DEVELOPMENT AND APPLICATION OF MADRID: A NEW AEROSOL MODULE IN MODELS-3/CMAQ

Yang Zhang*, Betty Pun, Krish Vijayaraghavan, Shiang-Yuh Wu and Christian SeigneurAtmospheric and Environmental Research, Inc., San Ramon, CA

Spyros N. PandisCarnegie-Mellon University, Pittsburgh, PA

Mark Z. JacobsonStanford University, Stanford, CA

Athanasios NenesGeorgia Institute of Technology, Atlanta, GA

John H. SeinfeldCalifornia Institute of Technology, Pasadena, CA

EPA Models-3/CMAQ Workshop, October 27-29, 2003

* Current address: North Carolina State University

Presentation Outline

• Background– Development of CMAQ-MADRID

– CMAQ vs. CMAQ-MADRID

• 3-D Application– Application for SCAQS Episode

– Sensitivity Study

– Performance Evaluation

• Summary

Development of CMAQ-MADRID

• Model for Aerosol Dynamics, Reaction, Ionization, and Dissolution– Review of thermodynamic modules

– Review of aerosol dynamics modules

– Selection and integration of the modules

• 3-D Host Model - EPA Models-3/CMAQ– Evaluation of 3-D models (SAQM, MAQSIP, CMAQ, and CAMx)

– Selection protocol (sciences, computation, ease-of-use, modularity, documentation, technical support and community status)

• Incorporation of MADRID and CMU Aqueous Module into CMAQ– Preserves features of EPA Models-3/CMAQ

– Advanced aerosol and cloud modules

– Provided to EPA in December 2002

CMAQ vs. CMAQ-MADRID: PM Treatment

Models-3/CMAQ• Size representation Modal (3 modes)

• Inorganic species NH4+, SO4

=, NO3-, Na+, Cl-

• Equilibrium MARS-A, ISORROPIA

• Coagulation Modal approach

• Nucleation Absolute rate

• Condensation Modal approach

• Mass transfer Full equilibrium

• Dry deposition Resistance transfer

• SOA formation Irreversible absorption (6 precursors) (Pandis et al., 1992)

or reversible absorption (6 precursors) (Schell et al., 2001)

CMAQ-MADRID

Sectional (2 or multiple sections)

NH4+, SO4

=, NO3-, Na+, Cl-

ISORROPIA

Not treated

Relative rate

Moving-center approach

CIT equilibrium and CMU hybrid

Revised flux approach

MADRID 1: Absorption (38 species)

(Odum et al., 1997; Griffin et al., 1999)

MADRID 2: Absorption & dissolution

(42 VOCs, 5 hydrophobic and 5

hydrophilic surrogate SOA)

(Pun et al., 2002)

CMAQ vs. CMAQ-MADRID: Chemical Mechanisms

Models-3/CMAQ

• Gas-phase CBM-IV, RADM2, chemistry SAPRC-99(1)

• Aqueous RADM

chemistry (Walcek and Taylor, 1986)

- 33 aqueous/ionic species

- 18 equilibria

- 5 kinetic reactions

- 55 species for wet deposition

• Heterogeneous Not treatedchemistry

CMAQ-MADRID

CBM-IV/RADM2 (MADRID 1)

CACM (MADRID 2)

CMU

(Seinfeld and Pandis, 1998)

- 55 aqueous/ionic species

- 34 equilibria

- 99 kinetic reactions

- 88 species for wet deposition

HO2, NO2, NO3, N2O5 on PM N2O5 in droplet (Jacob, 2000)

(1) available in July 2002 version of Models-3/CMAQ

Application of CMAQ-MADRID: SCAQS 1987 Episode

• Period 25-29 August 1987• Domain 63 x 28 grid cells• Horizontal resolution 5 km• Vertical resolution 15 layers• Meteorology

– MM5/FDDA– Nested grids (45, 15, 5 km)

• Emissions– NOx, SO2, CO, SO3, VOC

(Allen and Wagner, 1992)– NH3 and PM (Meng et al., 1998)

– Adjustment in VOC (Pai et al., 2000)• Initial and boundary conditions

– Gases (Pai et al., 2000)– PM (San Nicholas Island)

SCAQS Modeling Domain and Ozone/PM Measurement Sites

▲- sites with PM (5 samples/day) and ozone (hourly) measurements - sites with ozone (hourly) measurementsPink/Red - sites with ozone time series plotsBlue/Red - sites with 24-hr average PM concentrations/size distribution plots

ANAH

AZUSBURK

CELACLAR

HAWT

LBCC

RIVR

CRESELRI

POMAWSLA

BANN

COST

FONT

GLEN

HEMEINDOLGBH

LSAL

LYNN

NEWL

NORC

OJAI

PASA

PERI

PICO

PLSP

RDLD

SIMI

SNBOUPLA

VCTC

VENT

WHIT

HESP

RESE

PIRU

THSO

Observed vs. Simulated Ozone Mixing Ratios

POMA, central, rural

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

CELA, western, urban

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

RIVR, inland, urban

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

WSLA, watern, near coast

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

ELRI, northwestern, rural

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

CRES, northern, remote

0

50

100

150

200

250

300

0 4 8 12 16 20 24 28 32 36 40 44 48Time (Hours from 0000PST August 27, 1987)

[O3

], p

pb

Observed vs. Simulated PM2.5 Concentrations

24 hr-Avg. PM2.5 at HAWT, Aug. 27, 1987

0

5

10

15

20

25

30

35

PM Species

Mass c

on

c.,

g m

-3 Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

24 hr-Avg. PM2.5 at HAWT, Aug. 28, 1987

0

5

10

15

20

25

30

35

PM Species

Mass c

on

c.,

g m

-3 Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

24 hr-Avg. PM2.5 at CELA, Aug. 27, 1987

0

10

20

30

40

50

60

PM Species

Mass c

on

c.,

g m

-3

Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

24 hr-Avg. PM2.5 at CELA, Aug. 28, 1987

0

10

20

30

40

50

60

PM Species

Mass c

on

c.,

g m

-3

Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

24 hr-Avg. PM2.5 at RIVR, Aug. 27, 1987

0

20

40

60

80

100

PM Species

Mass c

on

c.,

g m

-3 Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

24 hr-Avg. PM2.5 at RIVR, Aug. 28, 1987

0

20

40

60

80

100

PM Species

Mass c

on

c.,

g m

-3 Observed

CMAQ-MADRID 1

Na+ SO4= NH4+ NO3- OMCl- EC PM2.5

MADRID 1 vs. MADRID 2 (Riverside)

28-August

27-August

Observed MADRID 1 MADRID 2

Nitrate OC

Sulfate EC

Ammonium Other

42%

9%13%

15%

4%

17%

37%

13%16%

9%

2%

23%

42%

10%13%

16%

4%

15%

42%

11%17%

8%

2%

20%

36%

13%16%

13%

2%

20%

33%

14%15%

14%

2%

22%

Condensational Growth (Moving-Center vs. Finite-Difference)

CLAR, 24-hr Average, August 28, 1987

0

20

40

60

80

0.01 0.1 1 10

Particle Diameter, Dp (m)

dM/d

log

Dp

(g

m-3

)

Observed

Moving-Center

Finite-Difference

RIVR, 24-hr Average, August 28, 1987

0

20

40

60

80

100

0.01 0.1 1 10

Particle Diameter, Dp (m)

dM/d

log

Dp

(g

m-3

)

Observed

Moving-Center

Finite-Difference

Gas/Particle Mass Transfer (Hybrid vs. Bulk Equilibrium)

CLAR, 24-hr Average, August 28, 1987

0

10

20

30

40

50

60

0.01 0.1 1 10

Particle Diameter, Dp (m)

dM/d

log

Dp

(

g m

-3)

ObservedCMU hybridCIT bulk equilibriumSimple bulk equilibrium

RIVR, 24-hr Average, August 28, 1987

0

20

40

60

80

100

0.01 0.1 1 10

Particle Diameter, Dp (m)

dM/d

log

Dp

(

g m

-3)

ObservedCMU hybridCIT bulk equilibriumSimple bulk equilibrium

Gas/Particle Mass Transfer (CIT Bulk Equilibrium vs. CMU Hybrid)

The CMU hybrid approach predicts more sodium nitrate in the coarse mode

The CIT bulk equilibrium approach distributes most nitrate within the fine mode (PM2.5)

HAWT, 24-hr Avg., Aug. 28, 1987, CMU Hybrid Approach

0

1

2

3

4

1 2 3 4 5 6 7 8

SectionCo

ncen

tratio

ns,

g m

-3 Cl-NO3-NH4+SO4=Na+

HAWT, 24-hr Avg, Aug. 28, 1987, CIT Hybrid Approach

0

1

2

3

4

1 2 3 4 5 6 7 8

Section

Conc

entra

tions

, g

m-3 Cl-

NO3-NH4+SO4=Na+

Model Performance for O3 and PM2.5

August 27-28 Other work* Gross

error,% Bias %

Gross error, %

Bias, %

O3 33.6 8.5 -35 to 50 -6.6 to 34 PM2.5 44.2 14.2 32 to 66 -26 to 46 Sulfate2.5 37.9 11 28.4 to 49 -47 to 3.7 Nitrate2.5 44.2 -37.8 29 to 187 -20.7 to 106 Ammonium2.5 52.3 25.3 18 to 67.8 -52.3 to 56 EC2.5 54.1 -20.2 15 to 77 -52 to 35 OM2.5 49.6 -21.3 38 to 126 -44.1 to 112

* Other work include UAM-IV/CALGRID/UAM-AERO (Kumar et al., 1994; Lurmann et al., 1997), GATOR (Jacobson, 1997), SMOG (Lu et al., 1997), CIT with SAPRC93 or LCC (Harley et al., 1993, 1997; Meng et al., 1998), SAQM-AERO (Pai et al., 2000).

Summary of SCAQS Application

• CMAQ-MADRID provides a realistic representation of atmospheric PM.

• Secondary organic aerosol predictions are sensitive to different SOA formulations.

• Jacobson’s moving-center approach is the most accurate among the condensational growth algorithms tested.

• The CMU hybrid and the CIT bulk equilibrium approaches predict a realistic particle size distribution under most conditions.

• Heterogeneous chemistry increases H2O2, HNO3, and sulfate; decreases SO2 and NO2; affects O3 and nitrate in both ways.

Acknowledgments

• EPRI: New aerosol & cloud modules• CARB: MADRID2 aerosol module• R. Griffin and D. Dabdub for providing source

codes used in MADRID• F. Binkowski and S. Leduc for discussions

regarding EPA Models-3/CAMQ• Project managers: N. Kumar (EPRI), A. Hansen

(EPRI), N. Motallebi (CARB)