neste ��mbito escolheram-se os seguintes reagentes para estudar a descontamina����o da ��gua: permanganato de pot��ssio, reagente de Fenton e nanopart��culas de ferro zero valente. Analisando os resultados obtidos nestas an��lises, verificou-se que o permanganato de pot��ssio n��o foi capaz de reduzir a concentra����o de ibuprofeno presente na ��gua. No entanto, o reagente de Fenton e as nanopart��culas produzidas a partir do extracto da casca de castanha e do ch�� conseguirem reagir com o ibuprofeno, apresentando taxas de degrada����o de 90 % e 77 %, respectivamente, nas melhores condi����es experimentadas. Com os resultados obtidos, passou-se a analisar solos contaminados com o ibuprofeno, utilizando o reagente de Fenton e as nanopart��culas produzidas a partir de um extracto de ch��. Verificou-se que estes reagentes conseguiram reduzir a concentra����o de ibuprofeno presente no solo (areia) para valores residuais, obtendo-se taxas de degrada����o acima de 95 % ap��s 5 dias de reac����o. Conclui-se que, o objectivo principal desta tese foi cumprido pois foi reduzida, e quase eliminada, a concentra����o do ibuprofeno presente no solo, recorrendo �� oxida����o/redu����o qu��mica.

Contribution of traffic and tobacco smoke in the distribution of polycyclic aromatic hydrocarbons on outdoor and indoor PM2.5

Traffic emissions and tobacco smoke are considered two main sources of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air. In this study, the impact of these sources on the level of fine particulate matter (PM2.5) and on the distribution of 15 PAHs regarded as priority pollutants by the US-EPA on PM2.5 were evaluated and compared. Outdoor and indoor PM2.5 samples were collected during winter 2008 in Oporto city in Portugal, for sampling periods of 12 and 24 hours, respectively. The outdoor PM2.5 were sampled at one site directly influenced by traffic emissions and the indoor PM2.5 samples were collected at one home directly influenced by tobacco smoke and another one without smoke. A methodology based on microwave-assisted extraction and liquid chromatography with fluorescence detection was applied for the efficient PAHs determination in indoor and outdoor PM2.5. PAHs in indoor PM2.5 concentrations were significantly influenced by the presence of traffic and tobacco smoking emissions. The mean of ��PAHs in the outdoor traffic PM2.5 was not significantly different from the value attained in the indoor without smoking site. The tobacco smoke increased significantly PAHs concentrations on average about 1000 times more, when compared with the outdoor profile samples suggesting that tobacco smoking may be the most important source of indoor PAHs pollution.

Polycyclic aromatic hydrocarbons in gas and particulate phases of indoor environments influenced by tobacco smoke: levels, phase distributions, and health risks

As polycyclic aromatic hydrocarbons (PAHs) have a negative impact on human health due to their mutagenic and/or carcinogenic properties, the objective of this work was to study the influence of tobacco smoke on levels and phase distribution of PAHs and to evaluate the associated health risks. The air samples were collected at two homes; 18 PAHs (the 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in gas phase and associated with thoracic (PM10) and respirable (PM2.5) particles. At home influenced by tobacco smoke the total concentrations of 18 PAHs in air ranged from 28.3 to 106 ngm 3 (mean of 66.7 25.4 ngm 3),���PAHs being 95% higher than at the non-smoking one where the values ranged from 17.9 to 62.0 ngm 3 (mean of 34.5 16.5 ngm 3). On average 74% and 78% of ���PAHs were present in gas phase at the smoking and non-smoking homes, respectively, demonstrating that adequate assessment of PAHs in air requires evaluation of PAHs in both gas and particulate phases. When influenced by tobacco smoke the health risks values were 3.5e3.6 times higher due to the exposure of PM10. The values of lifetime lung cancer risks were 4.1 10 3 and 1.7 10 3 for the smoking and nonsmoking homes, considerably exceeding the health-based guideline level at both homes also due to the contribution of outdoor traffic emissions. The results showed that evaluation of benzo[a]pyrene alone would probably underestimate the carcinogenic potential of the studied PAH mixtures; in total ten carcinogenic PAHs represented 36% and 32% of the gaseous ���PAHs and in particulate phase they accounted for 75% and 71% of ���PAHs at the smoking and non-smoking homes, respectively.

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: influence of air flow rate, water and natural organic matter content

Abstract This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.

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 ��PAHs 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.