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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 ([email protected])
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
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