influence of intense secondary aerosol formation and long range … · 2020. 8. 7. · 1 1...

1

Supplement for manuscript 1

Influence of Intense secondary aerosol formation and long 2

range transport on aerosol chemistry and properties in the 3

Seoul Metropolitan Area during spring time: Results from 4

KORUS-AQ 5

Hwajin Kim1,2 ,Qi Zhang3,4* and Jongbae Heo5 6

[1] Center for Environment, Health and Welfare Research, Korea Institute of Science and 7

Technology, Seoul, Korea 8

[2] Department of Energy and Environmental Engineering, University of Science and 9 Technology, Daejeon, Korea 10

[3] Department of Environmental Science and Engineering, Fudan University, Shanghai, China. 11

[4] Department of Environmental Toxicology, University of California, Davis, CA 95616, USA 12

[5] Center for Healthy Environment Education & Research, Graduate School of Public Health, 13

Seoul National University, Seoul, Korea 14

15

*Corresponding author: Qi Zhang 16

Department of Environmental Toxicology, University of California 1 Shields Avenue, Davis, 17 California 95616 18

Phone: (530)-752-5779 19

Email: [email protected] 20

21

22

23

24

25

2

Table S1. Comparison of the average O/C, H/C, and OM/OC ratios of total OA and the four OA 26

factors identified from PMF analysis calculated using the Aiken-Ambient method (Aiken et al., 27

2008) and the improved Canagaratna-Ambient method (Canagaratna et al., 2015). 28

29

Species Ratio Aiken-Ambient Canagaratna-Ambient

OA O/C 0.38 0.49 H/C 1.52 1.67 OM/OC 1.66 1.82

HOA O/C 0.11 0.15 H/C 1.85 2.00 OM/OC 1.31 1.37

COA O/C 0.15 0.19 H/C 1.68 1.83 OM/OC 1.34 1.41

SVOOA O/C 0.33 0.44 H/C 1.55 1.73 OM/OC 1.58 1.74

LVOOA O/C 0.51 0.91 H/C 1.41 1.46 OM/OC 1.84 2.36

30

Table S2. Comparison of aerosol properties and meteorological parameters at different stages 31 during haze period. 32

PM, particulate matter; NR-PM1, non-refractory submicrometer particulate matter; RH, relative humidity 33

34

Overall S1 S2 S3 S4

Average non-refractory submicrometer

particulate matter (NR-PM1) mass concentration

(µg m-3) (Average )

22.1 9.0 41.2 37.7 13.0

RH(%) / Temp(°C) 62/19 96/16 78/18 67/21 48/23

WS(m/s) 1.7 3.0 2.2 1.4 1.7

Trace gas conc.(CO (ppm) and /SO2/ NO2

O3/(ppb))

0.52/5.1/34/29

0.48/4.0/39/15

0.55/4.8/32/39

0.62/6.1/37/35

0.39/4.5/28.7/33

3

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

Figure S1. Wind Rose plots for every hour colored by wind speed. Radial scales correspond to the 58

frequency. 59

0

5

10

15

20

25

5 10 15 20 25

0

45

90

135

180

225

270

315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h1

0

5

10

15

20

25

5 10 15 20 25

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h2

0

5

10

15

20

25

5 10 15 20 25

0

45

90

135

180

225

270

315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h3

0

5

10

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20

25

5 10 15 20 25

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h4

0

5

10

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20

25

5 10 15 20 25

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h5

0

5

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25

5 10 15 20 25

0

45

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0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h6

0

5

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25

5 10 15 20 25

0

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135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h8

0

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30

5 10 15 20 25 30

0

45

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135

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0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h7

0

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30

5 10 15 20 25 30

0

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135

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0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h9

0

3

6

9

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18

3 6 9 12 15 18

0

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135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h10

0

5

10

15

20

25

30

5 10 15 20 25 30

0

45

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h11

0

10

20

30

40

10 20 30 40

0

45

90

135

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225

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h12

0

10

20

30

40

10 20 30 40

0

45

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135

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225

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h13

0

10

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40

10 20 30 40

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h14

0

5

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30

5 10 15 20 25 30

0

45

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135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h15

0

10

20

30

40

10 20 30 40

0

45

90

135

180

225

270

315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h16

0

10

20

30

40

10 20 30 40

0

45

90

135

180

225

270

315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h17

0

10

20

30

40

10 20 30 40

0

45

90

135

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225

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h18

0

5

10

15

20

25

30

5 10 15 20 25 30

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h19

0

10

20

30

40

10 20 30 40

0

45

90

135

180

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h20

0

5

10

15

20

25

30

5 10 15 20 25 30

0

45

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0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h21

0

5

10

15

20

25

5 10 15 20 25

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h22

0

5

10

15

20

25

5 10 15 20 25

0

45

90

135

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h23

0

5

10

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20

25

5 10 15 20 25

0

45

90

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315

0 - 0.6 0.6 - 1.2 1.2 - 1.8 1.8 - 2.4 2.4 - 3 3+

Wind Speed (m/s)

h24

4

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

Figure S2. (a) Time series of composition dependent collection efficiency (CDCE) and; (b) 75

histogram of CDCE, averaging 0.5 ± 0.01. 76

77

78

79

80

81

82

83

0.001

0.1

10

1000

Fre

qu

en

cy (

CD

CE

)

1.00.90.80.70.60.5CDCE

(b)

0.9

0.8

0.7

0.6

0.5

CD

CE

4/15

4/18

4/21

4/24

4/27

4/30 5/

35/

65/

95/

125/

155/

185/

215/

245/

275/

30 6/2

6/5

6/8

6/11

6/14

Date and Time (KST)

(a)

5

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

Figure S3. (a) Time series of total particulate matter (PM1), scanning mobility particle sizer 101

(SMPS) volume concentrations ; (b) Time series of the organic aerosol density estimated using the 102

method reported in Kuwata et al. (2012) 103

ρorg = [12 + 1•(H/C) + 16•(O/C)]/ [7 + 5•(H/C) + 4.15•(O/C)] 104

and bulk aerosol density estimated from the measured chemical composition, known inorganic 105

species density and the organic density estimated above (Zhang et al., 2005). (c) Scatter plot of the 106

total PM1 mass (NR-PM1 plus BC) versus SMPS volume, where the NR-PM1 mass concentrations 107

have been determined using the composition-dependent collection efficiencies; (d) histogram of 108

organic aerosol density (average = 1.21 g cm-3) and bulk aerosol density (average = 1.5 g cm-3). 109

1400

1200

1000

800

600

400

200

0

Fre

que

ncy

(Org

. Den

sity

)

1.601.401.201.000.80Density bin mid-point (g cm

-3)

1400

1200

1000

800

600

400

200

0

Fre

que

ncy (PM

den

sity)

Org density PM density

(d)

80

60

40

20

0

Ma

ss C

on

c.(µ

g/m

3 )

6050403020100

SMPS Volume (µm3/cm

3)

4/21/2016

5/11/2016

5/31/2016

Date&

Tim

e(KS

T)

r2 = 0.879

Slope = 1.237 ± 0.001(c)

1.8

1.6

1.4

1.2

1.0

0.8

PM

De

nsi

ty (

g/c

m3 )

4/15

4/18

4/21

4/24

4/27

4/30 5/

35/

65/

95/

125/

155/

185/

215/

245/

275/

30 6/2

6/5

6/8

6/11

6/14

Date&Time (KST)

1.8

1.6

1.4

1.2

1.0

0.8

Org

. De

nsity (g

/cm3)

80

60

40

20

0Ma

ss C

on

c. (

µg

/m3) 80

60

40

20

0

SM

PS

Vo

l. (µm

3/cm3)

Mass Conc. SMPS Vol.

PM density Org. density

(a)

(b)

6

110

111

112

113

114

115

Figure S4. Scatter plot of OM/OC, O/C, and H/C calculated with the Canagaratna method vs. 116

those with the Aiken-Ambient method. 117

118

119

120

121

122

123

124

2.0

1.5

1.0

0.5

0.0

Rat

ios

Ca

na

ga

ratn

a m

eth

od

2.52.01.51.00.50.0

RatiosAiken method

H/C

r2 = 0.984

Slope = 1.02 ± 0.001

OM/OC

r2 = 0.995

Slope = 1.28 ± 0.001

O/C

r2 = 0.997

Slope = 1.28 ± 0.001

7

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

100806040200

(R

esi

d2/

2)/

Qe

xp

120110100908070605040302010 m/z

CxHy CxHyO1 CxHyO2 HyO1CxHyNpCxHyOzNp

100806040200

(R

esid

2 /2 )/

Qex

p

4/21/2016 5/1/2016 5/11/2016 5/21/2016 5/31/2016 6/10/2016Date and Time (KST)

0.80.60.40.20.0

R

esi

du

al

(µg

/m3)

Residual = (Measured - Reconstructed)

403020100

Ma

ss C

on

c. (

µg

/m3

Measured Total Mass Reconstructed Total Mass

840

-4-8

Sca

led

Re

sid

ua

l

1101009080706050403020 m/z

(e)

(f)

(g)

(h)

(i)

1.0

0.8

0.6

0.4

0.2

0.0

Ma

ss fr

act

ion

-1-0

.9-0

.8-0

.7-0

.6-0

.5-0

.4-0

.3-0

.2-0

.1 00

.10

.20

.30

.40

.50

.60

.70

.80

.9 1

fPeak

Residual NO3 SO4 LV-OOA SV-OOA COA HOA

(c)0.6

0.4

0.2

0.0

-0.2

R, T

ime

Ser

ies

1.00.80.60.40.20.0R, Mass Spectra

1_2

1_32_3

1_4

2_4

3_4

1_5

2_5

3_5

4_51_6

2_63_6

4_6

5_6

(d)

15.3740

15.3730

15.3720

15.3710

Q/Q

exp

ect

ed

-1.0 -0.5 0.0 0.5 1.0fPeak or seed

Q for p 6 Current Solution min Q for fpeakOrSeed

(b)

24

20

16

Q/Q

exp

ecte

d

987654321

Number of factors (p)

Q for fPeak 0 Best Solution

(a)

8

147

Figure S5. Summary of the key diagnostic plots of the chosen 6-factor solution (4 OA factor 148

solution) from PMF analysis of the organic aerosol fraction: (a) Q/Qexp as a function of the number 149

of factors (p) explored in PMF analysis, with the best solution denoted by the open orange circle. 150

Plots b-i are for the chosen solution set, containing 4 factors: (b) Q/Qexp as a function of fPeak; (c) 151

mass fractional contribution to the total mass of each of the PMF factors, including the residual (in 152

purple), as a function of fPeak; (d) Pearson’s r correlation coefficient values for correlations among 153

the time series and mass spectra of the PMF factors. Here, 1 = NO3, 2 = SO4, 3 = LV-OOA, 4 = 154

SV-OOA, 5 = COA, 6 = HOA; (e) box and whiskers plot showing the distributions of scaled 155

residuals for each m/z; (f) time series of the measured mass and the reconstructed mass from the 156

sum of the 6 factors; (g) time series of the variations in the residual (= measured – reconstructed) 157

of the fit; (h) the Q/Qexp for each point in time; (i) the Q/Qexp values for each fragment ion. 158

9

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

10

183

184

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

Figure S6. Overview of two other solution sets and 6-factor solution including inorganic factors 200

and signals from inorganic included PMF analysis: (a)(b) High resolution mass spectra and time 201

series of the different OA factors from the 5-factor solution (3-OA); (c)(d) High resolution mass 202

spectra and time series of the different OA factors from the 6-factor solution (4-OA); (e)(f) High 203

resolution mass spectra and time series of the different OA factors from the 7-factor solution (5-204

OA). The mass spectra are colored by different ion families. 205

206

207

20

0100908070605040302010

m/z (amu)

20

0

20

0

10

0

10

0

10

0

10

0

Factor 1O/C = 0.82, H/C = 1.33, N/C = 0.030, OM/OC = 2.27







% o

f to

tal

CxHy CxHyO1 CxHyO2 HyO1CxHyNpCxHyOzNp SOx NOx NHx(e)

1510

50

4/21/2016 5/11/2016 5/31/2016

Date and Time (KST)

1612

840

12840

12840

Ma

ss C

once

ntr

atio

n (

µg/

m3 ) 5

43210

1086420

86420

(f)

11

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

Figure S7. Overview of the 4-factor solution (a and b) and the 5-factor solution (c and d) from 227

PMF analysis of the organic mass spectra only. The mass spectra are colored by different ion 228

families. 229

230

10

5

0100908070605040302010

m/z (amu)

1510

50

15

10

5

0

86420





% o

f to

tal

CxHy CxHyO1 CxHyO2 HyO1CxHyNpCxHyOzNp(a)

6

4

2

0

4/21/2016 5/11/2016 5/31/2016

Date and Time (KST)

12

8

4

0

8

6

4

2

0

8

6

4

2

0

Ma

ss C

on

cen

tra

tion

(µ

g/m

3 )

(b)

1050

100908070605040302010

m/z (amu)

1510

50

1510

50

86420

86420






% o

f to

tal

CxHy CxHyO1 CxHyO2 HyO1CxHyNpCxHyOzNp(c)

543210

4/21/2016 5/11/2016 5/31/2016

Date and Time (KST)

86420

6420

1086420

Ma

ss C

on

cen

tra

tion

(µ

g/m

3 )

6420

(d)

12

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

Figure S8. Averaged compositional pie chart of PM1 species (non-refractory-PM1 plus black 246 carbon (BC)) in different clusters from the five cluster solution. The trajectories were released at 247 half of the mixing height at the KIST (latitude: 37.60N; longitude: 127.05E) and the average 248 arriving height for the back trajectories for this study was approximately 190 m. 249

250

45%

19%

18% 12% 0%

6%

C2:21 µg/m3

44%

16%

21% 12% 0%

7%

C3:20 µg/m3

38%

18%

24% 13% 0%

7%

C1:24 µg/m3

54%

15%

16%

9% 0%

6%

C4:22 µg/m3

46%

15%

20% 11% 0%

8%

C5:18 µg/m3

• Cluster1 : 35% • Cluster2 : 22% • Cluster3 : 3% • Cluster4 : 21% • Cluster5 : 20%

13

251

252

253

Figure S9. Scatterplot that compares predicted NH4+ versus measured NH4

+ concentrations. The 254 predicted values were calculated assuming full neutralization of the anions (e.g., sulfate, nitrate, 255 and chloride). The data points are colored by date. 256

257

258

259

260

261

262

263

264

265

266

12

10

8

6

4

2

0

NH

4+ p

redi

cted

(µ

g/m

3 )=

SO

4 x

2 x

18

/96

+ N

O3 x

18

/62

+ C

l x 1

8/3

5.5

1086420

NH4+ measured (µg/m

3)

r2 = 0.997

Slope = 1.052 ± 0

4/21/2016

5/11/2016

5/31/2016

Date

14

267

268

269

270

271

272

273

274

275

276

Figure S10. Size distributions for (a) organic; (b) Sulfate: (c) Nitrate; (d) ammonium for every 277 hour. Y axis are shared for all distributions which are maximized to the axis. 278

279

280

281

282

283

284

285

286

287

288

289

290

Figure S11. One-hour averaged diurnal profiles of organics in (a) accumulation mode and (b) 291 fine mode. 292

6

4

2

0

Acc

ula

tion

mo

de

Org

.

(µg

/m3)

1 2 3 4 5 6 7 8 9101112131415161718192021222324Hour of Day

(a) 367-770 nm

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Fin

e m

od

e O

rg.

(µg

/m3 )

1 2 3 4 5 6 7 8 9101112131415161718192021222324Hour of Day

(b) 46-151 nm

dO

rg/d

log 1

0Dva

(µ

g m

-3)

3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

Dva(nm)

(a) 1h 2h 3h 4h 5h 6h 7h 8h 9h 10h 11h 12h 13h 14h 15h 16h 17h 18h 19h 20h 21h 22h 23h 24h

dSO

4/d

log

10D

va (

µg

m-3)

3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

Dva(nm)

(b) 1h 2h 3h 4h 5h 6h 7h 8h 9h 10h 11h 12h 13h 14h 15h 16h 17h 18h 19h 20h 21h 22h 23h 24h

dNO

3/d

log

10D

va (

µg

m-3)

3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

Dva(nm)

(c) 1h 2h 3h 4h 5h 6h 7h 8h 9h 10h 11h 12h 13h 14h 15h 16h 17h 18h 19h 20h 21h 22h 23h 24h

dNH

4/d

log

10D

va (

µg

m-3)

3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

Dva(nm)

(d) 1h 2h 3h 4h 5h 6h 7h 8h 9h 10h 11h 12h 13h 14h 15h 16h 17h 18h 19h 20h 21h 22h 23h 24h

15

293

294

295

296

297

298

299

300

301

302

303

304

305

306

307

308

309

310

311

312

313

314

Figure S12. Polar plots of hourly averaged PM1 species concentrations (top row), mass 315 concentrations of the five OA factors identified from PMF analysis (middle row), the mixing 316 ratios of various gas phase species (second row from the bottom), and the particle number 317 concentrations (bottom row) as a function of WS and direction. 318

0

2

4 ws

6

8

10

W

S

N

E

3 4 5 6 7 8 9 10 11

Organic mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

1 2 3 4 5

Nitrate mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

1 2 3 4 5 6

Sulfate mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.5 1 1.5 2 2.5 3 3.5

Ammonium mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.01 0.02 0.03 0.04 0.05

Chloride mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

BC mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.4 0.6 0.8 1 1.2 1.4 1.6

HOA mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.5 1 1.5 2 2.5

COA mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.5 1 1.5 2 2.5 3

SVOOA mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.5 1 1.5 2 2.5 3 3.5 4

LVOOA mass conc. (g m3)

0

2

4 ws

6

8

10

W

S

N

E

0.3 0.35 0.4 0.45 0.5 0.55CO (ppm)

0

2

4 ws

6

8

10

W

S

N

E

15 20 25 30 35NO2 (ppb)

0

2

4 ws

6

8

10

W

S

N

E

4 4.5 5 5.5 6SO2 (ppb)

0

2

4 ws

6

8

10

W

S

N

E

20 25 30 35 40 45O3 (ppb)

0

2

4 ws

6

8

10

W

S

N

E

4000 5000 6000 7000 8000 900010000110001200013000Number Conc.(#/cm3)

16

319

320

321

322

323

324

325

326

327

328

329

330

Figure S13. Scatterplot of the variations of fSO4 ratios as a function of RH (a) during winter 331 (Kim et al., 2017); (b) during spring in this study. 332

333

334

335

336

337

338

339

340

341

342

0.5

0.4

0.3

0.2

0.1

0.0

fSO

4

100806040200RH (%)

r2 = 0.274

Slope = 0.003 ± 0

4/21/2016

5/11/2016

5/31/2016Date

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

fSO

4

100806040200RH (%)

r2 = 0.594

Slope = 0.003 ± 0

12/11/201512/21/201512/31/20151/10/20161/20/2016

Da

te

(a)

17

343

344

345

346

347

348

349

350

351

352

353

354

355

356

357

358

359

360

361

Figure S14. Correlations between four OA factors and HRMS ions that are segregated into five 362

categories (CxHy+, CxHyO+, CxHyO2

+, CxHyNp+ and CxHyOzSq

+).From the top, HOA, COA, SV-363

OOA and LV-OOA. 364

1.0

0.8

0.6

0.4

0.2

0.0

R2

1101009080706050403020m/z

w6fact_ts_6_fp_0

1.0

0.8

0.6

0.4

0.2

0.0

R2

1101009080706050403020m/z

w6fact_ts_5_fp_0

1.0

0.8

0.6

0.4

0.2

0.0

R2

1101009080706050403020m/z

w6fact_ts_4_fp_0

1.0

0.8

0.6

0.4

0.2

0.0

R2

1101009080706050403020m/z

w6fact_ts_3_fp_0

18

365

366

Figure S15. Mass fractional contribution of the factors (four OA factors + two inorganic factors) 367 from PMF analysis to various ions that are relevant to each significant tracer. 368

369

370

371

372

Figure S16. (a) Compositional pie chart of the average fractional contribution of each of the OA 373 factors to the total OA over the campaign; (b) Average mass fractional contributions of seven ion 374 families to each of the OA factors and; (c) Average mass fractional contributions of four OA 375 factors to 4 each ion families 376

377

378

379

380

381

1.0

0.8

0.6

0.4

0.2

0.0

Ma

ss F

ract

ion

CO2 C2H3O SO SO2 NO NO2 C4H9 C5H11 C5H8O C6H10O C7H12O

43.99 43.018 47.967 63.962 29.998 45.993 57.07 71.086 84.058 98.073 112.09

HOA COA SV-OOA LV-OOA SO4 NO3

34%

27%

22%

17%

LVOOA

SVOOA

COA

HOA

(a) 100

80

60

40

20

0

Ma

ss P

erc

enta

ges

(%)

COA HOASVOOALVOOA

CxHy+

CxHyO1+

CxHyO2+

HyO1

CxHyNp

CxHyOzNp

CxHyOzSp

(b)

25.7%

42.7%

23.8%

4.3%

2.2%

47.7% 81.5%71.9%

41.2%11.6%21.0%

8.3%5.2% 4.9%

1.4% 0.78%

0.86%0.94% 0.86%

1.3% 0.47% 0.13% 0.08%

0.06%

0.94%

0.13%0.14% 0.02%100

80

60

40

20

0

Mas

s P

erc

enta

ges

(%)

COA

SVOOA

LVOOA

HOA

CxHyO1 CxHyNpCxHy CxHyO2

CxHyOzNp

25.9% 6.0% 6.7% 10.8% 2.1%

32.7% 15.4% 10.3% 17.0% 5.5%

25.3% 35.4% 19.0% 18.1% 22.2%

16.1% 43.2% 64.0% 54.0% 70.2%

(c)

19

382

383

384

385

386

387

388

389

390

391

392

393

394

395

396

Figure S17. Scatter plots of factors and relevant tracer ions colored by measurement date. 397

398

399

400

401

402

20

15

10

5

0

CO

A

0.200.150.100.050.00C3H5O

+(µg/m3)

r = 0.61Slope = 44.726 ± 0.535

4/21/2016

5/11/2016

5/31/2016

20

15

10

5

0

CO

A

50x10-3403020100

C5H8O+(µg/m3)

r = 0.89Slope = 356.36 ± 1.739

4/21/2016

5/11/2016

5/31/2016

25

20

15

10

5

0

LV

-OO

A

2.01.51.00.50.0CO2

+(µg/m3)

r = 0.78Slope = 10 ± 0.076

4/21/2016

5/11/2016

5/31/2016

25

20

15

10

5

0

LV

-OO

A

2.01.51.00.50.0C2H3O

+(µg/m3)

r = 0.74Slope = 10.854 ± 0.091

4/21/2016

5/11/2016

5/31/2016

20

15

10

5

0

CO

A

60x10-340200

C6H10O+(µg/m3)

r = 0.96Slope = 394.28 ± 1.044

4/21/2016

5/11/2016

5/31/2016

20

15

10

5

0

CO

A

8x10-36420

C7H12O+(µg/m3)

r = 0.70Slope = 1636.8 ± 15.656

4/21/2016

5/11/2016

5/31/2016

15

10

5

0

HO

A

6420BC(µg/m3)

r = 0.54Slope = 1.031 ± 0.015

4/21/2016

5/11/2016

5/31/2016

15

10

5

0

HO

A

0.60.40.20.0C4H9

+(µg/m3)

r = 0.95Slope = 21.789 ± 0.067

4/21/2016

5/11/2016

5/31/2016

15

10

5

0

HO

A

0.300.200.100.00C5H11

+(µg/m3)

r = 0.97Slope = 55.431 ± 0.141

4/21/2016

5/11/2016

5/31/2016

15

10

5

0

HO

A

0.80.60.40.20.0C3H7

+(µg/m3)

r = 0.87Slope = 14.054 ± 0.074

4/21/2016

5/11/2016

5/31/2016

15

10

5

0

HO

A

0.80.60.40.20.0C4H7

+(µg/m3)

r = 0.81Slope = 12.252 ± 0.083

4/21/2016

5/11/2016

5/31/2016

20

15

10

5

0

CO

A

0.40.30.20.10.0C3H3O

+(µg/m3)

r = 0.75Slope = 23.175 ± 0.189

4/21/2016

5/11/2016

5/31/2016

20

403

404

405

406

407

408

409

410

411

412

413

414

415

416

417

418

419

420

Figure S18. Triangular plots of (a) f44 versus f43 and (b) f44 versus f60 (c) f55,OOA sub versus f57, 421 OOA sub for the five OA factors and all of the measured OA data (dots), colored by the time of the 422 day. f43, f44, and f60 are the ratios of the organic signal at m/z = 43, 44, and 60 to the total organic 423 signal in the component mass spectrum, respectively. f55,OOA sub and f55,OOA sub are the ratios of 424 the organic signal at m/z 55, 57 after subtracting the contributions from SV-OOA and LV-OOA 425 (e.g., f55,OOA sub = m/z 55- m/z55SV-OOA - m/z55LV-OOA ; f57,OOA sub = m/z 57- m/z 57SV-OOA - m/z 57LV-426 OOA) 427

30

25

20

15

10

5

0

f44

(%

)

20151050f43 (%)

LVOOA

SVOOA

COA

HOA

(a)

4/21/2016

5/11/2016

5/31/2016

Date

12

10

8

6

4

2

0

f55 O

OA

,sub

(%

)

12840f57OOA,sub (%)

COA

LVOOA

HOA

COA line

HOA line

(b)

SVOOA

25

20

15

10

5

0

f44

(%)

6543210

f60 (%)

LVOOA

SVOOA

COA

HOA

(c)

21

428

429

430

431

432

433

434

435

436

437

438

439

440

441

442

Figure S19. Scatter plots of (a) LV-OOA vs. Ox; (b) SV-OOA vs Ox over the entire period in the 443 spring. Note that organic dominant period (5/20, 17:00 - 5/24, 0:00) are excluded. All scatter 444 plots are colored by measurement date. 445

446

447

448

449

8

6

4

2

0

LV-O

OA

(µ

g/m

3 )

100806040200

Ox (ppb)

r2 = 0.32

Slope = 0.067 ± 0.003

4/21/2016

5/11/2016

5/31/2016Date

(a) 12

10

8

6

4

2

0

SV

-OO

A (

µg

/m3 )

100806040200Ox (ppb)

r2

= 0.01Slope = 0.012 ± 0.003

4/21/2016

5/11/2016

5/31/2016Date

(b)

22

450

Figure S20. Overview of the temporal variations of submicron aerosols at the Korea Institute of 451

Science and Technology (KIST) in SMA from May 19 to May 25 including organic dominant 452

period colored by yellow (May 20, 17:00-May 24:0:00): (a) Time series of ambient air 453

temperature (T), relative humidity (RH), and precipitation (Precip.); (b) Time series of wind 454

direction (WD), with colors showing different wind speeds (WS); (c) Time series of CO and 455

SO2; (d) Time series of O3, and NO2; (e) Time series of total particulate matter (PM1), scanning 456

mobility particle sizer (SMPS) volume concentrations and also shown are the 24 h averaged 457

PM1+BC with bars. (f) Time series of the organic (Org.), nitrate (NO3-), sulfate (SO4

2-) , 458

ammonium (NH4+) and BC aerosols; (g) Time series of the mass fractional contribution of 459

organic aerosols (Org.), nitrate (NO3-), sulfate (SO4

2-), ammonium (NH4+), chloride (Cl-), and BC 460

to total PM1 together with isoprene and toluene time series; (h) Time series of each factor 461

Organic dominant period

30

15

0Org

an

ic &

NO

3 (

µg

/m3 )

604020

0

PM

1

(µg

/m3 )

5/19 5/20 5/21 5/22 5/23 5/24 5/25

Date&Time(KST)

10080604020

0% o

f P

M1

6040200

SM

PS

Vo

lum

e

(µm

3/cm3)

151050

SO

4 ,NH

4

(µg

/m3)

3025201510

T (

ºC) 8

6420

Prec. (m

)

360270180

900W

ind

(º)

9060300

RH

(%)

1.00.80.60.40.20.0

CO

(pp

m) 14

1210864

SO

2

(pp

b)

80

40

0

O3

(pp

b) 60

4020

NO

2

(pp

b)

10080604020

0

%O

A

12840L

V-O

OA

&

SV

-OO

A

(µg

/m3)

dat

241680

HO

A &

CO

A

(µg

/m3)

2.0

1.5OM

/OC

0.60.40.2

O/C

1.91.81.71.61.5

H/C

50x10-3

40302010

N/C

0.10

0.05

0.00

To

lun

e(p

pb

)

6x10-3

420

Isop

ren

e

(pp

b)

Org NO3 SO4 NH4 BC

3.02.01.0

ms

CO SO2

O3 NO2

HOA COA SVOOA LVOOA

23

derived from the positive matrix factorization (PMF) analysis; (i) Time series of the mass 462

fractional contribution to total organic aerosol (OA); (j) organic matter to organic carbon 463

(OM/OC), oxygen to carbon (O/C), hydrogen to carbon (H/C) and nitrogen to carbon (N/C) 464

(Canagaratna et al., 2015). 465

466

467

468

469

470

471

472

473

474

475

476

477

478

479

480

481

482

483

484

485

486

24

487

488

489

490

491

492

493

494

495

496

497

Figure S21. Long range transportation of plums from China to Korea during Haze period. Plots 498 are from MODIS, terra. 499

500

501

502

503

504

505

506

507

Figure S22. Two cluster solution of backtrajectroy analysis during haze period from (5/24 7:00-508 6/2 24:00). The trajectories were released at half of the mixing height at the KIST (latitude: 509 37.60N; longitude: 127.05E) and the average arriving height for the back trajectories for this 510 study was approximately 181 m. 511

25

512

513

514

515

516

517

518

519

520

521

Figure S23. Scatterplots between nitrate vs. RH during haze period. 522

523

524

525

526

527

528

529

530

531

532

533

20

15

10

5

0

NO

3

806040200RH

r2 = 0.477

Slope = 0.259 ± 0.022

5/25/2016

5/27/2016

5/29/2016

5/31/2016

26

References 534

535

Aiken, A. C., Decarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K. S., Ulbrich, I. M., 536 Mohr, C., Kimmel, J. R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A., Northway, M., Ziemann, P. J., 537 Canagaratna, M. R., Onasch, T. B., Alfarra, M. R., Prevot, A. S. H., Dommen, J., Duplissy, J., 538 Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC ratios of primary, secondary, and 539 ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry, 540 Environmental Science & Technology, 42, 4478-4485, 10.1021/es703009q, 2008. 541

Canagaratna, M. R., Jimenez, J. L., Kroll, J. H., Chen, Q., Kessler, S. H., Massoli, P., Hildebrandt Ruiz, 542 L., Fortner, E., Williams, L. R., Wilson, K. R., Surratt, J. D., Donahue, N. M., Jayne, J. T., and 543 Worsnop, D. R.: Elemental ratio measurements of organic compounds using aerosol mass 544 spectrometry: characterization, improved calibration, and implications, Atmospheric Chemistry and 545 Physics, 15, 253-272, 10.5194/acp-15-253-2015, 2015. 546

Kim, H., Zhang, Q., Bae, G. N., Kim, J. Y., and Lee, S. B.: Sources and atmospheric processing of winter 547 aerosols in Seoul, Korea: insights from real-time measurements using a high-resolution aerosol mass 548 spectrometer, Atmos. Chem. Phys., 17, 2009-2033, 10.5194/acp-17-2009-2017, 2017. 549

Kuwata, M., Zorn, S. R., and Martin, S. T.: Using Elemental Ratios to Predict the Density of Organic 550 Material Composed of Carbon, Hydrogen, and Oxygen, Environmental Science & Technology, 46, 551 787-794, 10.1021/es202525q, 2012. 552

Middlebrook, A. M., Bahreini, R., Jimenez, J. L., and Canagaratna, M. R.: Evaluation of Composition-553 Dependent Collection Efficiencies for the Aerodyne Aerosol Mass Spectrometer using Field Data, 554 Aerosol Science and Technology, 46, 258-271, 10.1080/02786826.2011.620041, 2012. 555

Zhang, Q., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., and Jimenez, J. L.: Time- and size-resolved 556 chemical composition of submicron particles in Pittsburgh: Implications for aerosol sources and 557 processes, Journal of Geophysical Research-Atmospheres, 110, 10.1029/2004jd004649, 2005. 558

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