Fine Particle (PM2.5) Composition and Trace Gas Measurements in the Yangtze Delta Region

In memoriam Dr. Glen Cass

K. Baumann, M.H. Bergin, W.L. Chameides, F. Ift, C.S. Kiang, J.Z. Zhao

School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta

K.S. Shao, X.Y. Tang, M.L. Wang, L.M. Zeng

Center for Environmental Sciences, Peking University, Beijing

Locations, tools, and data quality

Meteorological and trace gas characteristics at SheShan

Spatial trends in PM2.5 mass and composition

Seasonal comparison based on ChangShu data

2

Sampling Locations in the Yangtze Delta

3

Sampling Locations in the Yangtze Delta

SheShanLinAn

4

Continuous Trace Gas Measurements

Yangtse network station set-up

The inlet box, mounted on the roof of the SheShan observatory, allowed standard addition of NO, and NO2 (via GPT) calibration

gases. A single chemiluminescence detector was utilized, alternating between NO and NOy measure modes every 2 min with instrument zeroes overlapping every 15 min. The flow controller stream selector valve assembly was housed inside

resulting in a sample residence time of ~7 s. The NOy converter is a 35 cm long, 0.48 cm ID MoO tube, temperature controlled

at 330 ±2 oC. All air intake surfaces were Teflon coated and T-controlled at 40 oC.

SheShan Nov-99 intensive NO/NOy

5

Discrete PMfine Measurements via Particle Composition Monitor (PCM)

6

PCM Data Quality

Ca2+ Na+ K+ NH4+ Cl- NO3

- SO42- Acet Form Oxal OC EC

DL (ug m-3) 0.03 0.50 0.16 0.07 0.49 0.43 0.13 0.56 0.42 0.00 0.91 0.51

Bias (%) 60 56 20 30 15 21 17 53 186 34 11 33

STD (%) 30 39 22 18 11 15 13 41 39 30 7 25

7

Trace Gas Data Quality

NO NOy O3 SO2

DL (ppbv) 0.003 0.3 1 1

Precision (%) ± 10 ± 15 ± 2 ± 5

Accuracy (%) ± 10 ± 25 ± 2 ± 5

Note: values for NO/NOy are from GIT’s research grade analyzer, and

uncertainty in NOy arises from MoO conversion efficiency determined for NO2 Q(NO2) = 67 ±14 %.

8

Average PM2.5 and PM10 Concentrationsfor SheShan November 99

PM2.5 (ug m-3) PM10 (ug m-3) PM2.5/PM10

Na+ 0.31 ±0.12 0.89 ±0.43 0.41 ±0.21

K+ 2.19 ±1.41 n/a n/a

Ca2+ 0.43 ±0.25 1.25 ±0.76 0.32 ±0.08

NH4+ 6.49 ±3.78 5.99 ±2.20 1.05 ±0.32

SO42- 14.53 ±7.34 15.82 ±8.06 0.93 ±0.12

NO3- 9.04 ±5.49 8.83 ±5.02 1.01 ±0.17

Cl- 3.03 ±1.29 3.55 ±1.25 0.88 ±0.25

Acetate 2.33 ±2.38 4.40 ±4.60 0.66 ±0.35

Formate 0.01 ±0.01 0.19 ±0.08 n/a

Oxalate 0.29 ±0.11 0.30 ±0.13 1.04 ±0.31

± 1-sigma

Major ions represented

mainly in fine

fraction; bulk of

sodium and calcium in

coarse fraction

9

SheShan November 99Correlations with Wind, Wind Roses

N

E

S

W7.5 15

ppbv

NOy N

E

S

W10 20

ppbv

SO2

N

E

S

W3 6 m/s

Wind Speed

N

E

S

W3.5 7

%

WindFrequency

NOy indicative of influence from mobile sources, i.e.the Shanghai-Hangzhou Expressway to S and E,

and metropolitan Shanghai to NE

SO2 points to possible point sources to W and NE

10

SheShan November 99Meteorological, Trace Gas, and [PM2.5] Time Series

80

60

40

20

0

NO

NO

y O

3 (

pp

bv)

11/1/1999 11/6/1999 11/11/1999 11/16/1999 11/21/1999 11/26/1999 12/1/1999

Date (LT)

20

15

10

5

0

NO

3- (u

g/m3)

70

60

50

40

30

20

10

0

SO

4= (

ug/

m3 )

S

O2

(pp

bv) 350

300

250

200

150

100

50

0

Win

d D

irection (d

egN)

25

20

15

10

Tem

per

atu

re

(C

)

15

10

5

0

Win

d S

peed

(m/s)

11

SheShan PM2.5 and Met. Data November 99PCM Data

0

20

40

60

80

100

120

140

160

11

/2

11

/3

11

/4

11

/5

11

/6

11

/7

11

/8

11

/9

11

/10

11

/11

11

/12

11

/13

11

/14

11

/15

11

/16

11

/17

11

/18

11

/19

11

/20

11

/21

11

/22

11

/23

11

/24

11

/25

11

/26

11

/27

11

/28

11

/29

11

/30

Av

g

PM

2.5 [

ug

m-3]

0

10

20

30

40

50

60

70

80

O3 [p

pb

v]

Ca++ Na+ K+ NH4+ Cl-

NO3- SO4= Acetate Formate Oxalate

OC OOE EC O3-hrly max

0

5

10

15

20

25

11

/2

11

/3

11

/4

11

/5

11

/6

11

/7

11

/8

11

/9

11

/10

11

/11

11

/12

11

/13

11

/14

11

/15

11

/16

11

/17

11

/18

11

/19

11

/20

11

/21

11

/22

11

/23

11

/24

11

/25

11

/26

11

/27

11

/28

11

/29

11

/30

Av

g

T [o

C],

WS

[m

s-1

]

0

50

100

150

200

250

300

350

400

WD

[deg

]

Temperature Wind Speed Wind Direction

• Change in synoptic

conditions on 11/14 and 11/23

(cold fronts)accompanied by sharp drops in PM2.5 and O3, subsequent

recovery

• High mass on 11/24 due to agricultural

burning in close vicinity to the site

12

Sampling Locations in the Yangtze Delta

13

Regional Comparison of PM2.5 Composition

ChangShu Partisol November 99

0

20

40

60

80

100

120

140

160

11

/2

11

/3

11

/4

11

/5

11

/6

11

/7

11

/8

11

/9

11

/10

11

/11

11

/12

11

/13

11

/14

11

/15

11

/16

11

/17

11

/18

11

/19

11

/20

11

/21

11

/22

11

/23

11

/24

11

/25

11

/26

11

/27

11

/28

11

/29

11

/30

Av

g

PM

2.5 [

ug

m-3]

LinAn Andersen November 99

0

20

40

60

80

100

120

140

160

11/2

11/3

11/4

11/5

11/6

11/7

11/8

11/9

11/1

0

11/1

1

11/1

2

11/1

3

11/1

4

11/1

5

11/1

6

11/1

7

11/1

8

11/1

9

11/2

0

11/2

1

11/2

2

11/2

3

11/2

4

11/2

5

11/2

6

11/2

7

11/2

8

11/2

9

11/3

0

Av

g

PM

2.5

[u

g m

-3]

Ca++ Na+ K+ NH4+ Cl- NO3- SO4=

Acetate Formate Oxalate OC OOE EC

• Lowest levels at LinAn background

station,but temporal

fluctuations similar to ChangShu

• Regional influence by cold front

passages (11/14 and 11/23) noticeable at

both sites

• Signatures of sporadic local

influences on top of regional trend

14

Average Mass CompositionSheShan PCM November 99

NO3-11%

NH4+8%EC

3%

SO4=17%

Cl-4%

Organic Acids2%

OC36%

OOE15%

Na+0%

K+3%

Ca++1%

Average sum of components = 85.2 ug m-3

LinAn Andersen November 99

SO4=21%

NO3-8%

NH4+10%EC

4%

OC37%

OOE15%

Organic Acids1%

Na+0%

K+3%

Cl-1%

Ca++0%

Average sum of components = 75.7 ug m-3

ChangShu Partisol November 99

SO4=17%

NO3-9%

NH4+8%EC

3%

OC37%

OOE14%

Na+1%

K+3%

Ca++0%

Organic Acids

4% Cl-4%

Average sum of components = 112.3 ug m-3

No significant regional differences in November 99,

but noticeable seasonal differences at

ChangShu

ChangShu Partisol Spring 00

NO3-12%NH4+

11%

EC6%

SO4=25%

Cl-4%

Organic Acids

0%

Ca++0%

K+4%

Na+1%

OOE11%

OC26%

Average sum of components = 61.6 ug m-3

15

Seasonal/Regional Averages

PM2.5Charge Balance

-600

-400

-200

0

200

400

600

SheShan PCM Nov 99

LinAn Andersen Nov 99

ChangShu Partisol Nov 99

ChangShu Partisol Spring 00

[ne

m-3

]

SO4= NO3- NH4+ Net Acidity

• Seasonal differences in K+ due to post-harvest

biomass burning activities in November

• ChangShu highest Na+, Cl-, suggesting maritime influence

PM2.5 Concentrations

0102030405060708090

100110120

SheShan PCM Nov 99

LinAn Andersen Nov 99

ChangShu Partisol Nov 99

ChangShu Partisol Spring 00

Sta

cked

Co

nce

ntr

ati

on

s [u

g m

-3]

0

1

2

3

4

5

6

7

8

Ca

2+, N

a+, K

+, Cl - [u

g m

-3]

NH4+ NO3- SO4= Acetate Formate Oxalate OC

OOE EC Ca++ Na+ K+ Cl-

• Aerosol slightly acidic regionally; but lower variability at

LinAn

16

Comparison with Seasonal/Regional Averages at U.S. Sites

PM2.5 Mass Balance

0

5

10

15

20

25

30

35

40

AT

L P

M2.

5

AT

L O

3

HV

PM

2.5

HV

O3

DX

PM

2.5

DX

O3

HV

PM

2.5

HV

O3

DX

PM

2.5

DX

O3

HV

PM

2.5

HV

O3

DX

PM

2.5

DX

O3

[ug

m-3

]

0

20

40

60

80

100

120

[pp

bv]

Ca++ Na+ NH4+ Cl- NO3- SO4= AcetForm Oxal OC OOE EC Unid. O3-h max

Sum m er '99 Fall '99 Winter '99/'00

PM2.5 Charge Balance

-300

-200

-100

0

100

200

300

AT

L P

M 2

.5

HV

PM

2.5

DX

PM

2.5

HV

PM

2.5

DX

PM

2.5

HV

PM

2.5

DX

PM

2.5

[ne

m-3

]

SO4= NO3- NH4+ Net Acidity

Summer '99 Fall '99 Winter '99/'00

ATL: Atlanta, GA – urbanHV: H’ville, TN – suburbanDX: Dickson, TN - rural

• Significantly lower [PM2.5] at U.S. sites, even during

summer

• [O3] comparablein fall, much higher

in summer, esp.in urban Atlanta

•Slightly alkaline aerosolin fall and winter,

as opposed to Yangtze sites,probably due to different

emission patterns

17

Summary

• NH4+, SO4

2-, NO3-, and oxalate predominantly in fine mode (PM2.5); alkaline, alkaline earth

cations, Cl- and acetate represented indifferently between fine and coarse (PM10) modes

• Despite low photochemical activity during November period, O3 buildup along with PM2.5

concentrations after frontal passage

• During this buildup period, close correlation of gas phase SO2 and particle phase SO42- observed

• Apparent influence from roadways and point sources at SheShan indicated by NOy and SO2

• Average PM2.5 mass concentration levels highest at ChangShu, possibly due to close vicinity of

traffic sources; lowest in LinAn (background site)

• No regional differences in fine particle composition, but noticeable seasonal differences,

especially with respect to carbonaceous species and sulfate

• Seasonal differences most noticeable in K+ indicating influence of post-harvest burning in

November

• Significantly (~3x) lower PM2.5 in SE-US with tendency to slightly alcalinic aerosol in fall and

winter compared to slightly acidic conditions in the Yangtze Delta region

18

Acknowledgements

• Prof. Du HuiFang, Fudan University, ShangHai, for invaluable help preparing and

organizing the November intensive at SheShan

• Ms. Wu LiBo, Fudan University, ShangHai, for indispensable help and support at

the SheShan site

• Prof. Ding Guoan, CAMS Beijing, for patient help clearing research equipment

with Chinese customs

• The various local site operators at ChangShu, LinAn and SheShan for their

diligence and willingness to help us out with anything, anytime!!

19

SheShan November 99Diurnal Trends Related to Air Mass Transport

0.01

0.1

1

10

100

NO

(p

pb

v)

NO

0.8

0.6

0.4

0.2

0.0

NO

/NO

y (

-)

00:00 06:00 12:00 18:00

Time (LT)

NO/NOy

1

2

4

6

810

2

4

6

8100

NO

y (

pp

bv)

NOy

80

60

40

20

0

O3

(p

pb

v)

00:00 06:00 12:00 18:00

Time (LT)

O3

10

8

6

4

2

0Win

d Sp

eed

(m

/s)

10

8

6

4

2

0Win

d S

pee

d

(m/s

)

30025020015010050Wind Direction (deg)

Symbol code:

Size=WS / color=WD

• Winds driven by synoptic forces rather than convective

(no diurnal trend)

• Strong winds carry background [O3] ~30-40 ppbv

•NO peaks in morning and high levels carried into evening

• Weak photochemistry indicated by O3 and NO/NOy

20

PCM/Andersen Comparison SheShan 11/99 - Teflon

y = 0.6393x + 3.4553

R2 = 0.4913

0

2

4

6

8

10

12

14

16

18

0 2 4 6 8 10 12 14 16 18

PCM [ug m-3

]

Ande

rsen

[ug

m-3

]

NH4+ y = 1.3819x - 4.2158

R2 = 0.9064

0

5

10

15

20

25

30

35

0 5 10 15 20 25 30 35

PCM [ug m-3]

And

erse

n [u

g m

-3]

SO42-

y = 1.0185x - 0.5938

R2 = 0.839

0

5

10

15

20

25

0 5 10 15 20 25

PCM [ug m-3]

And

erse

n [u

g m

-3]

NO3-

21

PCM/Andersen Comparison SheShan 11/99 – Quartz

y = 0.9397x + 1.5508

R2 = 0.8943

0

10

20

30

40

50

60

70

80

0 10 20 30 40 50 60 70 80

PCM [ug m-3

]

And

erse

n [u

g m

-3]

OC y = 0.5211x + 0.7795

R2 = 0.6795

0

1

2

3

4

5

6

0 1 2 3 4 5 6

PCM [ug m-3]A

nder

sen

[ug

m-3

]

EC