Vehicular emissions of organic particulate matter in Sao Paulo, Brazil

Abstract

Abstract. Vehicular emissions have a strong impact on air pollution in big cities. Many factors affect these emissions: type of vehicle, type of fuel, cruising velocity, and brake use. This study focused on emissions of organic compounds by Light (LDV) and Heavy (HDV) duty vehicle exhaust. The study was performed in the city of Sao Paulo, Brazil, where vehicles run on different fuels: gasoline with 25 % ethanol (called gasohol), hydrated ethanol, and diesel (with 5 % of biodiesel). The vehicular emissions are an important source of pollutants and the principal contribution to fine particulate matter (smaller than 2.5 μm, PM2.5) in Sao Paulo. The experiments were performed in two tunnels: Janio Quadros (TJQ) where 99 % of the vehicles are LDV, and Rodoanel Mario Covas (TRA) where up to 30 % of the fleet was HDV. The PM2.5 samples were collected on quartz filters in May and July 2011 at TJQ and TRA, respectively, using two samplers operating in parallel. The samples were analyzed by Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometry (TD-PTR-MS), and by Thermal-Optical Transmittance (TOT). The organic aerosol (OA) desorbed at TD-PTR-MS represented around 30 % of the OA estimated by the TOT method, mainly due to the different desorption temperatures, with a maximum of 870 and 350 °C for TOT and TD-PTR-MS, respectively. Average emission factors (EF) organic aerosol (OA) and organic carbon (OC) were calculated for HDV and LDV fleet. We found that HDV emitted more OA and OC than LDV, and that OC emissions represented 36 and 43 % of total PM2.5 emissions from LDV and HDV, respectively. More than 700 ions were identified by TD-PTR-MS and the EF profiles obtained from HDV and LDV exhibited distinct features. Nitrogen-containing compounds measured in the desorbed material up to 350 °C contributed around 20 % to the EF values for both types of vehicles, possibly associated with incomplete fuel burning. Additionally, 70 % of the organic compounds measured from the aerosol filters with TD-PTR-MS were oxygenated for LDV and HDV, suggesting that the oxygenation occurs during fuel combustion and that the oxygen content of the fuel itself contributes. The thermal desorption analysis showed that HDV emitted compounds with higher volatility, mainly oxygenated (with up to 2 oxygen atoms) and longer chain hydrocarbons than LDV.