Eric Edgerton, ARA, Inc.

PM Model Performance Workshop

Chapel Hill, NC

February 10, 2004

SEARCH: Overview of Data for Model

Performance Evaluation

Photo

SEARCH: Southeastern Aerosol Research and Characterization Study

Oak Grove (OAK)

Centreville (CTR)

Pensacola (PNS)

Yorkville (YRK)

Jefferson Street (JST)

North Birmingham (BHM)

Gulfport (GFP)

Outlying Landing Field #8 (OLF)

rural urban suburban

SEARCH Objectives

Develop a Particulate Matter Climatology for 8 Sites Understand Composition and its Variability

– Year to Year, Season to Season (1999-2005)– Rural vs. Urban– Coastal vs. Inland

Test, Improve, and Deploy Measurement Methods for Pollutant Gases and Continuous PM Components

Estimate Source Contributions Understand Formation Processes

Provide Comprehensive Data Set for Use in SIP Development Collaborate with States and Others

SEARCH Measurements - Continuous

Category Observables

Temporal

Resolution

Trace Gases O3, NO, NO2, HNO3, NHx, NOy, CO, SO2, CO2

1 min.

Fine Particles Mass, BC, Bscat SO42-,NO3,

NH4+

TC

1 min. or

60 min. (TC)

Surface

Met.

T, RH, BP, WS, WD

SR, precip.

1 min.

SEARCH Measurements - Discrete

Category Analytes

Frequency(2000-2005)

PM2.5 Mass Daily

PM2.5 SO42-,NO3

-, NH4+

OC, EC, Trace Elem.

1/3

PMcoarse Mass 1/3

PMcoarse SO42-,NO3

-, NH4+

Trace Elem.

1/6

PMcoarse OC, EC 1/6 (2 sites)

Trace Gas NH3 (started 10/1/03) 1/3

Need to Benchmark Continuous Data with Filter Data

Example of SEARCH Continuous PM Data Validation Process – Raw Scatter

SO4 vs PCM1 Teflon

y = 0.59x + 0.31

R2 = 0.78

0123456789

10

0 1 2 3 4 5 6 7 8 9 10

PCM1 TEFLON SO4

CO

NTI

NU

OU

S S

O4

Example of SEARCH Continuous PM Data Validation Process – Raw Ratio Cont./Flt.

Ratio of C-SO4/PCM1 SO4

00.20.40.60.8

11.21.41.6

Example of SEARCH Continuous PM Data Validation Process – Adjusted Scatter

SO4 vs PCM1 Teflon

y = 1.05x - 0.25

R2 = 0.87

0123456789

10

0 1 2 3 4 5 6 7 8 9 10

PCM1 TEFLON SO4

CO

NTI

NU

OU

S S

O4

Example of SEARCH Continuous PM Data Validation Process – Adjusted Time Series

C-SO4 and PCM1 Tef SO4 Time-Series

0

5

10

15

20Ja

n-02

Feb-

02

Mar

-02

Apr

-02

May

-02

Jun-

02

Jul-0

2

Aug

-02

Sep

-02

Oct

-02

Nov

-02

Dec

-02

Mas

s, u

g/m

3

PCM1 Tef SO4 C-SO4

Time Series of Hourly SO42-

JST – August 2002

0

5

10

15

20

25

8/23

/02

0:00

8/23

/02

12:0

0

8/24

/02

0:00

8/24

/02

12:0

0

8/25

/02

0:00

8/25

/02

12:0

0

8/26

/02

0:00

8/26

/02

12:0

0

8/27

/02

0:00

8/27

/02

12:0

0

8/28

/02

0:00

8/28

/02

12:0

0

8/29

/02

0:00

8/29

/02

12:0

0

8/30

/02

0:00

8/30

/02

12:0

0

8/31

/02

0:00

8/31

/02

12:0

0

9/1/

02 0

:00

9/1/

02 1

2:00

9/2/

02 0

:00

9/2/

02 1

2:00

9/3/

02 0

:00

9/3/

02 1

2:00

9/4/

02 0

:00

9/4/

02 1

2:00

9/5/

02 0

:00

9/5/

02 1

2:00

9/6/

02 0

:00

9/6/

02 1

2:00

9/7/

02 0

:00

9/7/

02 1

2:00

9/8/

02 0

:00

ARA SO4 PILS SO4

SO

4 (u

g/m

3)

Time Series of Hourly NO3-

JST – August 2002

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

8/23

/02

0:00

8/23

/02

12:0

0

8/24

/02

0:00

8/24

/02

12:0

0

8/25

/02

0:00

8/25

/02

12:0

0

8/26

/02

0:00

8/26

/02

12:0

0

8/27

/02

0:00

8/27

/02

12:0

0

8/28

/02

0:00

8/28

/02

12:0

0

8/29

/02

0:00

8/29

/02

12:0

0

8/30

/02

0:00

8/30

/02

12:0

0

8/31

/02

0:00

8/31

/02

12:0

0

9/1/

02 0

:00

9/1/

02 1

2:00

9/2/

02 0

:00

9/2/

02 1

2:00

9/3/

02 0

:00

9/3/

02 1

2:00

9/4/

02 0

:00

9/4/

02 1

2:00

9/5/

02 0

:00

9/5/

02 1

2:00

9/6/

02 0

:00

9/6/

02 1

2:00

9/7/

02 0

:00

9/7/

02 1

2:00

9/8/

02 0

:00

ARA NO3 PILS NO3

NO

3 (u

g/m

3)

Continuous vs. Filter Data24-Hr Averages (JST)

MAE = median abs. error; MAPE = median abs. % error

FilterMean Mean %E MAE MAPE

SO4 (30) 5.59 5.26 -5.8 0.51 9.9

NH4 (19) 1.89 1.70 -10.2 0.29 12.6

NO3 (23) 0.45 0.33 -26.8 0.15 27.7

FilterMean Mean %E MAE MAPE

SO4 (36) 5.82 6.10 4.8 0.43 8.5

NH4 (32) 2.15 2.10 -2.1 0.20 9.6

NO3 (35) 0.45 0.54 22.0 0.13 34.5

PILS

ARA

Filter-based and Continuous PMcoarse JST: March-April 2003

0

3

6

9

12

15

18

21

PMc

Filter PMc TEOM PMc TEOM = 0.909*filter + 0.35

R2 = 0.952

0

3

6

9

12

15

18

21

0 3 6 9 12 15 18 21

filter PMc

TEO

M P

Mc

1:1 line

(units are µg/m3)

Filter-based and Continuous PMcoarse JST: October 2003

0

3

6

9

12

15

18

10/1/2003 10/4/2003 10/7/2003 10/10/2003 10/13/2003 10/16/2003 10/19/2003 10/22/2003 10/25/2003 10/28/2003

PMc

Filter PMc TEOM PMcTEOM = 0.954*filter + 0.23

R2 = 0.959

0

3

6

9

12

15

18

0 2 4 6 8 10 12 14 16 18

filter PMc

TEO

M P

Mc

1:1 line

(units are µg/m3)

Diurnal CO, NOy, O3 Profiles at Jefferson StreetJanuary 2002 (left), August 2002 (right)

0

200

400

600

800

1000

CO

(ppb

) .

0

20

40

60

80

100

NO

y, O

3 (p

pb)

.

CO O3 NOy

0

200

400

600

800

1000

CO

(ppb

) .

0

20

40

60

80

100

NO

y, O

3 (p

pb)

.

CO O3 NOy

Diurnal PM2.5 Profiles at Jefferson StreetJanuary 2002 (left), August 2002 (right)

0

3

6

9

12

15

18

Con

c. (u

g/m

3)

. OM

BC

SO4

NH4

NO3

0

3

6

9

12

15

18

Con

c. (u

g/m

3)

. OM

BC

SO4

NH4

NO3

SO2 Oxidation Rates

151

86

44

25

55

150

57/53

CFPPs in Vicinity of Yorkville(distances in km)

SO2 and NOy 8/20/02 Event

0

10

20

30

40

50

60

70

8/20/2002 0:00 8/20/2002 4:00 8/20/2002 8:00 8/20/2002 12:00 8/20/2002 16:00 8/20/2002 20:00

NOy SO2

SO2 vs. NOy 8/20/02 Event

SO2 = 4.69*NOy - 19.7R

2

= 0.991

0

10

20

30

40

50

60

70

0 5 10 15 20 25

NOy (ppb)

SO

2 (

pp

b)

3.0

3.5

4.0

4.5

5.0

5.5

6.0

SO2/

NOx

Ratio

(Mol

ar)

3-hour average = 4.86

Trajectory and CEM data point to Plant Bowen

Plant Bowen CEM Data

Bowen

SO2 and SO4 8/20/02 Event

0

10

20

30

40

50

60

70

8/20/2002 0:00 8/20/2002 4:00 8/20/2002 8:00 8/20/2002 12:00 8/20/2002 16:00 8/20/2002 20:00

SO

2 (p

pb)

0

1

2

3

4

5

SO

4 (p

pb)

SO2 SO4 ZERO

SO4 vs. SO2, 8/20/02 Event

SO4 = 0.074*SO2 + 1.09

R2 = 0.982

0

1

2

3

4

5

0 10 20 30 40 50 60

SO2 (ppb)

SO

4 (

pp

b)

Estimated transit time of 2.8 hours yields conversion rate of 2.5%/hour

Mean SO2 conversion rate by season and time of day

0

0.5

1

1.5

2

2.5

3

5:00 7:00 9:00 11:00 13:00 15:00 17:00 19:00

Co

nve

rsio

n R

ate

(%)

Fall-Winter Spring-Summer

0

0.5

1

1.5

2

2.5

3

5:00 7:00 9:00 11:00 13:00 15:00 17:00 19:00

Time Midpoint

Co

nve

rsio

n R

ate

(%)

Fall-Winter Spring-Summer

0

0.5

1

1.5

2

2.5

3

5:00 7:00 9:00 11:00 13:00 15:00 17:00 19:00

Co

nve

rsio

n R

ate

(%)

Fall-Winter Spring-Summer

0

0.5

1

1.5

2

2.5

3

5:00 7:00 9:00 11:00 13:00 15:00 17:00 19:00

Time Midpoint

Co

nve

rsio

n R

ate

(%)

Fall-Winter Spring-Summer

Urban vs. Biomass (ER)CO

NOy(ppb/ppm)

PM2.5(ug/m3/ppm)

TC(ug/m3/ppm)

Urban 137 (12) 38 (9) 11(2)

Biomass 23 (13) 220 (60) 69 (19)

U/B 6.0 0.17 0.16

Urban data from Jefferson Street, Atlanta, GA SEARCH Site

FUEL NOy (as NO) SO2 PM2.5 TC* BC*

Savannah/Grassland 60 5.4 83 57 3.1

Trop. Forest 15 5.5 88 64 6.4

non-Trop. Forest 28 9 121 78 5.2

Biofuels 27 3.5 92 51 7.6

Ag. Residues 27 4.3 42 36 7.5

This Study (Fires) 28+/-14 5.0 +/-2/7 195 +/- 54 63 +/- 14 15 +/- 6.1

This Study (Urban)# 147 +/-10 n.d. 33 +/- 8 9.6 +/- 2.1 n.d.

Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M)* A&M TC and BC based on TSP# Based on Jefferson Street, Atlanta, GA SEARCH data

ER (g/kg CO)

Comparison of ERs with Literature Values

Ammonia First Look (4th Quarter 2003)

SEARCH NH3 Measurements

Oak Grove

Centreville

Pensacola

Yorkville

Jefferson St.

N.Birmingham

Gulfport

OLF

rural urban suburban 24-hour denuder(1/3 day) all sitesStarting 10/1/03

Continuous at Yorkville (9/15/03)and Oak Grove(7/1/04)

SEARCH NH3 and %NHy 4th Quarter 2003

0.0

0.5

1.0

1.5

2.0

2.5

3.0

BHM CTR JST YRK GFP OAK PNS OLF

NH

3 (

pp

b)

0

16

32

48

64

80

% T

RN

NH3

% TRNurban-industrial

urban-res./ind.

rural-forested

rural-forested

rural-agricultural

urban-residential

urban-residential

suburban

0

5

10

15

20

25

01-Nov-03 04-Nov-03 07-Nov-03 10-Nov-03 13-Nov-03 16-Nov-03 19-Nov-03 22-Nov-03 25-Nov-03 28-Nov-03

Co

nc.

(p

pb

)

NH3 NH4

Hourly NH3 and particulate-NH4+

Yorkville, GA – November 2003

0

2

4

6

8

10

12

0 18 36 54 72 90 108 126 144 162 180 198 216 234 252 270 288 306 324 342

WD

Mea

n N

H3

(ppb

)

0

50

100

150

200

250

300

Cou

nt

NH3 n

Continuous NH3 vs. Wind DirectionYorkville, GA – November 2003

The Smoking Chicken

2 km1 km

Poultry operations within several km of Yorkville(crosshair) line up with NH3 spikes.

Continuous NH4+ and NO3

- vs. Wind DirectionYorkville, GA - November 2003

0.0

0.3

0.6

0.9

1.2

1.5

1.8

0 18 36 54 72 90 108 126 144 162 180 198 216 234 252 270 288 306 324 342

Co

nc

. (u

g/m

3)

.

NO3 NH4

Continuous NH4+ and NO3

-

Oak Grove 11/11/03

-0.5

0.0

0.5

1.0

1.5

2.0

11/11/03 0:00 11/11/03 6:00 11/11/03 12:00 11/11/03 18:00

Co

nc.

(u

g/m

3)

.

NO3 NH4

FUEL NOy (as NO) SO2 PM2.5 TC* BC*

Savannah/Grassland 60 5.4 83 57 3.1

Trop. Forest 15 5.5 88 64 6.4

non-Trop. Forest 28 9 121 78 5.2

Biofuels 27 3.5 92 51 7.6

Ag. Residues 27 4.3 42 36 7.5

This Study (Fires) 28+/-14 5.0 +/-2/7 195 +/- 54 63 +/- 14 15 +/- 6.1

This Study (Urban)# 147 +/-10 n.d. 33 +/- 8 9.6 +/- 2.1 n.d.

Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M)* A&M TC and BC based on TSP# Based on Jefferson Street, Atlanta, GA SEARCH data

ER (g/kg CO)

Comparison of ERs with Literature Values

http://www.firedetect.ssd.nesdis.noaa.gov/index.htm

HMS Fire and Smoke Summary for 2345 10/21/03

Emissions from Biomass Burning

Oak Grove

0

90

180

270

360

10/21/03 0:00 10/21/03 4:00 10/21/03 8:00 10/21/03 12:00 10/21/03 16:00 10/21/03 20:00

WD

R (

de

g.)

0.0E+00

2.5E-05

5.0E-05

7.5E-05

1.0E-04

Bs

p (

m**

-1)

WDR Bsp

Bsp

(m

-1)

WD and Bsp for Oak Grove – 10/21/03

FUEL NOy (as NO) SO2 PM2.5 TC* BC*

Savannah/Grassland 60 5.4 83 57 3.1

Trop. Forest 15 5.5 88 64 6.4

non-Trop. Forest 28 9 121 78 5.2

Biofuels 27 3.5 92 51 7.6

Ag. Residues 27 4.3 42 36 7.5

This Study (Fires) 28+/-14 5.0 +/-2/7 195 +/- 54 63 +/- 14 15 +/- 6.1

This Study (Urban)# 147 +/-10 n.d. 33 +/- 8 9.6 +/- 2.1 n.d.

Andreae and Merlet. Global Geochem Cyclec 15(4):955-966. 2001. (A&M)* A&M TC and BC based on TSP# Based on Jefferson Street, Atlanta, GA SEARCH data

ER (g/kg CO)

Comparison of ERs with Literature Values

Ammonium Sulfate

0

3

6

9

12

15

8/16/010:00

8/16/012:00

8/16/014:00

8/16/016:00

8/16/018:00

8/16/0110:00

8/16/0112:00

8/16/0114:00

8/16/0116:00

8/16/0118:00

8/16/0120:00

8/16/0122:00

SO

4, N

O3,

NH

4 (u

g/m

3)

0

10

20

30

40

50

PM

2.5

(ug

/m3)

SO4 NO3 NH4 PM2.5

Continuous PM at Jefferson StreetAugust 16, 2001

0

3

6

9

12

15

8/16/010:00

8/16/012:00

8/16/014:00

8/16/016:00

8/16/018:00

8/16/0110:00

8/16/0112:00

8/16/0114:00

8/16/0116:00

8/16/0118:00

8/16/0120:00

8/16/0122:00

SO

4, N

H4

(ug

/m3)

0.0

0.5

1.0

1.5

2.0

2.5

Mo

lar

Rat

io

SO4 NH4 Ratio

Ammonium sulfate

Ammonium bisulfate

Sulfuric acid

SO4, xsNH4 and Molar Ratio

0

2

4

6

8

10

12

14

8/16/01 0:00 8/16/01 4:00 8/16/01 8:00 8/16/01 12:00 8/16/01 16:00 8/16/01 20:00

SO

4 (

ug

/m3

)

0.0

0.5

1.0

1.5

2.0

2.5

ad

jRa

tio

SO4 adjRatio

Background adjusted Molar Ratio

Sources of Carbon

CO2 = 46.4*CO + 365

R2 = 0.79

NOy = 0.142*CO - 7.05

R2 = 0.91

0

100

200

300

400

500

600

0 500 1000 1500 2000 2500 3000 3500

CO (ppb)

CO

(p

pm

), N

Oy

(p

pb

)

CO2 NOy

Emission Ratios for CO2 and NOyJST 11/16-17/01

PM2.5 = 0.0156*CO + 49.363

R2 = 0.79

TC = 0.0093*CO + 12.5

R2 = 0.66

BC = 0.0025*CO + 0.89

R2 = 0.75

0

20

40

60

80

100

120

0 500 1000 1500 2000 2500 3000 3500

CO (ppb)

Co

nc

. ug

/m3

PM2.5 BC TC

Emission Ratios for PM2.5, TC and BCJST 11/16-17/01

Summary of Observed (ER)CO JST, Atlanta

NOy PM2.5 TC BCppb/ppm ug/m3-ppm ug/m3-ppm ug/m3-ppm

n 18 18 18 18

Mean 0.138 0.152 0.088 0.026

s.d. 0.009 0.022 0.015 0.005

CV (%) 6.5 14.5 17.0 19.2

Simplified Carbon Source Matrixand Applicable Tools

Sources of Primary OC in PM2.5

(F)(F/M ?)

(F)

(F)(M)(M)

(M)(Secondary F/M?)

Primary Carbon Speciation SitesSEARCH & EPA-STN

STN-UrbanSTN-RuralSTN-SuburbanSEARCH-UrbanSEARCH RuralSEARCH-Suburban

Carbon-14 and OC Data Atlanta, GA (JST)

0

4

8

12

16

20

7/1/

2001

7/4/

2001

7/7/

2001

7/10

/200

1

7/13

/200

1

7/16

/200

1

7/19

/200

1

7/22

/200

1

7/25

/200

1

7/28

/200

1

7/31

/200

1

8/21

/200

1

11/1

3/20

01

11/1

7/20

01

11/1

8/20

01

12/4

/200

1

12/5

/200

1

12/1

7/20

01

12/2

0/20

01

12/2

6/20

01

12/2

9/20

01

1/4/

2002

1/7/

2002

1/10

/200

2

1/13

/200

2

1/16

/200

2

1/19

/200

2

OC

(u

g/m

3)

0

0.2

0.4

0.6

0.8

1

F M

od

ern

OC F Modern

0.590.62

OC Source MatrixAtlanta, GA – January

* 2000 Data: Zheng et al., ES&T, 2002.

Primary*

Secondary

Total#

Modern

64

<5

61 +/-5

Fossil

36

<5

39 +/-5

# from 14Cdata

OC Source MatrixAtlanta, GA – July 2001

* Zheng et al. Source Apportionment of Fine Particles at Atlanta, GA, AAAR 2002

Primary*

Secondary

Total#

Modern

<5

>50

59 +/-5

Fossil

40*

<5

41 +/-5

# from 14C data

Five-year Trends

Annual Average Speciated PM2.5

-5

0

5

10

15

20

251

99

92

00

02

00

12

00

22

00

3

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

19

99

20

00

20

01

20

02

20

03

JST YRK BHM CTR PNS OLF GFP OAK

ug

/m3

Other

Major Metal Oxides

Organic Matter

Elemental Carbon

Ammonium

Nitrate

Sulfate

PM2.5

PMcoarse at Jefferson Street, GA(Inorganic Species Account for < 50% of Mass)

0

2

4

6

8

10

12

1999 2000 2001 2002 2003 5-Year mean

PM

coar

se (

ug

/m3)

.

Other

cNH4

cSO4

cNO3

cMMO

Plant (Carbon) Material in PMcoarse SampleCentreville, AL

3700x3700x

PMcoarse Speciation with OC and ECOM= OC*1.4, or OC*1.7, or OC*2.0

cMMO37%

OM1.433%

Other19%

cEC3%

cNH41%

cSO43%

cNO34%

cMMO38%

Other12%

cEC3%

cNH41%

cSO43%

cNO34%

OM1.739%

cMMO38%

Other5%

cEC3%

cNH41%

cSO43%

cNO34%

OM2.046%

Continuous NOy, PM2.5, TEOM PMcoarse

JST: January 21, 2004

0

40

80

120

160

200

240

0:00 4:00 8:00 12:00 16:00 20:00

NO

y, p

pb

.

0

10

20

30

40

50

60

PM

2.5,

TE

OM

PM

c, u

g/m

3

.

NOy PM2.5 TEOM PMc

FRM versus Best Estimate: Composition Recipes

• FRM Equivalent– Include Field Blank (0.3 µg/m3)– Use components from Teflon filter (PCM1)

and front Quartz filter (PCM3)• Best Estimate

– Blank correct all components– Add volatile NO3– Add volatile NH4 (equiv. to NO3)– Add estimated volatile OC (backup Quartz)

SEARCH FRM Equivalent and Best Estimate PM2.5 Composition (percent) Jefferson Street, Atlanta, GA 1999-2002

Average FRM Equivalent mass = 17.7 ug/m3 Average Best Estimate mass = 19.0 ug/m3

1.7%

27.3%

1.1%

9.6%

9.1%

33.7%

2.7%

14.7%

25.3%

5.6%

10.5%

8.5%

34.3%

2.5%

13.4%

Use Of SEARCH “Best Estimate” Fractions For DV Calculations

• Future-year PM2.5 design values are calculated using a combination of observed data and PM modeling results

• For this analysis, RRFs were calculated based on 1996 and 2010 IAQR modeling results from REMSAD

• To examine the uncertainties associated with the use of speciation measurements we calculated the 2010 DVs using

– FRM base values and fractions– FRM base values and “best estimate” fractions

Use of SEARCH “Best Estimate” Fractions For DV Calculations• FDVs calculated for all 8 SEARCH sites, with and without

assumption that 50% of “other” is PBW associated with nitrates and sulfates

• Over the four combinations, 2010 FDVs differ by as much as 0.5 gm-3

• For example:

11.9

12.3

14.5

16.4

11.8

12.0

14.4

16.1

12.012.113.6Pensacola

12.212.513.8Yorkville

14.614.717.1Atlanta

16.316.618.5Birmingham

FRM BEOBS FRMPBW BEPBW

Use of SEARCH “Best Estimate” Fractions For DV Calculations

• Considering the best estimate fraction for each species separately, the largest differences come from nitrate

• For the Birmingham site:

FRM BESulfate only 16.6 16.2

Nitrate only 16.6 17.4

Organics only 16.6 16.6

Black carbon only 16.6 16.5

Other inorganics only 16.6 16.5

Unattributed mass only 16.6 16.0

Summary• SEARCH network will provide comprehensive PM/trace gas data

through 2005• Filter data needed to characterize continuous PM technologies

– Data adjustments– Data uncertainty

• Carbon speciation work underway (primary vs.secondary, Modern vs. Fossil)

• NH3 measurements begun in the SE– Primary species: high and variable near sources, expect lower

and less variable near sinks• Combination of continuous PM and Gas measurements shows

promise– SO4 neutralization variability– Contributions from biomass burning– gas/particle conversion

• Differences between FRM Equivalent and Best Estimate are Significant and Need to be Understood– Model Evaluation– FDVs