Modeling of Organic Aerosol during the MEGAPOLI Summer Campaign in - - PowerPoint PPT Presentation

Modeling of Organic Aerosol during the MEGAPOLI Summer Campaign in the Paris Region

CHIMERE - Volatility Basis Set approach CHIMERE - Volatility Basis Set approach

Q.J.Zhang (1)*, M.Beekmann (1), L. Poulain (2), A. Held (2), A. Wiedensohler (2) , K. Kamilli (2), H. Herrmann (2), P. de Carlo (3), M. Crippa (3), R. Chirico (3), M. Heringa (3), Claudia Mohr (3), A. Prevot (3), U. Baltensperger (3), E. Freney (4), A. Schwarzenboeck (4), K. Sellegri (4), J.M. Pichon (4), L. Gomes (5), B. Bessagnet (6), S. Pandis (7), A. Hodzic(8) zhang@lisa.univ-paris12.fr (1) Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Université Paris Est et 7, CNRS, Créteil, France

1

2010/06/03

Créteil, France (2) Institute for Troposphärenforschung, Leipzig, Germany, (3) Paul Scherrer Institut, Villingen, Switzerland, (4) Laboratoire de Météorologie Physique, Clermont-Ferrand, France (5) Centre National de Recherche Météorologique, Toulouse, France (6) Institut National de l'EnviRonnement industriel et des rISques, Verneuil en Halatte, France (7) Foundation for Research and Technology, Hellas, University of Patras, Greece (8) National Center for Atmospheric Research, USA. * Also Aria technologies

Harmo13, Paris

• SOA (Secondary Organic Aerosol):

under-estimated in Chemistry Transport Models

Context & Objective

Comparison Model / Measurement, 05/2007-06/2007 LHVP , (urban MEGAPOLI site)

Volkamer et al., GRL, 2006

LHVP , (urban MEGAPOLI site)

Observed SOA (J. Sciare, LSCE) Simulated SOA (classic) Simulated anthropogenic SOA (classic)

2

Volatility Basis Set approach (VBS) ) Objective: Improve simulation of SOA in CHIMERE (regional CTM) MEGAPOLI Paris Campaign: Quantify primary and secondary sources of organic aerosols, in urban and in plume

Robinson et al., 2007 Lane et al. 2008 Compare with MEGAPOLI measurements

MEGAPOLI Campaign - Measurements

Forest ATR - 42 3 primary sites => suite of in situ measurements / + meteo at SIRTA. 3 secondary sites => lidar and spectroscopic measurements / or in situ

PARIS

• 20km

Forest

• !
• Matthias.BEEKMANN

(Tuesday 14h, Harmo13) 3 secondary sites => lidar and spectroscopic measurements / or in situ 3 mobile labs => full in situ measurements (PSI + MPI) + Univ Duisburg 1 mobile lab => lidar measurements (CEA) 1 mobile lab => MAXDOAS (MPI) 1 aircraft ATR-42 => full in situ measurements (SAFIRE, CNRS, MPI)

SOA scheme in CHIMERE

OH, O3, NO3

• Classic scheme based on “two-product” approach of Odum et al. 1996

VOC precursors α∑SVOC (Surrogated Semi-volatile VOC species with distinct volatilities) (Pun et Seigneur,2006, Bessagnet et al. 2008)

Phase Phase transfer

Aerosol

• VBS « Volatility Basis-Set » approach

VOC precursors n ∑ SVOC with defined volatility bins

OH

(Robinson et al., 2007, Lane et al. 2008, Murphy and Pandis. 2009)

4

1 0.4 0.5 0.8

0.6 0.7 0.8 0.9 1

VBS approach main features

Normalized

Classic POA emission partitioning of POA (SVOC) emissions additional IVOC emissions

Chemical aging +OH

0.030.060.090.140.18 0.3 0.4 0.5

0.1 0.2 0.3 0.4 0.5 0.6

Normalized emission factor with respect to classic POA emission

∆Hv (kJ mol-1) C* (µg m-3) at 298K Saturation concentration

+OH

Robinson et al., 2007, Murphy et

• Pandis. 2009

5

150 112 106 106 94 88 82 76 70 64

∆Hv (kJ mol-1)

Semivolatile-SOA (S-SOA)

domain Resolution CONT 0.5°× 0.5°

Model configuration

CHIMERE

GFS/MM5

Meteorology

Gocart/LMDz GN9 9km ×9km

CHIMERE

Gas phase mechanism, 50 species,120 reactions

MELCHIOR2

Inorganic mechanism (Nenes et al., 1998)

ISORROPIA

Two-product method / VBS approach

SOA Scheme

CONT3 GN9

Paris

CONT3 GN9

Paris

6

EMEP Anthropo genic MEGAN Biogenic

Emissions

Total SOA=Oxygenated OA

• Simulations with classic scheme (POA non-volatile)
• Simulations with VBS

Model simulations

Semivolatile-SOA Anthropogenic SOA Biogenic SOA (BSOA)

VBS VBS Classic

Partitioning of POA emissions (SVOC) + additional IVOC Lumped VOC (Aromatics, Higher Alkanes, etc.) according to SAPRC  4 volatility bins Isoprene, Terpene, α- pinene, β-pinene, Limonene, Ocimene, Humunene

7 (Lane et al. 2008) (Robinson et al., 2007, Murphy and Pandis. 2009) (Pun and Seigneur, 2006; Bessagnet al. 2008)

Chemical aging Chemical aging

AMS measurements

Aerodyne aerosol Mass spectrometer (AMS)

• Organic Aerosol (OA=POA+SOA)

LHVP: by IFT (urban site) Preliminary simplified PMF (Positive Matrix) Factorization (Poor man’s PMF) Paris Factorization (Poor man’s PMF) Hydrocarbon-like Organic Aerosol (HOA) Biomass Burning Organic Aerosol (BBOA) HOA+BBOA Primary Organic Aerosol (POA) Oxygenated Organic Aerosol (OOA) OOA SOA(S-SOA+ASOA+BSOA) SIRTA: upwind of Paris agglomeration, by PSI (suburban site) OA –LaMP (µg/m3)

8

Flight: by LaMP

10 15 20 25

POA Model-Classic

10 15 20 25

HOA Model-VBS

10 15 20 25

HOA/BBOA AMS Poor man’s PMF

Paris

Simulation results (LHVP-Urban site)

• vs. ground based AMS measurements

µg/m3

In VBS, POASVOC+IVOC => reduce POA levels

5 TIME 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22

• 5

5 TIME 7/2 7/3 7/4 7/5 7/6 7/7 7/8 7/9 7/10 7/11 7/12 7/13 7/14 7/15 7/16 7/17 7/18 7/19 7/20 7/21 7/22 5 TIME 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22

µg/m3 OOA AMS Poor man’s PMF

9 12

SOA Model -Classic

9 12 9 12

OOA Model -VBS 9

Continental Local

3 6 TIME 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22 3 6 TIME 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22 3 6 TIME 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22

OA =HOA+OOA (LHVP-Urban site)

10 15 20 25 30

OA-AMS OA_Classic OA_VBS µg/m3

Continental Classic over-estimate peaks, close at background concentration VBS close at peaks, underestimate background concentration

5 10 July 01 July 02 July 03 July 04 July 05 July 06 July 07 July 08 July 09 July 10 July 11 July 12 July 13 July 14 July 15 July 16 July 17 July 18 July 19 July 20 July 21 July 22

µg/m3

8 10 12 POA_VBS OPOA_VBS ASOA_VBS BSOA

S-SOA_VBS

10

S-SOA+BSOA POA+BSOA

2 4 6 8 J u ly 1 J u ly 2 J u ly 3 J u ly 4 J u ly 5 J u ly 6 J u ly 7 J u ly 8 J u ly 9 J u ly 1 J u ly 1 1 J u ly 1 2 J u ly 1 3 J u ly 1 4 J u ly 1 5 J u ly 1 6 J u ly 1 7 J u ly 1 8 J u ly 1 9 J u ly 2 J u ly 2 1 J u ly 2 2 BSOA

Simulation results (SIRTA-Suburban site)

• vs. ground based AMS measurements

Paris

OA AMS OA Model -Classic OA Model -VBS µg/m3

4 8 12 16 20

Upwind => background concentration is low

µg/m3

4 July 01 July 02 July 03 July 04 July 05 July 06 July 07 July 08 July 09 July 10 July 11 July 12 July 13 July 14 July 15 July 16 July 17 July 18 July 19 July 20 July 21 July 22

Downwind Mostly BSOA

6 9 12

POA _V BS OPOA _V BS A SOA _V BS BSOA

S-SOA_VBS 11 11

Continental

3 6 July 01 July 02 July 03 July 04 July 05 July 06 July 07 July 08 July 09 July 10 July 11 July 12 July 13 July 14 July 15 July 16 July 17 July 18 July 19 July 20 July 21 July 22

Diurnal Variation of OA (LHVP-Urban site)

10 12 14 OA_Classic_Diurnal_Variation OA_VBS_Diurnal_Variation OA_AMS_Diurnal_Variation µg/m3 2 4 6 8 10 12 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 Daytime (Hr )

Classic scheme: Wrong morning peak due to primary emissions (non-volatile) With VBS scheme: Peak in the morning corrected <=> distribution of POA into S/IVOC But OOA lacks in the evening

20,00 25,00

OA-AMS-Poor man's PMF OA_VBS OA_VBS_HY

High yield case (LHVP-Urban site)

• POA-SVOC/IVOC emissions *2 - Anthropogenic SOA yield *2

Paris

0,00 5,00 10,00 15,00 TIME 7/2 7/3 7/4 7/5 7/6 7/7 7/8 7/9 7/10 7/11 7/12 7/13 7/14 7/15 7/16 7/17 7/18 7/19 7/20 7/21 7/22 7/23

13

Background concentration underestimated Peak overestimated

Regional influence on OOA plume

Anthropogenic Biogenic Local

14 14

14

Local formation of OA vs. measurements on flight

Flight 32 20090721

y = 0,1631x - 2,4517

14

µg/m3

Measurement µg/m3 100KM

y = 0,0695x - 3,2018

2 4 6 8 10 12 14

Model-VBS

y = 0,1631x - 2,4517

2 4 6 8 10 12 14

Measurement

OA

µg/m3

Background concentration

Model VBS µg/m3

15 15

10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90

Ox=O3+NO2

ppb

Conclusion

The “Volatility Basis Set” VBS approach has been implemented into a regional CTM (CHIMERE)

and evaluated with measurements from the MEGAPOLI Paris summer campaign Urban / suburban sites

The VBS approach avoids an overestimation of urban HOA especially in the morning, OOA

lacks in the evening

OOA peaks with strong continental influx, and a local peak with strong simulated anthropogenic

aerosol are better simulated by VBS => important contribution from S-SOA vs. ASOA

Underestimation of OOA peaks with simulated BSOA origin,

underestimation of urban background concentrations.

High yield case overestimes OA peak, but still underestimes local OA background

Plume evolution (for one flight with strong OA formation in plume):

16 16

• VBS under-estimates background OA levels;

slope of ∆OA / ∆Ox plot is OK within a factor of two => OK considering VBS uncertainties OUTLOOK : Sensitivity tests under way (ASOA yield, chemical aging speed, POA emissions and volatility) Redo evaluation with full data set , including winter campaign

Acknowledgement

The research leading to these results has received funding from the European Community's Seventh Framework Programme FP/2007-2011 MEGAPOLI under grant agreement n°212520. The MEGAPOLI campaign has received additional grant agreement n°212520. The MEGAPOLI campaign has received additional support by French ANR and LEFE/CHAT programs, and by the Ile de France SEPPE program. IFT, PSI and LaMP teams are thanked for providing AMS measurement data.

17 17

Thank you !

Annexe

C* (µg m-3) at 300K Lumped VOC

1 10 100 1000

ALK4 0.01 ALK5 0.1 ARO1 0.01 0.03 0.075 0.25 ARO2 0.02 0.04 0.08 0.25 OLE1 0.001 0.002 0.023 0.045

ASOA

OLE2 0.003 0.006 0.023 0.076 (SAPRC99)

Context & Objective VBS approach in CHIMERE

Outline

CTM configuration Simulation results: (from 20090701-20090722)

• 1. Comparisons with ground based AMS measurements

Organic Aerosol (OA)

• LHVP (Urban)
• SIRTA (Suburban)
• 2. Regional/local plume of Oxygenated OA (OOA)

Conclusion