Emission factors for a biofuel impacted fleet in South America's largest metropolitan area.

The Metropolitan Area of São Paulo (MASP) is among the largest urban areas in the Southern Hemisphere. Vehicular emissions are of great concern in metropolitan areas and MASP is unique due to the use of biofuels on a large scale (sugarcane ethanol and biodiesel). In this work, tunnel measurements were employed to assess vehicle emissions and to calculate emission factors (EFs) for heavy-duty and light-duty vehicles (HDVs and LDVs). The EFs were determined for particulate matter (PM) and its chemical compounds. The EFs obtained for 2018 were compared with previous tunnel experiments performed in the same area. An overall trend of reduction of fine and coarse PM, organic carbon (OC), and elemental carbon (EC) EFs for both LDVs and HDVs was observed if compared to those observed in past years, suggesting the effectiveness of vehicular emissions control policies implemented in Brazil. A predominance of Fe, Cu, Al, and Ba emissions was observed for the LDV fleet in the fine fraction. Cu presented higher emissions than two decades ago, which was associated with the increased use of ethanol fuel in the region. For HDVs, Zn and Pb were mostly emitted in the fine mode and were linked with lubricating oil emissions from diesel vehicles. A predominance in the emission of three- and four-ring polycyclic aromatic hydrocarbons (PAHs) for HDVs and five-ring PAHs for LDVs agreed with what was observed in previous studies. The use of biofuels may explain the lower PAH emissions for LDVs (including carcinogenic benzo[a]pyrene) compared to those observed in other countries. The tendency observed was that LDVs emitted higher amounts of carcinogenic species. The use of these real EFs in air quality modeling resulted in more accurate simulations of PM concentrations, showing the importance of updating data with real-world measurements.

Evolution of Vehicle Emission Factors in a Megacity Affected by Extensive Biofuel Use: Results of Tunnel Measurements in São Paulo, Brazil.

Since 2001, four emission measurement campaigns have been conducted in multiple traffic tunnels in the megacity of São Paulo, Brazil, an area with a fleet of more than 7 million vehicles running on fuels with high biofuel contents: gasoline + ethanol for light-duty vehicles (LDVs) and diesel + biodiesel for heavy-duty vehicles (HDVs). Emission factors for LDVs and HDVs were calculated using a carbon balance method, the pollutants considered including nitrogen oxides (NOx), carbon monoxide (CO), and sulfur dioxide, as well as carbon dioxide and ethanol. From 2001 to 2018, fleet-average emission factors for LDVs and HDVs, respectively, were found to decrease by 4.9 and 5.1% per year for CO and by 5.5 and 4.2% per year for NOx. These reductions demonstrate that regulations for vehicle emissions adopted in Brazil in the last 30 years improved air quality in the megacity of São Paulo significantly, albeit with a clear delay. These findings, especially those for CO, indicate that official emission inventories underestimate vehicle emissions. Here, we demonstrated that the adoption of emission factors calculated under real-world conditions can dramatically improve air quality modeling in the region.

Nrf2 positively regulates autophagy antioxidant response in human bronchial epithelial cells exposed to diesel exhaust particles.

Diesel exhaust particles (DEP) are known to generate reactive oxygen species in the respiratory system, triggering cells to activate antioxidant defence mechanisms, such as Keap1-Nrf2 signalling and autophagy. The aim of this study was to investigate the relationship between the Keap1-Nrf2 signalling and autophagy pathways after DEP exposure. BEAS-2B cells were transfected with silencing RNA (siRNA) specific to Nrf2 and exposed to DEP. The relative levels of mRNA for Nrf2, NQO1, HO-1, LC3B, p62 and Atg5 were determined using RT-PCR, while the levels of LCB3, Nrf2, and p62 protein were determined using Western blotting. The autophagy inhibitor bafilomycin caused a significant decrease in the production of Nrf2, HO-1 and NQO1 compared to DEPs treatment, whereas the Nrf2 activator sulforaphane increased the LC3B (p = 0.020) levels. BEAS-2B cells exposed to DEP at a concentration of 50 µg/mL for 2 h showed a significant increase in the expression of LC3B (p = 0.001), p62 (p = 0.008), Nrf2 (p = 0.003), HO-1 (p = 0.001) and NQO1 (p = 0.015) genes compared to control. In siRNA-transfected cells, the LC3B (p < 0.001), p62 (p = 0.001) and Atg5 (p = 0.024) mRNA levels and the p62 and LC3II protein levels were decreased, indicating that Nrf2 modulated the expression of autophagy markers (R < 1). These results imply that, in bronchial cells exposed to DEP, the Nrf2 system positively regulates autophagy to maintain cellular homeostasis.

Cashew nut roasting: chemical characterization of particulate matter and genotocixity analysis.

BACKGROUND: Particulate matter (PM) is potentially harmful to health and related to genotoxic events, an increase in the number of hospitalizations and mortality from respiratory and cardiovascular diseases. The present study conducted the first characterization of elemental composition and polycyclic aromatic hydrocarbon (PAH) analysis of PM, as well as the biomonitoring of genotoxic activity associated to artisanal cashew nut roasting, an important economic and social activity worldwide. METHODS: The levels of PM2.5 and black carbon were also measured by gravimetric analysis and light reflectance. The elemental composition was determined using X-ray fluorescence spectrometry and PAH analysis was carried out by gas chromatography-mass spectrometry. Genotoxic activity was measured by the Tradescantia pallida micronucleus bioassay (Trad-MCN). Other biomarkers of DNA damage, such as nucleoplasmic bridges and nuclear fragments, were also quantified. RESULTS: The mean amount of PM2.5 accumulated in the filters (January 2124.2 µg/m(3); May 1022.2 µg/m(3); September 1291.9 µg/m(3)), black carbon (January 363.6 µg/m(3); May 70 µg/m(3); September 69.4 µg/m(3)) and concentrations of Al, Si, P, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Se, Br and Pb were significantly higher than the non-exposed area. Biomass burning tracers K, Cl, and S were the major inorganic compounds found. Benzo[k]fluoranthene, indene[1,2,3-c,d]pyrene, benzo[ghi]perylene, phenanthrene and benzo[b]fluoranthene were the most abundant PAHs. Mean benzo[a]pyrene-equivalent carcinogenic power values showed a significant cancer risk. The Trad-MCN bioassay revealed an increase in micronucleus frequency, 2-7 times higher than the negative control and significantly higher in all the months analyzed, possibly related to the mutagenic PAHs found. CONCLUSIONS: This study demonstrated that artisanal cashew nut roasting is a serious occupational problem, with harmful effects on workers׳ health. Those involved in this activity are exposed to higher PM2.5 concentrations and to 12 PAHs considered potentially mutagenic and/or carcinogenic. The Trad-MCN with T. pallida was sensitive and efficient in evaluating the genotoxicity of the components and other nuclear alterations may be used as effective biomarkers of DNA damage.

Occurrence of polycyclic aromatic hydrocarbons derivatives and mutagenicitys study in extracts of PM10 collected in São Paulo, Brazil / Ocorrência de derivados de hidrocarbonetos policíclicos aromáticos e estudo da sua mutagenicidade em extratos de PM10 coletado em São Paulo, Brasil

As frações nitro-HPA e oxi-HPA de extratos orgânicos de MP10 coletados na cidade de São Paulo, Brasil, (inverno, 2004) foram quimicamente e toxicologicamente analisadas. Alguns nitro-HPA emitidos por exaustão veicular foram quantificados. O 3-nitrofluoranteno, provavelmente co-eluido com o 2-nitrofluoranteno, um poluente secundário, apresentou níveis mais elevados (média: 0,16 ng m-3; concentração máxima: 0,26 ng m-3) que o 1-nitropireno (média: 0,031 ng m-3; concentração máxima: 0,054 ng m-3). O 6-nitrocriseno não foi encontrado em níveis detectáveis. Oxi-HPA não foram detectados provavelmente porque esses compostos estavam presentes em concentrações muito baixas. Ambas as frações, nitro-HPA e oxi-HPA apresentaram respostas mutagênicas semelhantes, do tipo deslocamento no quadro de leitura, com potencial maior na ausência de S9 quando comparado com a resposta na presença de S9, indicando a prevalência de mutágenos diretos para o teste Salmonella/microssoma...

Nitro-PAH and oxy-PAH fractions in organic extracts of PM10 collected in São Paulo City, Brazil (winter, 2004) were chemically and toxicologically analyzed. Some nitro-PAH compounds that are emitted from vehicular motor exhaust were quantified. The 3-nitrofluoranthene, which probably coeluted with the 2-nitrofluoranthene, a secondary pollutant, presented higher levels (average: 0.16 ng m-3; maximum concentration: 0.26 ng m-3) than 1-nitropyrene (average: 0.031 ng m-3; maximum concentration: 0.054 ngm-3). No detectable amount of 6-nitrocrysene was found. Oxy-PAH compounds were not detected probably because they were present at concentrations much low. Both nitro and oxy-PAH fractions have showed a similar frameshift mutagenic response with a higher potency in the absence of S9 compared to that in the presence of S9, indicating the prevalence of direct-acting compounds for the Salmonella/ microsome assay...