In 2011, the European Commission introduced a limit for nonvolatile particle number (PN) emissions >23 nm from light-duty (LD) vehicles and the stated intent is to implement similar legislation for on-road heavy-duty (HD) engines at the next legislative stage. This paper reviews the recent literature regarding the operation-dependent emission of PN from LD vehicles and HD engines, and the measurement procedure used for regulatory purposes. The repeatability of the PN method is of the order of 5% and higher scatter of the results can easily be explained by the effect of the vehicles or the aftertreatment devices on the PN emissions (e.g., the fill state of the diesel particulate filters). Reproducibility remains an issue since it may exceed 30%. These high-variability levels are mainly associated with calibration uncertainties of the PN instruments. Correlation measurements between the full-flow dilution tunnels (constant-volume samplers, CVS) and the proportional partial-flow dilution systems (PFDS) showed agreement within 15% for the PN method down to 1 × 10 11 p/kWh. At lower concentrations, the PN background of the CVS and/or the PFDS can result in larger inconsistencies. The filter-based particulate matter (PM) mass and the PN emissions correlate well down to 1-2 mg/km for LD vehicles and to 2-3 mg/kWh for HD applications. The correlation improves when only elemental carbon mass is considered: it is relatively good down to 0.1-0.3 mg/km or mg/kWh. ACRONYMS AND ABBREVIATIONS ACEA Association des Constructeurs Européens d'Auto mobiles (European Automobile Manufacturers' Association) AM Accumulation mode APC AVL particle counter

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We characterized the properties of combustion aerosol produced at different operating conditions of a mini-CAST burner that was treated in a Catalytic Stripper (CS) operating at 300• C. The goal was to establish a methodology for the production of soot particles resembling those emitted from internal combustion engines. Thermo-optical analysis of samples collected on Quartz filters revealed that the particles contained semi-volatile material that survived the CS. The amount of semi-volatile species strongly depended on the operating conditions ranging from less than 10% to as high as 30% of the particle mass. The mini-CAST operating conditions were also found to have a strong effect on the effective particle density (ρ e ). The ρ e , for example, ranged from as low as 0.3 to 1.05 g/cm 3 for mondisperse 80 nm particles, although the massmobility exponent remained relatively constant (2.1-2.25). These differences are indicative of differences in the primary particle diameter, which was estimated to range between 8.5 and 34 nm depending on the operating conditions. The different types of particles produced were also found to exhibit different affinities for butanol but also different light absorption per mass of elemental carbon which can, therefore, lead to inconsistencies in aerosol instrumentation calibrations (e.g., condensation and optical particle counters, photoacoustic sensors). The work highlights the importance of establishing a detailed and well-defined method in using the mini-CAST-CS approach for instrument calibration in ways mimicking various engine combustion sources.

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The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material.