The new WHO air quality guidelines for PM2.5: predicament for small/medium cities.

The global burden of disease estimated that approximately 7.1 million deaths worldwide were related to air pollution in 2016. However, only a limited number of small- and middle-sized cities have air quality monitoring networks. To date, air quality in terms of particulate matter is still mainly focused on mass concentration, with limited compositional monitoring even in mega cities, despite evidence indicating differential toxicity of particulate matter. As this evidence is far from conclusive, we conducted PM2.5 bioaccessibility studies of potentially harmful elements in a medium-sized city, Londrina, Brazil. The data was interpreted in terms of source apportionment, the health risk evaluation and the bioaccessibility of inorganic contents in an artificial lysosomal fluid. The daily average concentration of PM2.5 was below the WHO guideline, however, the chemical health assessment indicated a considerable health risk. The in vitro evaluation showed different potential mobility when compared to previous studies in large-sized cities, those with 1 million inhabitants or more (Curitiba and Manaus). The new WHO guideline for PM2.5 mass concentration puts additional pressure on cities where air pollution monitoring is limited and/or neglected, because decision making is mainly revenue-driven and not socioeconomic-driven. Given the further emerging evidence that PM chemical composition is as, or even more, important than mass concentration levels, the research reported in the paper could pave the way for the necessary inter- and intra-city collaborations that are needed to address this global health challenge.

The influence that different urban development models has on PM2.5 elemental and bioaccessible profiles.

Limited studies have reported on in-vitro analysis of PM2.5 but as far as the authors are aware, bioaccessibility of PM2.5 in artificial lysosomal fluid (ALF) has not been linked to urban development models before. The Brazilian cities Manaus (Amazon) and Curitiba (South region) have different geographical locations, climates, and urban development strategies. Manaus drives its industrialization using the free trade zone policy and Curitiba adopted a services centered economy driven by sustainability. Therefore, these two cities were used to illustrate the influence that these different models have on PM2.5 in vitro profile. We compared PM2.5 mass concentrations and the average total elemental and bioaccessible profiles for Cu, Cr, Mn, and Pb. The total average elemental concentrations followed Mn > Pb > Cu > Cr in Manaus and Pb > Mn > Cu > Cr in Curitiba. Mn had the lowest solubility while Cu showed the highest bioaccessibility (100%) and was significantly higher in Curitiba than Manaus. Cr and Pb had higher bioaccessibility in Manaus than Curitiba. Despite similar mass concentrations, the public health risk in Manaus was higher than in Curitiba indicating that the free trade zone had a profound effect on the emission levels and sources of airborne PM. These findings illustrate the importance of adopting sustainable air quality strategies in urban planning.

Assessing the impact of PM2.5 on respiratory disease using artificial neural networks.

Understanding the impact on human health during peak episodes in air pollution is invaluable for policymakers. Particles less than PM2.5 can penetrate the respiratory system, causing cardiopulmonary and other systemic diseases. Statistical regression models are usually used to assess air pollution impacts on human health. However, when there are databases missing, linear statistical regression may not process well and alternative data processing should be considered. Nonlinear Artificial Neural Networks (ANN) are not employed to research environmental health pollution even though another advantage in using ANN is that the output data can be expressed as the number of hospital admissions. This research applied ANN to assess the impact of air pollution on human health. Three well-known ANN were tested: Multilayer Perceptron (MLP), Extreme Learning Machines (ELM) and Echo State Networks (ESN), to assess the influence of PM2.5, temperature, and relative humidity on hospital admissions due to respiratory diseases. Daily PM2.5 levels were monitored, and hospital admissions for respiratory illness were obtained, from the Brazilian hospital information system for all ages during two sampling campaigns (2008-2011 and 2014-2015) in Curitiba, Brazil. During these periods, the daily number of hospital admissions ranged from 2 to 55, PM2.5 concentrations varied from 0.98 to 54.2 µg m-3, temperature ranged from 8 to 26 °C, and relative humidity ranged from 45 to 100%. Of the ANN used in this study, MLP gave the best results showing a significant influence of PM2.5, temperature and humidity on hospital attendance after one day of exposure. The Anova Friedman's test showed statistical difference between the appliance of each ANN model (p < .001) for 1 lag day between PM2.5 exposure and hospital admission. ANN could be a more sensitive method than statistical regression models for assessing the effects of air pollution on respiratory health, and especially useful when there is limited data available.

Health implications of atmospheric aerosols from asbestos-bearing road pavements traditionally used in Southern Brazil.

Serpentine and amphibole asbestos occur naturally in certain geologic settings worldwide, most commonly in association with ultramafic rocks, along associated faults. Ultramafic rocks have been used in Piên County, Southern Brazil for decades for the purpose of road paving in rural and urban areas, but without the awareness of their adverse environmental and health impact. The aim of this study was the chemical characterization of aerosols re-suspended in two rural roads of Piên, paved with ultramafic rocks and to estimate the pulmonary deposition of asbestos aerosols. Bulk aerosol samples were analyzed by means of X-ray fluorescence spectrometry and X-ray diffraction analysis, in order to characterize elemental composition and crystallinity. Single-particle compositions of aerosols were analyzed by computer-controlled electron-probe microanalysis, indicating the presence of a few percentages of serpentine and amphibole. Given the chemical composition and size distribution of aerosol particles, the deposition efficiency of chrysotile, a sub-group of serpentine, in two principal segments of the human respiratory system was estimated using a lung deposition model. As an important finding, almost half of the inhaled particles were calculated to be deposited in the respiratory system. Asbestos depositions were significant (∼25 %) in the lower airways, even though the selected breathing conditions (rest situation, nose breathing) implied the lowest rate of respiratory deposition. Considering the fraction of inhalable suspended chrysotile near local roads, and the long-term exposure of humans to these aerosols, chrysotile may represent a hazard, regarding more frequent development of lung cancer in the population of the exposed region.

Effectiveness of selective catalytic reduction systems on reducing gaseous emissions from an engine using diesel and biodiesel blends.

The aim of this investigation was to quantify organic and inorganic gas emissions from a four-cylinder diesel engine equipped with a urea selective catalytic reduction (SCR) system. Using a bench dynamometer, the emissions from the following mixtures were evaluated using a Fourier transform infrared (FTIR) spectrometer: low-sulfur diesel (LSD), ultralow-sulfur diesel (ULSD), and a blend of 20% soybean biodiesel and 80% ULSD (B20). For all studied fuels, the use of the SCR system yielded statistically significant (p < 0.05) lower NOx emissions. In the case of the LSD and ULSD fuels, the SCR system also significantly reduced emissions of compounds with high photochemical ozone creation potential, such as formaldehyde. However, for all tested fuels, the SCR system produced significantly (p < 0.05) higher emissions of N2O. In the case of LSD, the NH3 emissions were elevated, and in the case of ULSD and B20 fuels, the non-methane hydrocarbon (NMHC) and total hydrocarbon of diesel (HCD) emissions were significantly higher.

Methods, fluxes and sources of gas phase alkyl nitrates in the coastal air.

The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3-C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO2 levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.

Healthy environment--indoor air quality of Brazilian elementary schools nearby petrochemical industry.

The mitigation of pollution released to the environment originating from the industrial sector has been the aim of all policy-makers and its importance is evident if the adverse health effects on the world population are considered. Although this concern is controversial, petroleum refinery has been linked to some adverse health effects for people living nearby. Apart from home, school is the most important indoor environment for children and there is increasing concern about the school environment and its impact on health, also in developing countries where the prevalence of pollution is higher. As most of the children spend more than 40% of their time in schools, it is critical to evaluate the pollution level in such environment. In the metropolitan region of Curitiba, South Brazil, five schools nearby industries and highways with high density traffic, were selected to characterize the aerosol and gaseous compounds indoor and outdoor of the classrooms, during 2009-2011. Size segregated aerosol samples were collected for analyses of bulk and single particle elemental profiles. They were analyzed by electron probe X-ray micro-analysis (EPXMA), and by energy-dispersive X-ray fluorescence (EDXRF), to investigate the elemental composition of individual particles and bulk samples. The concentrations of benzene, toluene, ethylbenzene, and xylene (BTEX); NO2; SO2; acetic acid; and formic acid were assessed indoor and outdoor using passive diffusion tubes. BTEX were analyzed by GC-MS and other collected gasses by ion chromatography. Individual exposition of BTEX was assessed by personal passive diffusion tubes. Results are interpreted separately and as a whole with the specific aim of identifying compounds that could affect the health of the scholars. In view of the chemical composition and size distribution of the aerosol particles, local deposition efficiencies in the children's respiratory systems were calculated, revealing the deposition of particles at extrathoracic, tracheobronchial and pulmonary levels.

Indoor air quality of a museum in a subtropical climate: the Oscar Niemeyer museum in Curitiba, Brazil.

The assessment of damage to indoor cultural heritage, in particular by pollutants, is nowadays a major and growing concern for curators and conservators. Nevertheless, although many museums have been widely investigated in Europe, the effects of particulate matter and gaseous pollutants in museums under tropical and subtropical climates and with different economic realities are still unclear. An important portion of the world's cultural heritage is currently in tropical countries where both human and financial resources for preserving museum collections are limited. Hence, our aim is to assess the damage that can be caused to the artwork by pollution in hot and humid environments, where air quality and microclimatic condition differences can cause deterioration. As a case study, particulate matter as well as gases were collected at the Oscar Niemeyer Museum (MON) in Curitiba, Brazil, where large modern and contemporary works of art are displayed. NO2, SO2, O3, Acetic Acid, Formic Acids and BTEX, in the ambient air, were sampled by means of passive diffusive sampling and their concentrations were determined by IC or GC-MS. The particulate matter was collected in bulk form and analyzed with the use of energy dispersive X-ray fluorescence and aethalometer. The chemical compositions of individual particles were quantitatively elucidated, including low-Z components like C, N and O, as well as higher-Z elements, using automated electron probe microanalysis. The gaseous and particulate matter levels were then compared with the concentrations obtained for the same pollutants in other museums, located in places with different climates, and with some reference values provided by international cultural heritage conservation centers. Results are interpreted separately and as a whole with the specific aim of identifying compounds that could contribute to the chemical reactions taking place on the surfaces of artifacts and which could potentially cause irreversible damage to the artworks.

Particulate matter analysis at elementary schools in Curitiba, Brazil.

The particulate matter indoors and outdoors of the classrooms at two schools in Curitiba, Brazil, was characterised in order to assess the indoor air quality. Information concerning the bulk composition was provided by energy-dispersive x-ray fluorescence (EDXRF). From the calculated indoor/outdoor ratios and the enrichment factors it was observed that S-, Cl- and Zn-rich particles are of concern in the indoor environment. In the present research, the chemical compositions of individual particles were quantitatively elucidated, including low-Z components like C, N and O, as well as higher-Z elements, using automated electron probe microanalysis low Z EPMA. Samples were further analysed for chemical and morphological aspects, determining the particle size distribution and classifying them according to elemental composition associations. Five classes were identified based on major elemental concentrations: aluminosilicate, soot, organic, calcium carbonate and iron-rich particles. The majority of the respirable particulate matter found inside of the classroom was composed of soot, biogenic and aluminosilicate particles. In view of the chemical composition and size distribution of the aerosol particles, local deposition efficiencies in the human respiratory system were calculated revealing the deposition of soot at alveolar level. The results showed that on average 42% of coarse particles are deposited at the extrathoracic level, whereas 24% are deposited at the pulmonary region. The fine fraction showed a deposition rate of approximately 18% for both deposition levels.

Low-pressure gas chromatography-ion trap mass spectrometry for the fast determination of polycyclic aromatic hydrocarbons in air samples.

A low-pressure gas chromatography-ion trap mass spectrometry (LPGC-ITMS) method was investigated to shorten the analysis time for 18 US Environmental Protection Agency priority listed polycyclic aromatic hydrocarbons (PAHs). Their elution was optimised with a short, wide-bore column coupled to a deactivated capillary at the inlet end and with a long, conventional column to compare their analytical performance. The analytical figures of merit under optimal LPGC-ITMS conditions were determined with respect to chromatographic separation, S/N ratio, limit of detection and precision. The peak width at half height of 1.5s matched the ITMS duty cycle. Up to 16 PAHs in the molecular weight (MW) range of 128-278 Da could be separated in a very short time, i.e. less than 13 min using LPGC-ITMS, whereas with conventional GC-MS, it took approximately 40 min. However, LPGC-ITMS has a limited loss of separation power compared to that of conventional GC-MS due to the occurrence of three critical pairs for high-MW PAHs. For a practical evaluation, the LPGC-ITMS approach was applied to the determination of PAHs in gas and aerosol phase samples collected in the ambient air of Hasselt, Belgium.

Use of solid-phase microextraction for the detection of acetic acid by ion-trap gas chromatography-mass spectrometry and application to indoor levels in museums.

A simple and efficient method using solid-phase microextraction (SPME) and gas chromatography-ion trap mass spectrometry (GC-ITMS) was developed for the analysis of acetic acid in air. The choice of the SPME fibre revealed to be critical as well as the sampling and desorption time. A dilution vessel was used for calibration. The precision of the method was found to be 4.7% relative standard deviation (RSD) and the detection limit 5.7 microg m(-3). The SPME-GC-MS technique was applied to the analysis of acetic acid in museum atmospheres.

Fast chromatographic determination of polycyclic aromatic hydrocarbons in aerosol samples from sugar cane burning.

Sugar cane burning in Brazil causes remarkable amounts of organic compounds to be emitted amongst which the polycyclic aromatic hydrocarbons (PAHs) represent serious health hazards. Therefore, 24-h aerosol samples (< 10 microm aerodynamic diameter) were collected in Araraquara city (São Paulo state) during the harvest season using a Hi-Vol sampler. PAHs were recovered using an Accelerated Solvent Extractor and analyzed by low-pressure gas chromatography-ion trap mass spectrometry (LP-GC-IT-MS). The fully automated extraction process was performed in less than 25 min with a solvent consumption of approximately 20 ml. The use of a deactivated 0.6 m x 0.10 mm i.d. restrictor coupled to a 10 m wide-bore analytical column allowed most of the 16 PAHs in EPA's priority list to be identified and quantified in only 13 min. Concentrations of PAHs in Araraquara aerosols ranged between 0.5 and 8.6 ng m(-3).

Application of low-pressure gas chromatography-ion-trap mass spectrometry to the analysis of the essential oil of Turnera diffusa (Ward.) Urb.

Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 microm) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved.

Determination of butyltin compounds in surface sediments from the São Paulo State coast (Brazil) by gas chromatography-pulsed flame photometric detection.

Occurrence and the effects of butyltin compounds (BTs) have been studied for some years, mainly in countries of the Northern Hemisphere. Due to widespread use of tributyltin compounds (TBTs) and considering their deleterious effects, it is necessary to conduct studies on its occurrence, especially in the marine environment because of its excessive use in coatings of ship hulls to prevent fouling. Moreover, it was important to extend the evaluation to areas where there is no current information about their occurrence. The present work reports the occurrence of BTs in marine sediments of São Paulo state, Brazil. Commercial and leisure harbor sampling sites were selected because these areas are potentially exposed to BTs from antifouling paints used on ship hulls. Analytical conditions for organotin analysis in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits ranged from 8A to 66.3 ng g(-1) using a 610-nm filter, and the linearity range was 20-500 ng g(-1). Concentration levels of BTs were highest in Santos harbor (360 ng g(-1) TBT in average) and Guarujá marina (670 ng g(-1) TBT in average), which seems to be related to intensive boat traffic. Lower levels of BTs were observed in Cananéia, where only fishing boats are present (50 ng g(-1) TBT in average).

Occupational allergic contact dermatitis from bisphenol A in vinyl gloves.

Allergic contact dermatitis caused by polyvinyl chloride gloves is rarely reported, and in only 2 cases was bisphenol A considered to be the responsible sensitizer. We report a patient with occupational hand dermatitis after the use of a new type of high-density vinyl (HDV) gloves. Patch tests showed positive (++) reactions to both used and new HDV gloves and to bisphenol A. Chemical analysis by gas chromatography-mass spectrometry demonstrated the presence of bisphenol A in the HDV gloves. Replacement by nitrile rubber gloves resulted in complete clearance of the hand dermatitis.