Coagulation of combustion generated nanoparticles and their measurement behind vehicle engines: can they play a role as atmospheric pollutants?

Abstract. Based on photoionisation mass spectrometry two types of experiments were carried out. (i) In a fast flow reactor coupled to a low pressure flame as a particle source, rate coefficients for the coagulation of primary nanoparticles were measured through variation of the reactor residence time. The results are k_c (350K) = 3.5x10^-10cm³/s and k_c (573K) = 1.1x10^-9cm³/s, i.e. very high rate coefficients. It was also shown that coagulated nanoparticles can have masses beyond 50ku, corresponding to equivalent diameters between 4 to 5nm. These particles are easily fragmented during photoionisation. (ii) Using a second and mobile photoionisation mass spectrometer equipped with a fast flow inlet system, measurements were carried out behind three different vehicle engines, a two-stroke scooter engine, a four-stroke motorbike engine and a DI (direct injection) gasoline research engine. In all cases ion signals around 1000u were found that are clearly dependent on engine conditions. In the case of the DI engine, they correlate with the smoke number. These signals cannot be explained by PAHs due to their low volatility at the respective masses. Major contributions of soot or droplet fragmentation were ruled out through additional experiments using a heated inlet line and a filter. Consequently, these signals are interpreted as fragments of coagulated nanoparticles.