1. GEIA Conference – Nov. 18 th 2015 – Beijing- China Analyzing the spatial and temporal variability of the composition of anthropogenic VOC urban emissions from observations : a basis for the CMIP historical emission inventory a basis for the CMIP historical emission inventory A. Borbon 1*, Th. Salameh 1, C. Afif 2, S. Sauvage 3, N. Locoge 3, A. Waked 3, A. Baudic 4, V. Gros 4, F. Oztürk 5,, M. Keles 5, P. Dominutti 6, T. Nogueira 6, A. Fornaro 6 1 LISA, IPSL, CNRS, UMR 7583, University of Paris Est Créteil (UPEC) and Paris Diderot (UPD), Créteil, France, *now at LaMP, OPGC, CNRS UMR 6016, Univ. Blaise Pascal, Clermont-Ferrand, 2 Unité Environnement, Génomique Fonctionnelle et Études Mathématiques, Saint Joseph University, Beirut, Lebanon, 3 Mines Douai, SAGE, Douai, France, 4 LSCE, IPSL, CNRS, CEA, UVSQ, Gif-sur-Yvette, France, 5 AIBU, Faculty of Engineering and Architecture, Environmental Engineering Department, Bolu, Turkey, 6 Department of Atmospheric Sciences, University of São Paulo (IAG/USP), São Paulo, Brazil

2. spatial variability Consistency of urban emission composition by a factor of 2 (dominance of gasoline powered vehicles) except for alkanes and oxygenated VOCs (> factor of 10). Pretty good consistency of road transport emission profiles regardless of the region but OH-reactivity metric reveals significant differences for ozone and SOA precursors temporal variability low or high seasonality interannual variability : no significant change in emission speciation for trafic- related VOCs over the last decade. Emission controls would not affect speciation in time, at least for road transport. from Aït-Helal, PhD, 2014. Suburban Paris (MEGAPOLI)

3. Methods NMHC : alkanes, alkenes, aromatics, OVOC IVOC (up to C18) @ urban receptor sites - long-term and short-term - in-situ observations near source measurements (in situ, lab) recently collected up-coming from literature (Wang et al., 2014 ; Simpson et al., 2014) VOCs Instrumentation On-line and off-line : GC-FID, GC-MS, PTRMS, HPLC, canisters, sorbent tubes

4. Methods = combined diagnostic tools Source emission profiles derived from near source measurements (real conditions) (Salameh et al., 2014) Urban enchancement emission ratios vs CO and acetylene (Warneke et al., 2007 ; Borbon et al., 2013)

5. Spatial variability : urban emission ratios ER vs. CO : Beirut vs. Paris vs. LA vs Beijing Consistency within a factor of 2 except for the unburned fraction (alkanes) and oxygenated VOCs (when available, > factor of 10) Dominance of gasoline-powered vehicle Extends and confirms Borbon et al., 2013 between US cities (incl. LA) and European cities (incl. Paris) Salameh et al., in prep. for ACP

6. Spatial variability : road transport profiles Good consistency but, in term of reactivity, spatial variability turns significant by a factor of 2 to 8 for alkenes and to a less extent aromatics (toluene and xylenes)

7. Temporal variability seasonal interannual from French AASQA/EMEP (6 stations) Low seasonality (±30%) ≠ high seasonality in French urban areas for the fuel unburned fraction (Boynard et al., 2014) Trafic related compounds (ethylene, BTX) : no significant changes in emission composition NG related C2-C3 alkanes : +1.8% to +10% Fuel-evaporation related C4-C5-alkanes : constant or +1% to +12% Waked et al., in prep. for AE

8. references Methods : Aït Helal et al., Atmos. Chem. Phys., 14, 10439–10464, 2014, www.atmos-chem- phys.net/14/10439/2014/ Detournay et al., J. Environ. Monitor., 13, 983–990, 2011. Borbon et al., 2013, J. Geophys. Res., vol. 118, 2041–2057, doi:10.1002/jgrd.50059, 2013 Salameh, T., et al., Environ. Sci. Pollut. R., 21, 10867–10877, doi: 10.1007/s11356-014- 2978-5, 2014. VOC emission composition, source apportionment, trends, evaluation of emission inventories : Salameh, T., et al., Environ. Chem, 12, 316–328, doi: 10.1071/EN14154, 2015a. Salameh, T., et al., Atmos. Chem. Phys. Discuss., 15, 26795-26837, doi: 10.5194/acpd-15- 26795-2015, 2015b. Salameh et al., Composition of organic carbon during ECOCEM : new observational constraints for VOC/OVOC anthropogenic emission evaluation in the Middle East region. 2016, in prep for ACP Boynard et al., 2014, Atmos. Envir., doi.org/10.1016/j.atmosenv.2013.09.039, 2014 Simpson et al., doi.org/10.1021/es5017476 | Environ. Sci. Technol. 2014, 48, 8529−8537 Waked et al., 2016, Multi-year trend inferred from observations in French urban and rural atmospheres, in prep for Atmos. Envir. Wang et al., ACP, doi:10.5194/acp-14-5871-2014, 2014