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Mixing ratios and fluxes of six selected volatile organic compounds (VOCs)were measured above the city of Manchester (UK) during the summer of 2006. Aproton transfer reaction-mass spectrometer was used for the measurement ofmixing ratios, and fluxes were calculated from these using both the disjunctand the virtual disjunct eddy covariance techniques. The two flux systems,which operated in alternate half hours, showed good agreement, with R2values ranging between 0.74 and 0.9 for the individual analytes. On average,fluxes measured in the disjunct mode were approximately 20% lower than thosemeasured in the virtual mode. This difference is due to both the dampening ofthe VOC signal by the disjunct flux sampler and carry over from one sample tothe next. Correcting for these effects reduced the difference to less than7%. Observed fluxes are thought to be largely controlled by anthropogenicsources, with vehicle emissions the major contributor. However, bothevaporative and biogenic emissions may account for some of the VOCs present.Concentrations and fluxes of the oxygenated compounds were highest onaverage, ranging between 0.15 to 1 mg m−2 h−1; the fluxes ofaromatic compounds were lower, between 0.12 to 0.28 mg m−2 h−1.The observed fluxes were up-scaled to give city wide emission estimates foreach compound and the results compared to estimates made by the NationalAtmospheric Emission Inventory (NAEI) for the same flux footprint. Fluxes oftoluene and benzene compared most closely differing by approximately 50%,while in contrast the oxygenated fluxes were found to be between 3.6–6.3times larger than the annual average predicted by the NAEI

Mixing ratios and eddy covariance flux measurements of volatile organic compounds from an urban canopy (Manchester, UK)