Detailed Speciation of Non-Methane Volatile Organic Compounds in Exhaust Emissions from Diesel and Gasoline Euro 5 Vehicles Using Online and Offline Measurements.

The characterization of vehicle exhaust emissions of volatile organic compounds (VOCs) is essential to estimate their impact on the formation of secondary organic aerosol (SOA) and, more generally, air quality. This paper revises and updates non-methane volatile organic compounds (NMVOCs) tailpipe emissions of three Euro 5 vehicles during Artemis cold urban (CU) and motorway (MW) cycles. Positive matrix factorization (PMF) analysis is carried out for the first time on proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) datasets of vehicular emission. Statistical analysis helped to associate the emitted VOCs to specific driving conditions, such as the start of the vehicles, the activation of the catalysts, or to specific engine combustion regimes. Merged PTR-ToF-MS and automated thermal desorption gas chromatography mass spectrometer (ATD-GC-MS) datasets provided an exhaustive description of the NMVOC emission factors (EFs) of the vehicles, thus helping to identify and quantify up to 147 individual compounds. In general, emissions during the CU cycle exceed those during the MW cycle. The gasoline direct injection (GDI) vehicle exhibits the highest EF during both CU and MW cycles (252 and 15 mg/km), followed by the port-fuel injection (PFI) vehicle (24 and 0.4 mg/km), and finally the diesel vehicle (15 and 3 mg/km). For all vehicles, emissions are dominated by unburnt fuel and incomplete combustion products. Diesel emissions are mostly represented by oxygenated compounds (65%) and aliphatic hydrocarbons (23%) up to C22, while GDI and PFI exhaust emissions are composed of monoaromatics (68%) and alkanes (15%). Intermediate volatility organic compounds (IVOCs) range from 2.7 to 13% of the emissions, comprising essentially linear alkanes for the diesel vehicle, while naphthalene accounts up to 42% of the IVOC fraction for the gasoline vehicles. This work demonstrates that PMF analysis of PTR-ToF-MS datasets and GC-MS analysis of vehicular emissions provide a revised and deep characterization of vehicular emissions to enrich current emission inventories.

Euro 6 Unregulated Pollutant Characterization and Statistical Analysis of After-Treatment Device and Driving-Condition Impact on Recent Passenger-Car Emissions.

This study aims to measure and analyze unregulated compound emissions for two Euro 6 diesel and gasoline vehicles. The vehicles were tested on a chassis dynamometer under various driving cycles: Artemis driving cycles (urban, road, and motorway), the New European Driving Cycle (NEDC) and the World Harmonized Light-Duty Test Cycle (WLTC) for Europe, and world approval cycles. The emissions of unregulated compounds (such as total particle number (PN) (over 5.6 nm); black carbon (BC); NO2; benzene, toluene, ethylbenzene, and xylene (BTEX); carbonyl compounds; and polycyclic aromatic hydrocarbons (PAHs)) were measured with several online devices, and different samples were collected using cartridges and quartz filters. Furthermore, a preliminary statistical analysis was performed on eight Euro 4-6 diesel and gasoline vehicles to study the impacts of driving conditions and after-treatment and engine technologies on emissions of regulated and unregulated pollutants. The results indicate that urban conditions with cold starts induce high emissions of BTEX and carbonyl compounds. Motorway conditions are characterized by high emissions of particle numbers and CO, which mainly induced by gasoline vehicles. Compared with gasoline vehicles, diesel vehicles equipped with catalyzed or additive DPF emit fewer particles but more NOx and carbonyl compounds.