A new parameterization of biogenic SOA formation based
on smog chamber data: 3D testing in CMAQ
Manuel Santiago1, Ariel F. Stein2, Marta G. Vivanco1, Yunsoo Choi3 and Rick Saylor4
1 CIEMAT (Research Center for Energy, Environment and Technology). Madrid. SPAIN2 ERT on assignment of NOAA/ARL, Silver Spring MD
3 NOAA/ARL, Silver Spring, MD4 NOAA/ARL, Atmospheric Turbulence and Diffusion Division, Oak Ridge, TN
2011 CMAS Conference [email protected]
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
Terpene SOA in CMAQ v4.7
Based on the partition parameters obtained by Griffin et al. 1999
1 ,1 2 ,2
,1 ,2
. .
1 . 1 .om om
oom o om o
K KY M
K M K M
Two Product Model for different BVOCs
Griffin et al., 1999
Terpene SOA in CMAQ v4.7
Compound wght alpha1 Kom1 alpha2 Kom2 ---------- ---- ------ ------ ------ ------ a-pinene 0.4 .038 .171 .326 .0040b-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?
Semiempirical Parameterization
Theoretical Kom,i calculation for individual SOA constituents
-pin + limo yield calculation
Two product model fit(Based on theoretical constraints)
Comparison with current CMAQ parameters
Smog Chamber Experiments
Outdoor chamber EUPHORE (CEAM, Valencia, Spain)
Approximated volume of 200 m3
Biogenic VOCs mixture photooxidation experiments:
(isoprene + -pinene + limonene) + HONO
Smog Chamber Experiments
ppbCHAMBER : ppbRURAL ATM. = 102 – 103
Exp. ISO APIN LIMO HONO NO NO2 SO2 ppbC/ppbNOx T RHppb ppb ppb ppb ppb ppb ppb K %
250608 190 100 100 170 23 15.3 299 11
240609 107 66 58 99 34 128 6.8 302 0.5
141009 92 50 50 87 48 10.8 298 30
261009 122 71 40 53 41 18.3 300 19
271009 63 65 101 32 9.6 298 8
291009 99 59 53 307 150 3.5 297 8
111109 87 50 51 40 244 89 513 3.9 294 19
070610 88 79 76 165 198 461 5.5 302 20
-pinene SOA products(Kamens and Jaoui, 2001)
poL,i
(Torr)Kom,i
(m3.g-1)Limonene SOA products(Jaoui et al., 2006)
poL,i
(Torr)Kom,i
(m3.g-1)
Pinic acid 7.6E-07 0.1450 Limonic acid 6E-07 0.1860
10-Hydroxypinonic acid 7.1E-07 0.1560 7-hydroxylimononic acid 5.5E-07 0.2000
Ketolimonic acid 2.4E-07 0.4710
Ketonorlimononic acid 6.2E-07 0.1770
Pinonic acid 1.1E-04 0.0010 5-hydroxyketolimononic acid 2.2E-07 0.5070
Norpinonic acid 2.9E-04 0.0004
4-oxopinonic acid 1.3E-05 0.0088 Limononic acid 8.4E-05 0.0013
10-hydroxypinonaldehyde 1.1E-04 0.0010 Ketolimononic acid 3.3E-05 0.0033
Organic nitrate 1.2E-04 0.0009 Organic nitrate 1E-04 0.0011
0.1 m3/g < Kom,1 < 0.5 m3/g
0.01 m3/g < Kom,2 < 0.001 m3/g
Individual Kom,i calculation
The contribution method SIMPOL.1 (Pankow and Asher, 2008) was used for the calculation of individual po
L,i and Kom,i
0 100 200 3000.0
0.1
0.2
0.3
0.4TRP (-pin + limo) SOA YIELD
YT
RP
MoTRP
(g/m3)
0 100 200 300 4000.0
0.1
0.2
0.3
Y
Mo (g/m3)
GENERAL SOA YIELD
, .o trp o isoprene isopreneM M ROG Y
,
lim( )o trp
TRPonene pinene
MY
ROG ROG
Yisoprene = 0.02
-pin + limo Yield Calculation
1 ,1 2 ,2
,1 ,2
. .
1 . 1 .om om
oom o om o
K KY M
K M K M
0MYROG
1 = 0.1939 Kom,1 = 0.1106 m3.g-1
2 = 0.2 Kom,2 = 0.0056 m3.g-1
0 100 200 3000.0
0.1
0.2
0.3
0.4TRP (-pin + limo) SOA YIELD
YTR
P
MoTRP
(g/m3)
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)
1 Kom,1,298K
(m3.g-1)cstar
(m3.g-1)2 Kom,2,298K
(m3.g-1)cstar (m3.g-1)
TRP_original APIN 0.0494 0.3529 0.4238 0.0083
LIMO 0.3107 0.1135 0.4719 0.0109
TRP 0.1801 0.1302 7.68 0.4479 0.0097 103.596
TRP_revised APIN 0.0269 0.5618 0.3089 0.0131
LIMO 0.5819 0.0431
TRP 0.3044 0.0483 20.7 0.1544 0.0131 76.182
TRP_fit TRP 0.1939 0.1106 9.04 0.2 0.0056 180.08
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)
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
Chamber Experiments Simulations
0 30 60 900
200
400
600
800
1000
0 60 120 180 240 3000
100
200
300
400
500
0 60 120 180 240 3000
100
200
300
400
500
0 60 120 180 240 3000
100
200
300
400
500
SMPS (d=1.3g/cc) TRP_original TRP_revised TRP_fit
250608
SOA
(
g/m
3 )
time (min)
240609
SOA
(
g/m
3 )
time (min)
141009
SOA
(
g/m
3 )
time (min)
261009
SOA
(
g/m
3 )
time (min)
0 60 120 180 240 3000
100
200
300
400
500
0 60 120 180 240 3000
100
200
300
400
500
0 60 120 180 240 3000
100
200
300
400
0 60 1200
100
200
300
400
500
600
SOA
(
g/m
3 )
time (min)
271009 291009
SOA
(
g/m
3 )
SMPS (d=1.3g/cc) TRP_original TRP_revised TRP_fit
time (min)
111109
SOA
(
g/m
3 )
time (min)
070610
SOA
(
g/m
3 )
time (min)
TRP_original TRP_revised TRP_fit250608 147.3 93.8 48.2240609 70.2 36.7 8.0141009 72.0 38.0 3.0261009 96.3 57.2 18.0271009 101.0 55.8 11.4291009 101.5 60.3 23.7111109 81.9 40.6 4.8070610 82.0 43.4 7.9
Normalized Mean Bias (%)
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
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