Ground-Based and Airborne Measurements of Nonmethane Hydrocarbons in BERLIOZ: Analysis and Selected Results

During the Berlin Ozone Experiment BERLIOZ in July–August 1998 quasi-continuous measurements ofC₂–C₁₂ nonmethane hydrocarbons (NMHCs) were carried out at 10 sites in and around the city of Berlin using on-line gas-chromatographic systems (GCs) with a temporal resolution of 20–120 minutes. Additional airborne NMHCmeasurements were made using canister sampling on three aircraft and an on-line GC system on a fourth aircraft. The ground based data are analyzed to characterize the different sites and to identify the influence of emissions from Berlin on its surroundings. Benzene mixing ratios at the 4 rural sites were rather low (<0.5 ppbv). Berlin (and the surrounding highway ring) was identified as the main source of anthropogenic NMHCs at Eichstädt and Blossin, whilst other sources were important at the furthermost site Menz. The median toluene/benzene concentration ratio in Berlin was 2.3 ppbv/ppbv, agreeing well with measurements in other German cities. As expected, the ratios at the background sites decreased with increasing distance to Berlin and were usually around one or below. On 20 and 21 July, the three northwesterly sites were situated downwind of Berlin and thus were influenced by its emissions. Considering the distance between the sites and the windspeed, the city plume was observed at reasonable time scales, showing decreasing toluene/benzene ratios of 2.3, 1.6 and 1.3 with increasing distance from Berlin. Isoprene was the only biogenic NMHC measured at BERLIOZ. It was themost abundant compound at the background sites on the hotter days, dominating the local NMHC reactivity with averaged contributions to the total OH loss rate of 51% and 70% at Pabstthum and Blossin, respectively. Emissionratios (relative to CO and to the sum of analysed NMHCs) were derived from airborne measurements. The comparison with an emission inventory suggests traffic-related emissions to be the predominating source of the considered hydrocarbon species. Problems were identified with the emission inventory for propane, ethene and pentanes.