Supplement of Atmos. Chem. Phys., 16, 8309–8329, 2016http://www.atmos-chem-phys.net/16/8309/2016/doi:10.5194/acp-16-8309-2016-supplement© Author(s) 2016. CC Attribution 3.0 License.

Supplement of

Primary and secondary aerosols in Beijing in winter: sources, variationsand processesYele Sun et al.

Correspondence to: Yele Sun (sunyele@mail.iap.ac.cn)

The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence.

2

Table S1. A summary of non-refractory submicron aerosol composition and OA factors from AMS measurements in Beijing China.

Sampling sites: Chinese Academy of Meteorological Sciences (CAMS); Peking University (PEK); Institute of Atmospheric Physics (IAP). References: 1(Sun et al., 2010); 2(Huang et al., 2010); 3(Hu et al., 2016); 4(Sun et al., 2012); 5(Sun et al., 2013); 6(Zhang et al., 2015a); 7(Zhang et al., 2014); 8This study; 9(Zhang et al., 2015b); 10(Xu et al., 2015).

Site 1CAMS 2PEK 3PEK 4PEK 5IAP 6IAP 6IAP 7IAP 8IAP 9IAP 10IAP

AMS Q-AMS HR-AMS HR-AMS ACSM ACSM HR-AMS HR-AMS HR-AMS HR-AMS HR-AMS HR-AMS

Season Summer Summer/Autumn Winter Summer Winter Summer Fall Winter Winter Winter Fall

Date 9 - 21 Jul,

2006 24 Jul - 20 Sep,

2008 22 Nov - 22 Dec, 2010

26 Jun - 28 Aug, 2011

21 Nov - 20 Jan, 2012

1 - 31 Aug, 2012

1- 31 Oct, 2012

1 - 31 Jan, 2013

16 Dec, 2013- 17 Jan, 2014

1 Jan - 3 Feb, 2014

14 Oct -12 Nov,

2014

Index S, 2006 S-F, 2008 W, 2010 S, 2011 W, 2011-2012

S, 2012 F, 2012 W, 2013 W, 2013-2014

W, 2014 F, 2014

Organics 28.1 23.9 34.5 20.0 34.4 49.1 38.1 27.3 29.4 Sulfate 20.3 16.8 8.7 9.0 9.3 19.6 9.4 8.6 9.1 Nitrate 17.3 10.0 6.8 12.4 10.9 12.5 7.2 8.1 17.8 Ammonium 13.1 10.0 7.7 8.0 8.6 8.9 5.4 4.5 7.8 Chloride 1.1 0.6 5.8 0.5 3.5 3.6 4.0 2.0 2.9 NR-PM1 80 61 64 50 67 94 64 51 67 HOA 11.5 4.3 4.7 7.1 5.8 2.9 3.0 5.4 3.9 4.4 3.4 COA 5.8 6.7 6.6 3.0 7.8 9.8 6.7 3.8 7.5 CCOA 8.2 11.3 9.3 7.6 4.6 BBOA 4.1 3.3 4.1 OOA 12.7 10.7 7.2 SV-OOA 4.3 5.7 4.3 6.3 12.8 12.1 9.8 7.0 LV-OOA 12.3 8.1 6.2 10.2 13.8 4.4 4.1 7.9 OA 28 24 35 20 34 13 27 51 38 27 30

3

Figure S1. Correlation between measured NH4+ and predicted NH4

+ (=18× (2×SO42-/96 + NO3

-

/62 + Chl/35.5)).

Figure S2. Comparison of the elemental ratios calculated from the A-A method (Aiken et al., 2008) with those from the recently updated I-A method (Canagaratna et al., 2015).

40

35

30

25

20

15

10

5

0

Mea

sure

d N

H4 (

µg

m-3

)

6050403020100

Predicted NH4 (µg m-3

)

f(x) = 0.69x

r2 = 0.98

80

60

40

20

RH

(%)

2.5

2.0

1.5

1.0

0.5

0.0

Ele

men

tal R

atio

s, I

-A

2.01.51.00.50.0

Elemental Ratios, A-A

O/C

r2 = 0.998

Slope = 1.28

H/C

r2 = 0.97

Slope = 1.10

OM/OC

r2 = 0.998

Slope = 1.24Intercept = -0.25

4

Figure S3. A summary of PMF diagnostic plot: (a) Q/Qexp as a function of number of factors, (b) mass fractions of OA factors as a function of fpeak, (c) scaled residual for each fragment ion, (d) a comparison of measured and PMF reconstructed mass, (e) time series of residual, and (f) time series of Q/Qexp.

14

12

10

8

6

Q/Q

expe

cted

87654321Number of factors

1.0

0.8

0.6

0.4

0.2

0.0

Mas

s F

ract

ion

-1 -0.5 0 0.5 1

fPeak

80

40

0

-40Sca

led

Re

sid

ua

l

14012010080604020m/z120

80

40

0

Tot

al M

ass

12/16 12/21 12/26 12/31 1/5 1/10 1/15

Measured Reconstructed

2.0

1.0

0.0

-1.0Σ R

esi

d

12/16 12/21 12/26 12/31 1/5 1/10 1/15Date & Time

50403020100

Σ (R

esi

d2 /σ

2 )/Q

exp

aq-OOA

BBOA

CCOA

COAHOA

OOA

(a) (b)

(c)

(f)

(e)

(d)

5

Figure S4. Correlations of six OA factors with other tracers.

Figure S5. Comparisons of time series of six OA factors from PMF analysis of V-mode and W-mode.

1.00.80.60.40.20.0

1.00.80.60.40.20.0

1.00.80.60.40.20.0

1.00.80.60.40.20.0

1.00.80.60.40.20.0

1.00.80.60.40.20.0

SN

AS

O4

NO

3N

H4

Chl

PA

HC

O2

C2H

4O2

C2H

3OC

3H5O

C6H

10O

C3H

7C

4H6

C4H

7C

4H9

C8H

5C

H4N

C2H

6NC

3H8N

CH

3SO

2S

O2

O3

Ox

NO

xC

O

(f) aq-OOA

(e) OOA

(d) CCOA

(c) BBOA

(b) COA

(a) HOA

R2 O

A F

acto

rs v

s. T

race

r S

peci

es

40

30

20

10

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode HOA

200

150

100

50

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode COA

60

40

20

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode CCOA

40

30

20

10

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode WCOA

40

30

20

10

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode LVOOA

60

50

40

30

20

10

0

12/21/2013 12/26/2013 12/31/2013 01/05/2014 01/10/2014 01/15/2014dat

W-mode V-mode SVOOA

HOA

COA

CCOA

BBOA

OOA

Aq-OOA

6

Figure 6. Mass spectra comparisons between UMR-PMF and HMR-PMF.

12

8

4

0120110100908070605040302010

m/z (amu)

12840

6420

6420

86420

1086420

43210

543210

86420

86420

12840

86420

(f) aq-OOA

(e) OOA

(d) CCOA

(c) BBOA

(b) COA

(a) HOA

% o

f T

ota

l Sig

na

l

HMR UMR

% o

f To

tal S

ign

al

7

Figure S7. Correlations of organics at different sizes with six OA factors, sulfate and nitrate.

Figure S8. Variations of (a) mass concentrations and (b) mass fractions of OA factors as a function of RH.

1.0

0.8

0.6

0.4

0.2

0.0

R2

3 4 5 6 7 8100

2 3 4 5 6 7 81000

2

Dva (nm)

aq-OOA HOA COA CCOA BBOA OOA NO3 SO4

80

60

40

20

0

Ma

ss C

onc.

(µ

g m

-3)

8070605040302010RH (%)

HOA COA BBOA CCOA OOA aq-OOA1.0

0.8

0.6

0.4

0.2

0.0

Mas

s F

ract

ion

8070605040302010RH (%)

HOA COA BBOA CCOA OOA aq-OOA(a) (b)

8

Figure S9. Correlations of six OA factors with each unit m/z.

0.8

0.6

0.4

0.23803403002602201801401006020

m/z (amu)

1.00.80.60.40.2

1.0

0.8

0.6

0.4

0.60.50.40.30.2

0.8

0.6

0.4

0.2

1.0

0.8

0.6

0.4

(f) aq-OOA

(e) OOA

(d) CCOA

(c) BBOA

(b) COA

(a) HOA

R2 O

A F

acto

rs v

s. m

/z

9

Figure S10. Contributions of six OA factors to each m/z.

Figure S11. Bivariate polar plot of BBOA.

1.0

0.8

0.6

0.4

0.2

0.0

Fra

ctio

n o

f m/z

3803403002602201801401006020m/z (amu)

HOA COA CCOA BBOA OOA aq-OOA

0

10

20

30

40

50

10 20 30 40 50

0

45

90

135

180

225

270

315

N

NE

E

SE

S

SW

W

NW

12.5 25 37.5

6

5

4

3

2

1

0

BB

OA

(μg m

-3)

10

Figure S12. Average diurnal cycles of OA/CO for six OA factors.

Figure S13. Variations of SO2+/SO3

+ and SO+/SO2+ ratios as a function of RH.

References:

Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K. S., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Onasch, T. B., Alfarra, M. R., Prevot, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with High-Resolution Time-of-Flight Aerosol Mass Spectrometry, Environ. Sci. Technol., 42, 4478-4485, 2008.

Canagaratna, M. R., Jimenez, J. L., Kroll, J. H., Chen, Q., Kessler, S. H., Massoli, P., Hildebrandt Ruiz, L., Fortner, E., Williams, L. R., Wilson, K. R., Surratt, J. D., Donahue, N. M., Jayne, J. T., and Worsnop, D. R.: Elemental ratio measurements of organic compounds using

16

12

8

4

0

OA

/ΔC

O (

µg

m-3

pp

m-1

)

24201612840Hour of Day

HOA COA BBOA CCOA OOA aq-OOA

7

6

5

4

3

2

1

SO

2+/S

O3

+

8070605040302010

RH (%)

1.0

0.8

0.6

0.4

0.2

0.0

SO

+/SO

2+

SO2+/SO3

+ SO

+/SO2

+

11

aerosol mass spectrometry: characterization, improved calibration, and implications, Atmos. Chem. Phys., 15, 253-272, 10.5194/acp-15-253-2015, 2015.

Hu, W., Hu, M., Hu, W., Jimenez, J. L., Yuan, B., Chen, W., Wang, M., Wu, Y., Chen, C., Wang, Z., Peng, J., Zeng, L., and Shao, M.: Chemical composition, sources and aging process of sub-micron aerosols in Beijing: contrast between summer and winter, Journal of Geophysical Research: Atmospheres, 121, n/a-n/a, 10.1002/2015JD024020, 2016.

Huang, X. F., He, L. Y., Hu, M., Canagaratna, M. R., Sun, Y., Zhang, Q., Zhu, T., Xue, L., Zeng, L. W., Liu, X. G., Zhang, Y. H., Jayne, J. T., Ng, N. L., and Worsnop, D. R.: Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer, Atmos. Chem. Phys., 10, 8933-8945, 10.5194/acp-10-8933-2010, 2010.

Sun, J., Zhang, Q., Canagaratna, M. R., Zhang, Y., Ng, N. L., Sun, Y., Jayne, J. T., Zhang, X., Zhang, X., and Worsnop, D. R.: Highly time- and size-resolved characterization of submicron aerosol particles in Beijing using an Aerodyne Aerosol Mass Spectrometer, Atmos. Environ., 44, 131-140, 2010.

Sun, Y. L., Wang, Z., Dong, H., Yang, T., Li, J., Pan, X., Chen, P., and Jayne, J. T.: Characterization of summer organic and inorganic aerosols in Beijing, China with an Aerosol Chemical Speciation Monitor, Atmos. Environ., 51, 250-259, 10.1016/j.atmosenv.2012.01.013, 2012.

Sun, Y. L., Wang, Z. F., Fu, P. Q., Yang, T., Jiang, Q., Dong, H. B., Li, J., and Jia, J. J.: Aerosol composition, sources and processes during wintertime in Beijing, China, Atmos. Chem. Phys., 13, 4577-4592, 10.5194/acp-13-4577-2013, 2013.

Xu, W. Q., Sun, Y. L., Chen, C., Du, W., Han, T. T., Wang, Q. Q., Fu, P. Q., Wang, Z. F., Zhao, X. J., Zhou, L. B., Ji, D. S., Wang, P. C., and Worsnop, D. R.: Aerosol composition, oxidation properties, and sources in Beijing: results from the 2014 Asia-Pacific Economic Cooperation summit study, Atmos. Chem. Phys., 15, 13681-13698, 10.5194/acp-15-13681-2015, 2015.

Zhang, J., Wang, Y., Huang, X., Liu, Z., Ji, D., and Sun, Y.: Characterization of organic aerosols in Beijing using an aerodyne high-resolution aerosol mass spectrometer, Advances in Atmospheric Sciences, 32, 877-888, 10.1007/s00376-014-4153-9, 2015a.

Zhang, J. K., Sun, Y., Liu, Z. R., Ji, D. S., Hu, B., Liu, Q., and Wang, Y. S.: Characterization of submicron aerosols during a month of serious pollution in Beijing, 2013, Atmos. Chem. Phys., 14, 2887-2903, 10.5194/acp-14-2887-2014, 2014.

Zhang, J. K., Ji, D. S., Liu, Z. R., Hu, B., Wang, L. L., Huang, X. J., and Wang, Y. S.: New characteristics of submicron aerosols and factor analysis of combined organic and inorganic aerosol mass spectra during winter in Beijing, Atmos. Chem. Phys. Discuss., 15, 18537-18576, 10.5194/acpd-15-18537-2015, 2015b.