TM4-ECPL modeling activities

Transcription

1 TM-meeting, May 2011, ISPRA TM4-ECPL modeling activities Stelios Myriokefalitakis, Nikos Daskalakis, Kanakidou Maria Environmental Chemical Process Laboratory (ECPL), Department of Chemistry, University of Crete Kostas Tsigaridis NASA,GISS & Uni Columbia, NY

2 1. Multiphase chemistry (Stelios) 2. Interannual model evaluation & AEROCOM (Nikos) 3. Other ongoing and future activities (Maria)

3 SOA formation via aqueous-phase chemistry in TM4-ECPL Myriokefalitakis et al, ACPD, 11,485, VOC photo-oxidation in the gas-phase 2. Production of water-soluble organic compounds in the gas-phase (e.g. aldehydes, organic acids) 3. Phase transfer between the gas and the aqueous phase 4. Production of low volatile compounds in the aqueous-phase (e.g. oxalic acid) 5. Upon cloud evaporation new organic particulate matter is formed OH VOC O 3 R-CHO Henry NO 3

4 The Revised Aqueous-Phase Chemical Scheme in TM4- ECPL 1. NO 3 Aqueous-phase Oxidation of Aldehydes and Organic Acids 2. Lower Henry Constant of OH radicals ( mol lt -1 atm -1 -> 30 mol lt -1 atm -1 ) 3. Different cloud droplet radius over land (5 μm) and over oceans (10 μm) 4. Simultaneously S(IV) and Organic molecules aqueous-phase oxidation using EBI solver

5 ph Dependence of S(IV) oxidation by ozone TM4-ECPL does not take into account the different forms of the sulfuric acid (SO 2.H 2 O, HSO 3-, SO 3-2 )., in order to take into account the different forms and reaction rates, we use the mole fraction (ξ) of each acid as a function of ph. The total mass of S(IV) is calculated as S(IV)=SO 2.H 2 O + HSO 3- + SO SO. H O 2 2 [ SO2 H 2O] Keq1 Keq1Keq 1 2 [ S( IV )] [ H ] [ H ] 2 1 HSO 3 [ HSO3 ] [ H ] Keq 2 1 [ ( )] 1 [ ] S IV Keq H 1 SO 2 3 [ SO 1 [ ( )] S IV Keq ] [ H ] [ H ] 2 Keq Keq For 25 o C, the oxidation of SO 2.H 2 O, HSO 3-, SO -2 3 accounts a rate of Keq 1 = mol -1 lt s -1, Keq 2 = mol -1 lt s -1 and Keq 3 = mol -1 lt s -1 proportionally (Seinfeld and Pandis,1998). Ktotal(SIV)=Keq1*ξ SO2.H2O + Keq2*ξ ΗSΟ3- + Keq 3 *ξ SO3= mol -1 lt s E E E E E E E+04 S(IV) Oxidation Rate - TM4-ECPL Keq1 Keq2 Keq3 Ktotal 1.00E E ph

6 Inorganic Aqueous-Phase Chemistry Aqueous Phase Reactions 1 Ο 3 + hv (+ H 2 O) H 2 O 2 + O 2 2 H 2 O 2 + hv 2OH 3 NO 3- + hv (+ H + ) ΝΟ 2 + ΟΗ 4 HO 2 + HO 2 H 2 O 2 + O 2 5 HO 2 + O 2- (+ H + ) H 2 O 2 + O 2 6 O 3 + O 2- (+ H + ) OH + 2O 2 7 O 3 + OH HO 2 + O 2 8 HO 2 + OH O 2 + H 2 O 9 OH + OH H 2 O 2 10 H 2 O 2 + OH HO 2 + H 2 O 11 NO 3 + HO - NO 3- + OH 12 S(IV) + H 2 O 2 SO S(IV) + O 3 SO 2-4

7 SO4 2- (ngs m -3 ) SO4 2- (ngs m -3 ) SO4 2- (ngs m -3 ) SO validation in TM4-ECPL SO4 2- (ngs m -3 ) SO4 2- (ngs m -3 ) Finokalia (35N, 25E) SO4 (ngs/m³ ) - Measurements SO4 (ngs/m3) S1 SO4 (ngs/m3) ACPD_S1 250 Amsterdam Island (37S, 77E) SO4 (ngs/m³ ) - Measurements SO4 (ngs/m3) - S1 SO4 (ngs/m3) - S1_ACPD J F M A M J J A S O N D Puy De Dome (45N, 2E) SO4 (ngs/m³ ) - Measurements SO4 (ngs/m3) S1 SO4 (ngs/m3) ACPD_S1 0 J F M A M J J A S O N D Schauinsland (45N, 7E) 2500 SO4 (ngc/m³ ) - Measurements SO4 (ngs/m3) S1 SO4 (ngs/m3) ACPD_S J F M A M J J A S O N D K. Pustza (46N, 19E) SO4 (ngs/m³ ) - Measurements SO4 (ngs/m3) S1 SO4 (ngs/m3) ACPD_S1 J F M A M J J A S O N D SO4 2- (ngs m -3) 0 J F M A M J J A S O N D Azores (38N, 27W) SO4 (ngs/m³ ) - Measurements SO4 (ngs/m3) S1 SO4 (ngs/m3) S1 J F M A M J J A S O N D

8 Organic Aqueous-Phase Chemical Scheme Aldehydes (C1-C3) Aqueous Phase Reactions 14 CH 2 (OH) 2 + OH (+ O 2 ) HCOOH + HO 2 + H 2 O 15 CH 2 (OH) 2 + NO 3 (+ O 2 ) HCOOH + HO 2 + NO 3- + H + 16 GLYAL + OH (+ O 2 ) GLY + HO 2 17 GLYAL + 2 OH (+ 2 O 2 ) GLX + 2HO H 2 O 18 GLYAL + NO 3 (+ O 2 ) GLX + HO 2 + NO 3- + H + 19 GLYAL + 2 NO 3 (+ O 2 ) GLY + 2 NO H + + H 2 O 20 GLY + OH (+ O 2 ) GLX + HO 2 + H 2 O 21 GLY + OH 0.03GLX OXL+ H 2 O 22 GLY + NO 3 (+ O 2 ) GLX + HO 2 + NO 3- + H + 23 GLY + hv/oh aerosol water) (only in 0.2OXL + 0.8OLIGOMERIC-SOA 24 GLY + NH + 4 aerosol water) (only in OLIGOMERIC-SOA 25 MGLY + OH (+ O 2 ) 0.92PRV GLX + HO 2 + H 2 O 26 MGLY + NO 3 (+ O 2 ) 0.92PRV GLX + HO 2 + NO 3- + H +

9 Organic Aqueous-Phase Chemical Scheme Organic Acids Aqueous Phase Reactions HCOOH + OH (+ O 2 ) CO 2 + HO 2 + H 2 O HCOO - + OH (+ O 2 ) CO 2 + H 2 O (+ O 2- ) HCOOH + NO 3 (+ O 2 ) CO 2 + NO H + (+ O 2- ) HCOO - + NO 3 (+ O 2 ) CO 2 + NO 3- + H + (+ O 2- ) CH 3 COOH + OH (+ O 2 ) 0.85GLX CH 2 (OH) 2 CH 3 COO - + OH (+ O 2 ) 0.85GLX CH 2 (OH) 2 CH 3 COOH + NO 3 (+ O 2 ) 0.85GLX CH 2 (OH) 2 + NO 3- + H + CH 3 COO - + NO 3 (+ O 2 ) 0.85GLX CH 2 (OH) 2 + NO 3- + H + PRV + OH (+ O 2 ) CH 3 COOH + HO 2 + CO 2 PRV - + OH CH 3 COO - + HO 2 + CO 2 PRV + NO 3 (+ O 2 + H 2 O) CH 3 COOH + CO 2 + HO 2 + NO 3- + H + PRV - + NO 3 (+ O 2 + H 2 O) CH 3 COO - + CO 2 + HO 2 + NO 3- + H + GLX + OH (+ O 2 ) OXL + HO 2 + H 2 O GLX - + OH (+O 2 ) OXL - + HO 2 + H 2 O GLX + NO 3 (+ O 2 ) OXL + HO 2 + NO 3- + H + GLX - + NO 3 (+ O 2 ) OXL HO 2 + NO3 - + H + OXL + 2OH 2CO 2 + 2H 2 O OXL - + OH (+ O 2 ) 2CO 2 + H 2 O (+ O 2- ) OXL 2- + OH (+ O 2 ) 2CO 2 + HO - (+ O 2- ) OXL + 2NO 3 2CO 2 + 2NO H + OXL - + NO 3 (+ O 2 ) 2CO 2 + NO 3- + H + (+ O 2- ) OXL 2- + NO 3 (+ O 2 ) 2CO 2 + NO 3- (+ O 2- )

10 OXL Calculated Distributions

11 Latitude OXL Observation Sites Longitude 1.E+04 Global OXL Validations Global Urban Sites Sites Simulation Slope r 2 N a F-value Urban S1 0.64± Rural S1 0.92± Marine S1 1.13± Rural + Marine S1 1.16± All Observations S1 1.29± Model - ng(oxl) m -3 1.E+03 1.E+02 1.E+01 Rural Sites Marine Sites 1.E+00 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 Observations - ng(oxl) m -3

12 OXL (ngc m -3 ) OXL (ngc m -3 ) OXL (ngc m -3 ) OXL Validations OLD(ACPD) Vs. Revised Simulations OXL (ngc m -3 ) OXL (ngc m -3 ) 120 Finokalia (35N, 25E) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) S1 OXL (ngc/m3) ACPD_S1 10 Amsterdam Island (37S, 77E) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) - S1 OXL (ngc/m3) - S1_ACPD J F M A M J J A S O N D 50 Puy De Dome (45N, 2E) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) S1 OXL (ngc/m3) ACPD_S1 OXL (ngc m -3) 0 J F M A M J J A S O N D Azores (38N, 27W) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) S1 OXL (ngc/m3) S J F M A M J J A S O N D K. Pustza (46N, 19E) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) S1 OXL (ngc/m3) ACPD_S1 0.0 J F M A M J J A S O N D 200 Schauinsland (45N, 7E) OXL (ngc/m³ ) - Measurements OXL (ngc/m3) S1 OXL (ngc/m3) ACPD_S J F M A M J J A S O N D 0 J F M A M J J A S O N D

13 Global Oxalate Distributions Myriokefalitakis et al., ACPD, 2011, 485 JJA JJA μg/m 3 μg/m 3 Oxalate OC contribution to total_oc (C-ratio) Annual mean Annual mean

14 Global Oxalate Distributions Myriokefalitakis et al., ACPD, 2011, 485 JJA JJA Multiphase μg/m net 3 chemical source is (about Oxalate OC contribution to total_oc (C-ratio) μg/m 3 5%-9% of total WSOC calculated in the model) in-cloud ~21-37 Tg yr -1 in aerosol ~ 1-2 Tg yr -1 Annual mean Annual mean

15 1. Multiphase chemistry (Stelios) 2. Interannual model evaluation & AEROCOM (Nikos) 3. Other ongoing and future activities (Maria)

16 Changes in TM4ECPL anthropogenic emissions updated to CIRCE database ( ) Interannual , 2010 (projection), interpolated 0.1x0.1 ascii files 1x1 hdf files land emissions (2d) BC, CO, NH 3, NOx, OC, SO 2, NMVOC ship emissions (2d) BC, CO, NOx, OC, SO 2, NMVOC aircraft emissions (3d) BC, CO, NOx, OC, SO 2, NMVOC All 3 categories with speciated NMVOC speciation based on POET NMVOC speciation species:acetone, butane, butene, C 2 H 2, C 2 H 5 OH, C 2 H 6, C 3 H 6, C 3 H 8, CH 2 O, CH 3 CHO, CH 3 OH, MEK, toluene, benzene, xylene Global Fire Emission Database v2 ( ) Gridded 1x1 netcdf files used, already speciated nmvocs (van der Werf) Vertical elevation of Biomass Burning emissions based on Dentener et al, 2006 AEROCOM runs re-done Interannual 6x4 ( ) x2

17 Model evaluation updated version (CIRCE anthropogenic, GFED v2, ERA meteorology, Organic Carbon (comparison at all available stations) (ug/m3)

18 Organic Carbon -evaluation Model evaluation after the changes CIRCE anthropogenic Poet biogenic GFED v2 operational meteo data Model evaluation after the changes CIRCE anthropogenic Poet biogenic GFED v2 ERA meteo data Model evaluation before the changes POET anthropogenic Poet biogenic GFED v2 CO and BC operational meteo data

19 Greece Finokalia Italy Ispra Spain Viznar

20 France Peyrusse Vieille Germany Schauinsland Belgium Offagne

21 Hungary K-puszta Finland Pallas (Sammaltunturi) Austria Illmitz

22 Ireland Mace Head United Kingdom Strath Vaich Dam Norway Spitsbergen Zeppelinfjell

23 TM4-ECPL 3x2 TM4-ECPL-6x4 measurements Greece Finokalia Italy Ispra Spain Viznar

24 TM4-ECPL 3x2 TM4-ECPL-6x4 measurements France Peyrusse Vieille Germany Schauinsland Belgium Offagne

25 TM4-ECPL 3x2 TM4-ECPL-6x4 measurements Hungary K-puszta Finland Pallas (Sammaltunturi) Austria Illmitz

26 TM4-ECPL 3x2 TM4-ECPL-6x4 measurements Ireland Mace Head United Kingdom Strath Vaich Dam Norway Spitsbergen Zeppelinfjell

27 1. Multiphase chemistry (Stelios) 2. Interannual model evaluation & AEROCOM (Nikos) 3. Other ongoing and future activities (Maria)

28 Organic aerosol - new perspectives based on element ratios transformation transport Changes in H:C, O:C, N:C, OM:OC ratios Volatility, hygroscopicity secondary OC, ON transformation OC, ON, OP primary OC, ON, OP bioaerosols VOCs NOx deposition OA carrier of nutrients Kanakidou et al., to be submitted to GBC, 2011

29 OA carrier of nutrients Kanakidou et al., to be submitted to GBC, 2011 Contribution to GESAMP WG38 Organic aerosol - new perspectives based on element ratios

30 Further work at ECPL 1. Sensitivity of model results to meteo, emissions, OA parameterisations 2. Interannual trends in oxidants + PM (past 20 years) 3. Oxidant and PM levels simulations focus on Mediterranean 4. Budget analysis / import/export fluxes 5. Improve chemistry relevant parameterisations: 1. OA parameterisations (volatility of POA, heterogeneous reactions, multiphase chemistry) 2. oxidant chemistry (HOx recycling) 6. Sensitivity to emission location & height / geographic distribution/source receptor relationship/lifetime dependence 7. Impact of atmospheric deposition to the marine ecosystem (Mediterranean)