Verification of the contribution of vehicular traffic to the total NMVOC emissions in Germany and the importance of the NO3 chemistry in the city air

In 1997 and 1998 several field campaigns for monitoring non-methane volatile organic compounds (NMVOCs) and nitrogen oxides (NOx) were carried out in a road traffic tunnel and in the city center of Wuppertal, Germany. C-2-C-10 aliphatic and aromatic hydrocarbons were monitored using a compact GC instrument. DOAS White and long path systems were used to measure aromatic hydrocarbons and oxygenated aromatic compounds. A formaldehyde monitor was used to measure formaldehyde. Chemiluminescence NO analysers with NO2 converter were used for measuring NO and NO2. The high mixing ratios of the NMVOCs observed in the road traffic tunnel, especially 2.9 ppbv phenol, 1.5 ppbv para-cresol and 4.4 ppbv benzaldehyde, in comparison with the measured background concentration clearly indicate that these compounds were directly emitted from road traffic. Para-Cresol was for the first time selectively detected as primary pollutant from traffic. From the measured data a NMVOC profile of the tunnel air and the city air, normalised to benzene (ppbC/ppbC), was derived. For most compounds the observed city air NMVOC profile is almost identical with that obtained in the traffic tunnel. Since benzene originates mainly from road traffic emission, the comparison of the normalised emission ratios indicate that the road traffic emissions in Wuppertal have still the largest impact on the city air composition, which is in contrast to the German emission inventory. In both NMVOC profiles, aromatic compounds have remarkably large contributions of more than 40 ppbC%. In addtion, total NMVOC/NOx ratios from 0.6 up to 3.0 ppbC/ppb in the traffic tunnel air and 3.4+/-0.5 in the city air of Wuppertal were obtained. From the observed para-cresol/toluene and ortho-cresol/toluene ratios in the city air, evidence was found that also during daytime NO3 radical reactions play an important role in urban air.