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This work aims to characterize personal exposure of firefighters to polycyclic aromatic hydrocarbons (PAHs) in non-fire work environments (fire stations), and assesses the respective risks. Eighteen PAHs (16 considered by USEPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were monitored in breathing zones of workers at five Portuguese fire stations during a normal shift. The obtained levels of PAHs fulfilled all existent occupational exposure limits as well as air quality guidelines with total concentrations (ΣPAHs) in range of 46.8-155ngm -3 . Light compounds (2-3 rings) were the most predominant congeners (74-96% of ΣPAHs) whereas PAHs with 5-6 rings accounted 3-9% of ΣPAHs. Fuel and biomass combustions, vehicular traffic emissions, and use of lubricant oils were identified as the main sources of PAHs exposure at the studied fire corporations. Incremental lifetime cancer risks were below the recommend USEPA guideline of 10 -6 and thus negligible for all the studied subjects, but WHO health-based guideline level of 10 -5 was exceeded (9-44 times) at all fire corporations. These results thus show that even during non-fire situations firefighters are exposed to PAHs at levels that may promote some adverse health outcomes; therefore the respective occupational exposures to these compounds should be carefully controlled., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This study evaluated concentrations of main air pollutants in a Portuguese preschool (indoors/outdoors) environment, with emphasis on elemental characterization of different PM fractions, and estimated risks for the pupils (aged 3-5 years). With exception to total volatile organic compounds, levels of PM10, PM2.5, CO, CO2, and formaldehyde were below legislative guidelines. Calcium, sodium, aluminium, and potassium were the most abundant elements in indoor PM (82-84% of the analysed content) resulting mainly from crustal sources. Carcinogenic elements (1-2% of the indoor analysed content) were mostly PM2.5-bound (83-91%). Indoor-to-outdoor ratios of individual elements indicated contributions of indoor origin and from penetration of outdoor emissions indoors; trace metals were associated with ambient anthropogenic emissions (namely traffic). Non-carcinogenic and carcinogenic risks from overall preschool exposure were acceptable for children; for adults carcinogenic risks exceeded (4-11 times) the USEPA recommend value of 10(-6), being 8-40 times higher than for children., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The evaluation of benzene in different environments such as indoor (with and without tobacco smoke), a city area, countryside, gas stations and near exhaust pipes from cars running on different types of fuels was performed. The samples were analyzed using gas chromatography (GC) with flame ionization detection (FID) and tandem mass spectrometric detection (MS/MS) (to confirm the identification of benzene in the air samples). Operating conditions for the GC-MS analysis were optimized as well as the sampling and sample preparation. The results obtained in this work indicate that i) the type of fuel directly influences the benzene concentration in the air. Gasoline with additives provided the highest amount of benzene followed by unleaded gasoline and diesel; ii) the benzene concentration in the gas station was always higher than the advisable limit established by law (5 μg m⁻³) and during the unloading of gasoline the achieved concentration was 8371 μg m⁻³; iii) the data from the countryside (Taliscas) and the urban city (Matosinhos) were below 5 μg m⁻³ except 5 days after a fire on a petroleum refinery plant located near the city; iv) it was proven that in coffee shops where smoking is allowed the benzene concentration is higher (6 μg m⁻³) than in coffee shops where this is forbidden (4 μg m⁻³). This method may also be helpful for environmental analytical chemists who use GC-MS/MS for the confirmation or/and quantification of benzene.

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) accounted for 87 % of the total concentration (Σ) with 3-ringed compounds being the most abundant (66 % of gaseous Σ). PAHs with 5 rings were the most abundant ones in the particulate phase (PM; mean of 6.89 ± 2.85 ng m) being predominantly found in PM (78 % particulate Σ). 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 but slightly higher than WHO-based guideline. [ABSTRACT FROM AUTHOR]

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 ∑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 façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

The concentrations of respirable particulate matter (PM) and the impact on indoor air quality in occupational settings remains poorly characterized. This study assesses, for the first time, the cumulative and non-cumulative concentrations of 14 fractions of coarse (3.65–9.88 μm), fine (0.156–2.47 μm), and ultrafine (0.015–0.095 μm) PM inside the garage of heavy vehicles, firefighting personal protective equipment' storage room, bar, and a common area of seven Portuguese fire stations. Sampling campaigns were performed during a regular work week at the fire stations. Levels of daily total cumulative PM ranged from 277.4 to 413.2 μg/m3 (maximum values of 811.4 μg/m3), with the bar (370.1 μg/m3) and the PPE' storage room (361.3 μg/m3) presenting slightly increased levels (p > 0.05) than the common area (324.8 μg/m3) and the garage (339.4 μg/m3). The location of the sampling site, the proximity to local industries and commercial activities, the layout of the building, the heating system used, and indoor sources influenced the PM concentrations. Fine (193.8–301.0 μg/m3) and ultrafine (41.3–78.2 μg/m3) particles were predominant in the microenvironments of all fire stations and accounted for 71.5% and 17.8% of daily total cumulative levels, respectively; coarse particles (23.3–47.1 μg/m3) represented 10.7% of total PM. The permissible exposure limit (5.0 mg/m3) defined by the Occupational Safety and Health Organization for respirable dust was not overcome in the evaluated fire stations. Results suggest firefighters' regular exposure to fine and ultrafine PM inside fire stations which will contribute to cardiorespiratory health burden. Further studies are needed to characterize firefighters' exposure to fine and ultrafine PM inside fire stations, identify main emission sources, and evaluate the contribution of exposures at fire stations to firefighters' occupational health risks. [Display omitted] • Coarse, fine and ultrafine PM were for the first time assessed at fire stations. • Location, building layout, indoor sources and heating systems impacted PM levels. • The bar and the PPE' storage room presented the highest levels of respirable PM. • Fine and ultrafine PM were the predominant fractions in all microenvironments. • OSHA guidelines were not exceeded in fire stations. [ABSTRACT FROM AUTHOR]

The concentrations of six urinary monohydroxyl metabolites (OH-PAHs) of polycyclic aromatic hydrocarbons, namely 1-hydroxynaphthalene, 1-hydroxyacenaphthene, 2-hydroxyfluorene, 1-hydroxyphenanthrene, 1-hydroxypyrene (1OHPy), and 3-hydroxybenzo[a]pyrene, were assessed in the post-shift urine of wildland firefighters involved in fire combat activities at six Portuguese fire corporations, and compared with those of non-exposed subjects. Overall, median levels of urinary individual and total OH-PAHs (ΣOH-PAHs) suggest an increased exposure to polycyclic aromatic hydrocarbons during firefighting activities with ΣOH-PAH levels in exposed firefighters 1.7-35 times higher than in non-exposed ones. Urinary 1-hydroxynaphthalene and/or 1-hydroxyacenapthene were the predominant compounds, representing 63-98% of ΣOH-PAHs, followed by 2-hydroxyfluorene (1-17%), 1-hydroxyphenanthrene (1-13%), and 1OHPy (0.3-10%). A similar profile was observed when gender discrimination was considered. Participation in fire combat activities promoted an increase of the distribution percentage of 1-hydroxynaphthalene and 1-hydroxyacenaphthene, while contributions of 1-hydroxyphenanthrene and 1OHPy decreased. The detected urinary 1OHPy concentrations (1.73×10-2 to 0.152μmol/mol creatinine in exposed subjects versus 1.21×10-2 to 5.44×10-2μmol/mol creatinine in non-exposed individuals) were lower than the benchmark level (0.5μmol/mol creatinine) proposed by the American Conference of Governmental Industrial Hygienists. This compound, considered the biomarker of exposure to PAHs, was the less abundant one from the six analyzed biomarkers. Thus the inclusion of other metabolites, in addition to 1OHPy, in future studies is suggested to better estimate firefighters' occupational exposure to PAHs. Moreover, strong to moderate Spearman correlations were observed between individual compounds and ΣOH-PAHs corroborating the prevalence of an emission source. [ABSTRACT FROM AUTHOR]

Abstract: 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±39.7ngm−3 with 3–4 rings PAHs accounting for 75% of the total ΣPAHs. 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 ΣPAHs. 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. [Copyright &y& Elsevier]

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 (∑PAHs) 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. [ABSTRACT FROM AUTHOR]