1. A new parameterization of biogenic SOA formation based on smog chamber data: 3D testing in CMAQ Manuel Santiago 1, Ariel F. Stein 2, Marta G. Vivanco 1, Yunsoo Choi 3 and Rick Saylor 4 1 CIEMAT (Research Center for Energy, Environment and Technology). Madrid. SPAIN 2 ERT on assignment of NOAA/ARL, Silver Spring MD 3 NOAA/ARL, Silver Spring, MD 4 NOAA/ARL, Atmospheric Turbulence and Diffusion Division, Oak Ridge, TN 2011 CMAS Conference manuel.santiago@ciemat.es

2. Motivation  Biogenic SOA, accounts for the largest fraction of the global atmospheric aerosol  EUPHORE smog chamber experiments: CMAQ paramaters that govern SOA originated by terpenes clearly overestimate our experimental data.  Here, a semi-empirical parameterization based on product distribution given by BVOCs oxidation pathways is presented for  -pinene + limonene SOA

3. Terpene SOA in CMAQ v4.7  Based on the partition parameters obtained by Griffin et al. 1999 Two Product Model for different BVOCs Griffin et al., 1999

4. Terpene SOA in CMAQ v4.7 Compound wght alpha1 Kom1 alpha2 Kom2 ---------- ---- ------ ------ ------ ------ a-pinene 0.4.038.171.326.0040 b-pinene 0.25.13.044.406.0049 d3-carene 0.15.054.043.517.0042 sabinene 0.1.067.258.399.0038 limonene 0.1.239.055.363.0053 alpha1 cstar1 alpha2 cstar2 ------ ------ ------ ------ CMAQ TERPENE.1123 7.466.5013 110.77 Straighforward implementation Lack of known of the product distributions for all the identified SOA precursor pathways Why two-product model?

5. Semiempirical Parameterization Theoretical K om,i calculation for individual SOA constituents  -pin + limo yield calculation Two product model fit (Based on theoretical constraints) Comparison with current CMAQ parameters

6. Smog Chamber Experiments  Outdoor chamber EUPHORE (CEAM, Valencia, Spain)  Approximated volume of 200 m 3  Biogenic VOCs mixture photooxidation experiments: (isoprene +  -pinene + limonene) + HONO

7. Smog Chamber Experiments ppb CHAMBER : ppb RURAL ATM. = 10 2 – 10 3 Exp.ISOAPINLIMOHONONONO 2 SO 2 ppbC/ppbNOxTRH ppb K% 250608190100 1702315.329911 240609107665899341286.83020.5 1410099250 874810.829830 2610091227140534118.330019 2710096365101329.62988 2910099959533071503.52978 11110987505140244895133.929419 0706108879761651984615.530220

8.  -pinene SOA products (Kamens and Jaoui, 2001) p o L,i (Torr) K om,i (m 3.  g -1 ) Limonene SOA products (Jaoui et al., 2006) p o L,i (Torr) K om,i (m 3.  g -1 ) Pinic acid 7.6E-070.1450 Limonic acid 6E-070.1860 10-Hydroxypinonic acid 7.1E-070.1560 7-hydroxylimononic acid 5.5E-070.2000 Ketolimonic acid 2.4E-070.4710 Ketonorlimononic acid 6.2E-070.1770 Pinonic acid 1.1E-040.0010 5-hydroxyketolimononic acid 2.2E-070.5070 Norpinonic acid 2.9E-040.0004 4-oxopinonic acid 1.3E-050.0088 Limononic acid 8.4E-050.0013 10-hydroxypinonaldehyde 1.1E-040.0010 Ketolimononic acid 3.3E-050.0033 Organic nitrate 1.2E-040.0009 Organic nitrate 1E-040.0011 0.1 m 3 /  g < K om,1 < 0.5 m 3 /  g 0.01 m 3 /  g < K om,2 < 0.001 m 3 /  g Individual K om,i calculation The contribution method SIMPOL.1 (Pankow and Asher, 2008) was used for the calculation of individual p o L,i and K om,i

9. Y isoprene = 0.02  -pin + limo Yield Calculation  1 = 0.1939 K om,1 = 0.1106 m 3.  g -1  2 = 0.2 K om,2 = 0.0056 m 3.  g -1

10. Model Description CMAQ v4.7 simplified version: only gas phase chemistry and aerosol formation  Domain: 4 x 4 cell grid located in Valencia, Spain (LAT: 39, LON: 0)  Meteorology: Hourly T, P and QV values measured in the chamber  CCTM Conditions: Gas/Aerosol mechanism: CB05-AERO5 Solver: SMVGEAR Temporal Resolution: 000100 (hhmmss)

11. 11 K om,1,298K (m 3.  g -1 ) cstar (m 3.  g -1 ) 22 K om,2,298K (m 3.  g -1 ) cstar (m 3.  g -1 ) TRP_originalAPIN0.04940.35290.42380.0083 LIMO0.31070.11350.47190.0109 TRP0.18010.13027.680.44790.0097103.596 TRP_revisedAPIN0.02690.56180.30890.0131 LIMO0.58190.0431 TRP0.30440.048320.70.15440.013176.182 TRP_fitTRP0.19390.11069.040.20.0056180.08 Parameterizations to test TRP_original : Current parameters in CMAQ v4.7 (scale up of  i to consider 1.3 g/cc density) TRP_revised: re-derived parameters for 1.3 g/cc density (Carlton et al.2010) TRP_fit: parameters obtained in this work (Santiago et al., 2011, submitted to ES&T)

12. data alpha / 0.0718, ! SV_ALK & 0.0386, 0.1119, ! SV_XYL1, SV_XYL2 & 0.0758, 0.1477, ! SV_TOL1, SV_TOL2 & 0.0942, 1.162, ! SV_BNZ1, SV_BNZ2 & 0.1123, 0.5013, ! SV_TRP1, SV_TRP2 & 0.232, 0.0288, ! SV_ISO1, SV_ISO2 & 1.3 / ! SV_SQT data cstar / 0.020, ! SV_ALK & 1.314, 34.483, ! SV_XYL1, SV_XYL2 & 2.326, 21.277, ! SV_TOL1, SV_TOL2 & 0.302, 111.11, ! SV_BNZ1, SV_BNZ2 & 7.466, 110.77, ! SV_TRP1, SV_TRP2 & 116.01, 0.617, ! SV_ISO1, SV_ISO2 & 12.193 / ! SV_SQT Model Description orgaer5.f

13. Chamber Experiments Simulations

14. TRP_originalTRP_revisedTRP_fit 250608 147.393.848.2 240609 70.236.78.0 141009 72.038.03.0 261009 96.357.218.0 271009 101.055.811.4 291009 101.560.323.7 111109 81.940.64.8 070610 82.043.47.9 Normalized Mean Bias (%)

15. CMAQ v4.7 3D Settings  Study Period: August 2009  Emissions: based on NEI 2005  Meteorology: NAM  Horizontal/Vertical Resolution: 12 km/22 layers  Boundary Conditions: GEOSCHEM monthly average  Chemical/Aerosol Mechanism: CB05-AE5

16. TRP_original SOA Monthly Average

17. Effect of different parameters TRP_original – TRP_revised TRP_original – TRP_fit

18.  A 2 product parameterization for SOA from  -pinene and limonene has been calculated with a mixed theoretical-experimental approach  Mechanistic considerations considered in TRP_fit represent an improvement of the treatment of SOA from  -pinene and limonene  Parameters re-derived by Carlton et al. 2010 (TRP_revised) reduce original parameters bias by 50%. Still an overprediction is observed (NOx dependent SOA?) Summary  Differences in the chamber experiment simulations do not drive to substantial changes on the model response on SOA monthly average concentration  TRP_revised and TRP_fit show a similar reduction of the original CMAQ values (TRP_original).  Only  -pinene and limonene parameters have been calculated in this work. The same procedure should be done for the rest of terpenes SMOG CHAMBER EXPERIMENTS 3-D AUGUST 2009 SIMULATION