1. Measurement and Evaluation of VOC emissions Carsten Warneke NOAA Earth System Research Laboratory and CIRES, University of Colorado Boulder, Colorado Outline: 1.Biogenic emission inventory validation 2.Anthropogenic emission ratios 3.Biomass burning Outline: 1.Biogenic emission inventory validation 2.Anthropogenic emission ratios 3.Biomass burning

2. Isoprene emissions: Available Data and Inventories SOS 1999 ICARTT 2004 TEXAQS 2006 TEXAQS 2000 Isoprene emissions inventories: BEIS3.12 (EPA) BEIS3.13 (EPA) MEGAN (Guenther et al)

3. Chemistry and Mixing Method Emissions from concentration measurements (Mixed Boundary Layer Method) Emissions from inventories (using aircraft data for light and temperature) BEIS3.12 and BEIS3.13: MEGAN: c t and c l temperature and light dependence of emissions  t,  l,  LAI and  age temperature, light, leaf area index and leaf age dependence

4. Comparison: Isoprene Emissions All Data Values above 1: inventories are larger MEGAN always higher than BEIS Texas: inter-annual variability in agreement factor of two

5. Summary Quantitative Comparison of Biogenic Emissions MEGAN > measurements > BEIS3.12 no clear recommendation due to uncertainties (ensemble) state of the art inventory validation Warneke et al in press

6. 1. Determine photochemical age from ratios between toluene and benzene: 2. Extrapolate hydrocarbon emission ratios to a zero photochemical age de Gouw et al., JGR, 2005, Warneke et al., JGR 2007 Determination of Anthropogenic VOC Emission Ratios Ron Brown data from ICARTT2004 and NEAQS-ITCT2002 EPA NEI99 CO emission data J. Roberts

7. Intercepts give the emission ratios: Benzene / acetylene = 0.21(2004: 0.17) Ethyl benzene / acetylene = 0.11(2004: 0.09) Determination of Anthropogenic VOC Emission Ratios

8. Urban VOC Emission Inventory Inventory: - based on EPA NEI-99 Ver. 3 - on-road, non-road, area, point sources - box around Boston, New York, Los Angeles, Houston and Dallas - ratio with CO Emissions inventory: S. McKeen and G. Frost

9. Emission inventory for this area Comparison with Emission Inventory CO data: B. Lerner, E. Williams

10. Emission inventory for this area  Small alkanes underestimated in inventory  Similar to findings of Sive et al. in 2002 Comparison with Emission Inventory

11. Emission inventory for this area  Inventory underestimates oxygenates  Oxygenates are low in vehicle exhaust  What are the primary urban sources? Comparison with Emission Inventory

12. Emission inventory for this area Inventory overestimates toluene by factor of ~2.5 Comparison with Emission Inventory Warneke et al 2007 and de Gouw et al 2005

13. Biomass Burning emissions Instrument platform

14. Biomass Burning emissions Emission ratios or emission factors for various fuel types of over 100 different VOCs Veres et al in prep Roberts et al in prep

15. Biomass Burning emissions FLEXPART total BB CO Fire counts in Russia total amounts of BB CO, aerosol and VOCs in different regions BB emissions verified using comparisons with measurements Agrees to within 30% for Alaska Warneke et al 2009, Warneke et al in press

16. Summary: - capabilities for VOC emission determination and inventory validation What can we do better? What would be helpful to improve inventories?