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.

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.

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.

Spatial-temporal variability of metal pollution across an industrial district, evidencing the environmental inequality in São Paulo.

Although air pollution decreased in some cities that shifted from an industrial to a service-based economy, and vehicular emission regulation became more restrictive, it is still a major risk factor for mortality worldwide. In central São Paulo, Brazil, air quality monitoring stations and tree-ring analyses revealed a decreasing trend in the concentrations of particulate matter and metals. Such trends, however, may not be observed in industrial districts located in the urban periphery, where the usual mobile sources may be combined with local stationary sources. To evaluate environmental pollution in an industrial district in southeastern São Paulo, we assessed its spatial variability, by measuring magnetic properties and concentrations of Al, Ba, Ca, Cl, Cu, Fe, K, Mg, Mn, P, S, Sr, Zn in the bark of 62 trees, and its temporal trends, by measuring Cd, Cu, Ni, Pb, V, Zn in tree rings of three trees. Source apportionment analysis based on tree barks revealed two clusters with high concentrations of metals, one related to vehicular and industrial emissions (Al, Ba, Cu, Fe, Zn) in the east side of the industrial cluster, and the other related to soil resuspension (Cu, Zn, Mn) in its west side. These patterns are also supported by the magnetic properties of bark associated with iron oxides and titanium-iron alloy concentrations. Dendrochemical analyses revealed that only the concentrations of Pb consistently decreased over the last four decades. The concentrations of Cd, Cu, Ni, V, and Zn did not significantly decrease over time, in contrast with their negative trends previously reported in central São Paulo. This combined biomonitoring approach revealed spatial clusters of metal concentration in the vicinity of this industrial cluster and showed that the local population has not benefited from the decreasing polluting metal concentrations in the last decades.