Methylsiloxanes from Vehicle Emissions Detected in Aerosol Particles.

Methylsiloxanes have gained growing attention as emerging pollutants due to their toxicity to organisms. As man-made chemicals with no natural source, most research to date has focused on volatile methylsiloxanes from personal care or household products and industrial processes. Here, we show that methylsiloxanes can be found in primary aerosol particles emitted by vehicles based on aerosol samples collected in two tunnels in São Paulo, Brazil. The aerosol samples were analyzed with thermal desorption-proton transfer reaction-mass spectrometry (TD-PTR-MS), and methylsiloxanes were identified and quantified in the mass spectra based on the natural abundance of silicon isotopes. Various methylsiloxanes and derivatives were found in aerosol particles from both tunnels. The concentrations of methylsiloxanes and derivatives ranged 37.7-377 ng m-3, and the relative fractions in organic aerosols were 0.78-1.9%. The concentrations of methylsiloxanes exhibited a significant correlation with both unburned lubricating oils and organic aerosol mass. The emission factors of methylsiloxanes averaged 1.16 ± 0.59 mg kg-1 of burned fuel for light-duty vehicles and 1.53 ± 0.37 mg kg-1 for heavy-duty vehicles. Global annual emissions of methylsiloxanes in vehicle-emitted aerosols were estimated to range from 0.0035 to 0.0060 Tg, underscoring the significant yet largely unknown potential for health and climate impacts.

Assessing socioeconomic bias of exposure to urban air pollution: an autopsy-based study in São Paulo, Brazil.

Background: The characterisation of individual exposure to air pollution in urban scenarios is a challenge in environmental epidemiological studies. We investigated if the city's pollution monitoring stations over or underestimate the exposure of individuals depending on their socioeconomic conditions and daily commuting times. Methods: The amount of black carbon accumulated in the lungs of 604 deceased who underwent autopsy in São Paulo was considered as a proxy for PM10. The concentrations of PM10 in the residence of the deceased were estimated by interpolating an ordinary kriging model. These two-exposure metrics allowed us to construct an environmental exposure misclassification index ranging from -1 to 1. The association between the index and daily commuting, socioeconomic context index (GeoSES), and street density as predictors was assessed by means of a multilevel linear regression model. Findings: With a decrease of 0.1 units in GeoSES, the index increases, on average, by 0.028 units and with an increase of 1 h in daily commuting, the index increases, on average, by 0.022 units indicating that individual exposure to air pollution is underestimated in the lower GeoSES and in people with many hours spent in daily commuting. Interpretation: Reduction of health consequences of air pollution demands not only alternative fuel and more efficient mobility strategies, but also should include profound rethink of cities. Funding: São Paulo Research Foundation (FAPESP-13/21728-2) and National Council for Scientific and Technological Development (CNPq-304126/2015-2, 401825/2020-5).

Particulate matter fingerprints in biofuel impacted tunnels in South America's largest metropolitan area.

This study characterized the chemical composition of particulate matter (PM) from light- (LDV) and heavy-duty (HDV) vehicles based on two traffic tunnel samplings carried out in the megacity of São Paulo (Brazil), which has >7 million vehicles and intense biofuel use. The samples were collected with high-volume samplers and analyzed using chemical characterization techniques (ion and gas chromatography, thermal-optical analysis, and inductively coupled plasma mass spectroscopy). Chemical source profiles (%) were calculated based on the measurements performed inside and outside the tunnels. Identifying a high abundance of Fe and Cu for traffic-related PM in the LDV-impacted tunnel was possible, linked with the emission of vehicles powered by ethanol and gasohol (gasoline and ethanol blend). We calculated diagnostic ratios (e.g., EC/Cu, Fe/Cu, pyrene/benzo[a]pyrene, pyrene/benzo[b]fluoranthene, and fluoranthene/benzo[b]fluoranthene) characteristic of fuel exhausts (diesel/biodiesel and ethanol/gasohol), allowing their use in the assessment of the temporal variation of the fuel type used in urban sites. Element diagnostic ratios (Cu/Sb and Fe/Cu) pointed to the predominance of LDVs exhaust-related copper and can differentiate LDVs exhaust from brake wear emissions. The carbonaceous fraction EC3 was suggested as an HDV emission tracer. A higher total polycyclic aromatic hydrocarbons (PAHs) fraction of traffic-related PM2.5 was observed in the HDV-impacted tunnel, with a predominance of diesel-related pyrene and fluoranthene, as well as higher oxy-PAHs (e.g., 9,10-anthraquinone, associated with biodiesel blends) abundances. However, carcinogenic species presented higher abundances for the LDV-impacted tunnel (e.g., benzo[a]pyrene). These findings highlighted the impact of biofuels on the characteristic ratios of chemical species and pointed to possible markers for LDVs and HDVs exhausts.

Accumulation of trace element content in the lungs of Sao Paulo city residents and its correlation to lifetime exposure to air pollution.

Heavy metals are natural and essential elements of the environment and living beings, produced from natural (e.g. volcanic activity and cosmic ray-induced spallation) and anthropogenic processes (e.g. industrial and fossil fuel combustion). High-concentrations of heavy metals and radionuclides are also originated from anthropogenic activities in urban and industrial areas. In this preliminary study, we analyzed the levels of heavy metals and Polonium-210 (210Po) in lung tissues in autopsies from residents of the city of Sao Paulo, SP, Brazil. In order to identify the link among sources of the heavy metals in lungs, factor analysis was performed. Of the first four factors, which explain 66% of the total variability, three were associated with vehicular sources. The fitting of a regression model with 210Po as the response variable and with the four factors as explanatory variables, controlling for age, sex and tobacco, showed a significant association between the concentration of polonium and the first factor that is generated by catalysts and brakes (coefficient = 0.90, standard error = 0.33, p = 0.016). Our findings suggest an association between traffic-related trace metals and 210Po in lung autopsies.

Improving the assessment of RDE dynamics through vehicle-specific power analysis.

Vehicles are an important source of air pollutants and greenhouse gases. Their emissions have been controlled since the 1970s by laboratory tests but there are often found divergences to real-world emissions. Real driving emissions procedure is in implementation in many countries, for evaluating vehicles closer to actual operation. In order to reduce the dispersion of the results, some dynamic parameters, such as speed, acceleration, and CO2 emissions, are controlled; however, sometimes they are into the limits but divergences remain. This paper has the goal of applying VSP as an additional parameter for improving the evaluation of the vehicle dynamics, because it can better represent the engine power required for running as well as the road grade influence.

Chemical characterization of PM2.5 from region highly impacted by hailstorms in South America.

The chemical composition of particulate material plays an important role in the atmosphere, providing cloud and ice nuclei for storm development. This study aims to evaluate and infer the sources of ions, metals, and metalloids in the fine atmospheric particulate matter (PM2.5) from triple border Paraná, Santa Catarina (Brazil), and northeastern Argentina, which is among those with the highest hail incidence in the world. Among the ions, the concentrations presented the following sequence in decreasing order: [Formula: see text]> K+> [Formula: see text]> [Formula: see text]> Ca2+> Cl-> Na+> Mg2+. Regarding the metals and metalloid concentrations, the order was of S > Si > Al > Fe > P > Ti, Cr, Cu, and Zn > Br > Mn, and Ni. The main sources, supported by positive matrix factorization results, are soil and agricultural activities, as well as vehicular emissions due to the agricultural machinery and the displacement of residents. Besides, the influence of aerosols from biomass burning and industrial activities was observed, possibly come from long-distance transport. The composition of PM2.5 presents one or more elements considered present ice nuclei (IN) activity, such as Al, Mn, Cu, Co, Ni, and V (in form of oxides), corroborating with other studies, also, with high hail incidence. However, further studies are needed to verify the role of aerosol characteristics in the formation of IN and, consequently, hail.

Potential health risks due to in-car aerosol exposure across ten global cities.

Car microenvironments significantly contribute to the daily pollution exposure of commuters, yet health and socioeconomic studies focused on in-car exposure are rare. This study aims to assess the relationship between air pollution levels and socioeconomic indicators (fuel prices, city-specific GDP, road density, the value of statistical life (VSL), health burden and economic losses resulting from exposure to fine particulate matter ≤2.5 µm; PM2.5) during car journeys in ten cities: Dhaka (Bangladesh); Chennai (India); Guangzhou (China); Medellín (Colombia); São Paulo (Brazil); Cairo (Egypt); Sulaymaniyah (Iraq); Addis Ababa (Ethiopia); Blantyre (Malawi); and Dar-es-Salaam (Tanzania). Data collected by portable laser particle counters were used to develop a proxy of car-user exposure profiles. Hotspots on all city routes displayed higher PM2.5 concentrations and disproportionately high inhaled doses. For instance, the time spent at the hotspots in Guangzhou and Addis Ababa was 26% and 28% of total trip time, but corresponded to 54% and 56%, respectively, of the total PM2.5 inhaled dose. With the exception of Guangzhou, all the cities showed a decrease in per cent length of hotspots with an increase in GDP and VSL. Exposure levels were independent of fuel prices in most cities. The largest health burden related to in-car PM2.5 exposure was estimated for Dar-es-Salam (81.6 ± 39.3 µg m-3), Blantyre (82.9 ± 44.0) and Dhaka (62.3 ± 32.0) with deaths per 100,000 of the car commuting population per year of 2.46 (2.28-2.63), 1.11 (0.97-1.26) and 1.10 (1.05-1.15), respectively. However, the modest health burden of 0.07 (0.06-0.08), 0.10 (0.09-0.12) and 0.02 (0.02-0.03) deaths per 100,000 of the car commuting population per year were estimated for Medellin (23 ± 13.7 µg m-3), São Paulo (25.6 ± 11.7) and Sulaymaniyah (22.4 ± 15.0), respectively. Lower GDP was found to be associated with higher economic losses due to health burdens caused by air pollution in most cities, indicating a socioeconomic discrepancy. This assessment of health and socioeconomic parameters associated with in-car PM2.5 exposure highlights the importance of implementing plausible solutions to make a positive impact on peoples' lives in these cities.

Characterization of particles emitted by pizzerias burning wood and briquettes: a case study at Sao Paulo, Brazil.

The burning of biomass in pizza ovens can be an important source of air pollution. Fine particulate matter represents one of the most aggressive pollutants to human health, besides the potential to interfere with global radiative balance. A study in real-world condition was performed in three pizzerias in São Paulo city. Two of the pizzerias used eucalyptus timber logs and one used wooden briquettes. The results from the three pizzerias revealed high average concentrations of PM2.5: 6171.2 µg/m3 at the exit of the chimney and 68.2 µg/m3 in indoor areas. The burning of briquette revealed lower concentrations of PM2.5. BC represented approximately 20% and 30% of the PM2.5 mass concentration in indoor and at chimney exhaust, respectively. Among the trace elements, potassium, chlorine and sulphur were the most prevalent in terms of concentration. Scanning electron microscopy (SEM) analysis revealed particles with an individual and spherical morphology, i.e. the conglomeration of spherical particles, flattened particles in the formation of fibres, the overlapping of layers and the clustering of particles with sponge-like qualities. The average emission factors for PM2.5 and BC due to the burning of logs were 0.38 g/kg and 0.23 g/kg, respectively. The total emissions of PM2.5 and BC were 116.73 t/year and 70.65 t/year, respectively, in the burning of timber logs.

A two decades study on ozone variability and trend over the main urban areas of the São Paulo state, Brazil.

In this paper, we analyze the variability of the ozone concentration over São Paulo Macrometropolis, as well the factors, which determined the tendency observed in the last two decades. Time series of hourly ozone concentrations measured at 16 automated stations from an air quality network from 1996 to 2017 were analyzed. The temporal variability of ozone concentrations exhibits well-defined daily and seasonal patterns. Ozone presents a significant positive correlation between the number of cases (thresholds of 100-160 µg m-3) and the fuel sales of gasohol and diesel. The ozone concentrations do not exhibit significant long-term trends, but some sites present positive trends that occurs in sites in the proximity of busy roads and negative trends that occurs in sites located in residential areas or next to trees. The effect of atmospheric process of transport and ozone formation was analyzed using a quantile regression model (QRM). This statistical model can deal with the nonlinearities that appear in the relationship of ozone and other variables and is applicable to time series with non-normal distribution. The resulting model explains 0.76% of the ozone concentration variability (with global coefficient of determination R1 = 0.76) providing a better representation than an ordinary least square regression model (with coefficient of determination R2 = 0.52); the effect of radiation and temperature are the most critical in determining the highest ozone quantiles.

WRF-SMOKE-CMAQ modeling system for air quality evaluation in São Paulo megacity with a 2008 experimental campaign data.

Atmospheric pollutants are strongly affected by transport processes and chemical transformations that alter their composition and the level of contamination in a region. In the last decade, several studies have employed numerical modeling to analyze atmospheric pollutants. The objective of this study is to evaluate the performance of the WRF-SMOKE-CMAQ modeling system to represent meteorological and air quality conditions over São Paulo, Brazil, where vehicular emissions are the primary contributors to air pollution. Meteorological fields were modeled using the Weather Research and Forecasting model (WRF), for a 12-day period during the winter of 2008 (Aug. 10th-Aug. 22nd), using three nested domains with 27-km, 9-km, and 3-km grid resolutions, which covered the most polluted cities in São Paulo state. The 3-km domain was aligned with the Sparse Matrix Operator Kernel Emissions (SMOKE), which processes the emission inventory for the Models-3 Community Multiscale Air Quality Modeling System (CMAQ). Data from an aerosol sampling campaign was used to evaluate the modeling. The PM10 and ozone average concentration of the entire period was well represented, with correlation coefficients for PM10, varying from 0.09 in Pinheiros to 0.69 in ICB/USP, while for ozone, the correlation coefficients varied from 0.56 in Pinheiros to 0.67 in IPEN. However, the model underestimated the concentrations of PM2.5 during the experiment, but with ammonium showing small differences between predicted and observed concentrations. As the meteorological model WRF underestimated the rainfall and overestimated the wind speed, the accuracy of the air quality model was expected to be below the desired value. However, in general, the CMAQ model reproduced the behavior of atmospheric aerosol and ozone in the urban area of São Paulo.

Heavy truck restrictions and air quality implications in São Paulo, Brazil.

This study quantified the effects of traffic restrictions on diesel fuel heavy vehicles (HVs) on the air quality of the Bandeirantes corridor using hourly data obtained by continuous monitoring of traffic and air quality at sites located on this avenue. The study addressed the air quality of a city impacted by vehicular emissions and that PM10 and NOX concentrations are mainly due to diesel burning. Data collection was split into two time periods, a period of no traffic constraint on HVs (Nov 2008 and 2009) and a period of constraint (Nov 2010, 2011 and 2012). We found that pollutants on this corridor, mainly PM10 and NOX, decreased significantly during the period from 2008 to 2012 (28 and 43%, 15.8 and 86.9 ppb) as a direct consequence of HV traffic restrictions (a 72% reduction). Rebound effects in the form of increased traffic of light vehicles (LVs) during this time had impacts on the concentration levels, explaining the differences between rates of reduction in HV traffic and pollutants. Reductions in the number of trucks resulted in longer travel times and increased traffic congestion as a consequence of the modal shift towards LVs. We found that a 51% decrease in PM10 (28.8 µg m-3) was due to a reduction in HV traffic (vehicle emissions were estimated to be 71% of total sources, 40.1 µg m-3). This percentage was partially offset by 10% more PM10 emissions related to an increase in LV traffic, while other causes, such as climatic conditions, contributed to a 13% increase in PM10 concentrations. The relationships analyzed in this research served to highlight the need to apply urban transport policies aimed at decreasing pollutant concentrations in São Paulo, especially in heavily congested urban corridors on working days.

The relationship between aerosol particles chemical composition and optical properties to identify the biomass burning contribution to fine particles concentration: a case study for São Paulo city, Brazil.

The air quality in the Metropolitan Area of São Paulo (MASP) is primarily determined by the local pollution source contribution, mainly the vehicular fleet, but there is a concern about the role of remote sources to the fine mode particles (PM2.5) concentration and composition. One of the most important remote sources of atmospheric aerosol is the biomass burning emissions from São Paulo state's inland and from the central and north portions of Brazil. This study presents a synergy of different measurements of atmospheric aerosol chemistry and optical properties in the MASP in order to show how they can be used as a tool to identify particles from local and remote sources. For the clear identification of the local and remote source contribution, aerosol properties measurements at surface level were combined with vertical profiles information. Over 15 days in the austral winter of 2012, particulate matter (PM) was collected using a cascade impactor and a Partisol sampler in São Paulo City. Mass concentrations were determined by gravimetry, black carbon concentrations by reflectance, and trace element concentrations by X-ray fluorescence. Aerosol optical properties were studied using a multifilter rotating shadowband radiometer (MFRSR), a Lidar system and satellite data. Optical properties, concentrations, size distributions, and elemental composition of atmospheric particles were strongly related and varied according to meteorological conditions. During the sampling period, PM mean mass concentrations were 17.4 ± 10.1 and 15.3 ± 6.9 µg/m3 for the fine and coarse fractions, respectively. The mean aerosol optical depths at 415 nm and Ångström exponent (AE) over the whole period were 0.29 ± 0.14 and 1.35 ± 0.11, respectively. Lidar ratios reached values of 75 sr. The analyses of the impacts of an event of biomass burning smoke transport to the São Paulo city revealed significant changing on local aerosol concentrations and optical parameters. The identification of the source contributions, local and remote, to the fine particles in MASP can be more precisely achieved when particle size composition and distribution, vertical profile of aerosols, and air mass trajectories are analyzed in combination.

Urban air pollution: a representative survey of PM(2.5) mass concentrations in six Brazilian cities.

In urban areas of Brazil, vehicle emissions are the principal source of fine particulate matter (PM(2.5)). The World Health Organization air quality guidelines state that the annual mean concentration of PM(2.5) should be below 10 µg m(-3). In a collaboration of Brazilian institutions, coordinated by the University of São Paulo School of Medicine and conducted from June 2007 to August 2008, PM(2.5) mass was monitored at sites with high traffic volumes in six Brazilian state capitals. We employed gravimetry to determine PM(2.5) mass concentrations, reflectance to quantify black carbon concentrations, X-ray fluorescence to characterize elemental composition, and ion chromatography to determine the composition and concentrations of anions and cations. Mean PM(2.5) concentrations and proportions of black carbon (BC) in the cities of São Paulo, Rio de Janeiro, Belo Horizonte, Curitiba, Recife, and Porto Alegre were 28.1 ± 13.6 µg m(-3) (38% BC), 17.2 ± 11.2 µg m(-3) (20% BC), 14.7 ± 7.7 µg m(-3) (31% BC), 14.4 ± 9.5 µg m(-3) (30% BC), 7.3 ± 3.1 µg m(-3) (26% BC), and 13.4 ± 9.9 µg m(-3) (26% BC), respectively. Sulfur and minerals (Al, Si, Ca, and Fe), derived from fuel combustion and soil resuspension, respectively, were the principal elements of the PM(2.5) mass. We discuss the long-term health effects for each metropolitan region in terms of excess mortality risk, which translates to greater health care expenditures. This information could prove useful to decision makers at local environmental agencies.

Long-range ozone transport and its impact on respiratory and cardiovascular health in the north of Portugal.

Ozone dynamics depend on meteorological characteristics such as wind, radiation, sunshine, air temperature and precipitation. The aim of this study was to determine ozone trajectories along the northern coast of Portugal during the summer months of 2005, when there was a spate of forest fires in the region, evaluating their impact on respiratory and cardiovascular health in the greater metropolitan area of Porto. We investigated the following diseases, as coded in the ninth revision of the International Classification of Diseases: hypertensive disease (codes 401-405); ischemic heart disease (codes 410-414); other cardiac diseases, including heart failure (codes 426-428); chronic obstructive pulmonary disease and allied conditions, including bronchitis and asthma (codes 490-496); and pneumoconiosis and other lung diseases due to external agents (codes 500-507). We evaluated ozone data from air quality monitoring stations in the study area, together with data collected through HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model analysis of air mass circulation and synoptic-scale zonal wind from National Centers for Environmental Prediction data. High ozone levels in rural areas were attributed to the dispersion of pollutants induced by local circulation, as well as by mesoscale and synoptic scale processes. The fires of 2005 increased the levels of pollutants resulting from the direct emission of gases and particles into the atmosphere, especially when there were incoming frontal systems. For the meteorological case studies analyzed, peaks in ozone concentration were positively associated with higher rates of hospital admissions for cardiovascular diseases, although there were no significant associations between ozone peaks and admissions for respiratory diseases.

Characterization of metal and trace element contents of particulate matter (PM10) emitted by vehicles running on Brazilian fuels-hydrated ethanol and gasoline with 22% of anhydrous ethanol.

Emission of fine particles by mobile sources has been a matter of great concern due to its potential risk both to human health and the environment. Although there is no evidence that one sole component may be responsible for the adverse health outcomes, it is postulated that the metal particle content is one of the most important factors, mainly in relation to oxidative stress. Data concerning the amount and type of metal particles emitted by automotive vehicles using Brazilian fuels are limited. The aim of this study was to identify inhalable particles (PM(10)) and their trace metal content in two light-duty vehicles where one was fueled with ethanol while the other was fueled with gasoline mixed with 22% of anhydrous ethanol (gasohol); these engines were tested on a chassis dynamometer. The elementary composition of the samples was evaluated by the particle-induced x-ray emission technique. The experiment showed that total emission factors ranged from 2.5 to 11.8 mg/km in the gasohol vehicle, and from 1.2 to 3 mg/km in the ethanol vehicle. The majority of particles emitted were in the fine fraction (PM(2.5)), in which Al, Si, Ca, and Fe corresponded to 80% of the total weight. PM(10) emissions from the ethanol vehicle were about threefold lower than those of gasohol. The elevated amount of fine particulate matter is an aggravating factor, considering that these particles, and consequently associated metals, readily penetrate deeply into the respiratory tract, producing damage to lungs and other tissues.