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<p>Changes in engine technologies and after-treatment devices can profoundly alter the chemical composition of the emitted pollutants. To investigate these effects, we characterized the emitted particles' chemical composition of three diesel and four gasoline Euro 5 light-duty vehicles tested at a chassis dynamometer facility. The dominant emitted species was black carbon (BC) with emission factors (EFs) varying from 0.2 to 7.1 mg km<span class="inline-formula">⁻¹</span> for direct-injection gasoline (GDI) vehicles, from 0.02 to 0.14 mg km<span class="inline-formula">⁻¹</span> for port fuel injection (PFI) vehicles, and 0.003 to 0.9 mg km<span class="inline-formula">⁻¹</span> for diesel vehicles. The organic matter (OM) EFs varied from 5 to 103 <span class="inline-formula">µ</span>g km<span class="inline-formula">⁻¹</span> for GDI gasoline vehicles, from 1 to 8 <span class="inline-formula">µ</span>g km<span class="inline-formula">⁻¹</span> for PFI vehicles, and between 0.15 and 65 <span class="inline-formula">µ</span>g km<span class="inline-formula">⁻¹</span> for the diesel vehicles. The first minutes of cold-start cycles contributed the largest PM fraction including BC, OM, and polycyclic aromatic hydrocarbons (PAHs).</p> <p>Using a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS), we identified more than 40 PAHs in both diesel and gasoline exhaust particles including methylated, nitro, oxygenated, and amino PAHs. Particle-bound PAHs were 4 times higher for GDI than for PFI vehicles. For two of the three diesel vehicles the PAH emissions were below the detection limit, but for one, which presented an after-treatment device failure, the average PAHs EF was 2.04 <span class="inline-formula">µ</span>g km<span class="inline-formula">⁻¹</span>, similar to the GDI vehicle's values.</p> <p>During the passive regeneration of the catalysed diesel particulate filter (CDPF) vehicle, we measured particles of diameter around 15 nm mainly composed of ammonium bisulfate. Transmission electron microscopy (TEM) images revealed the presence of ubiquitous metal inclusions in soot particles emitted by the diesel vehicle equipped with a fuel-borne-catalyst diesel particulate filter (FBC-DPF). X-ray photoelectron spectroscopy (XPS) analysis of the particles emitted by the PFI vehicle showed the presence of metallic elements and a disordered soot surface with defects that could have consequences on both chemical reactivity and particle toxicity.</p> <p>Our findings show that different after-treatment technologies have an important effect on the emitted particles' levels and their chemical composition. In addition, this work highlights the importance of particle filter devices' condition and performance.</p>