Secondary organic aerosol formed by EURO 5 gasoline vehicle emissions: chemical composition and gas-to-particle phase partitioning

Abstract. In this study we investigated the photo-oxidation of EURO 5 gasoline vehicle emissions during cold urban, hot urban and motorway Artemis cycles. The experiments were conducted in an environmental chamber with average OH concentrations ranging between 6.6x10⁵–2.3x10⁶ molecules cm^-3, relative humidity (RH) 40–55 % and temperatures between 22–26 °C. A proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and the chemical analysis of aerosol on-line (CHARON) inlet coupled with a PTR-ToF-MS were used for the gas and particle phase measurements respectively. This is the first time that CHARON inlet was used for the identification of the secondary organic aerosol (SOA) produced from vehicle emissions. The secondary organic gas phase products ranged between C₁ and C₉ with 1 to 4 atoms of oxygen and were mainly composed of small oxygenated C₁–C₃ species. The formed SOA contained compounds from C₁ to C₁₄, having 1 to 6 atoms of oxygen and the products’ distribution was centered at C₅. Organonitrites and organonitrates contributed 6–7 % of the SOA concentration. Relatively high concentrations of ammonium nitrate (35–160 µg m^-3) were formed. The nitrate fraction related to organic nitrate compounds was 0.12–0.20, while ammonium linked to organic ammonium compounds was estimated only during one experiment reaching a fraction of 0.19. The produced SOA exhibited logC^* values between 2 and 5. Comparing our results to the theoretical estimations, we observed differences of 1–3 orders of magnitude indicating that additional parameters such as RH, particulate water content, aerosol hygroscopicity, and possible reactions in the particulate phase may affect the gas-to-particle partitioning.