Supplementary
Factor Analysis of Combined Organic and Inorganic Aerosol Mass Spectra
from High Resolution Aerosol Mass Spectrometer Measurements
Y. L. Sun1, Q. Zhang2, J. J. Schwab3, T. Yang1, N. L. Ng4, K. L. Demerjian3
1
State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric
Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing,
China
2
3
Department of Environmental Toxicology, University of California, Davis, California,
USA
Atmospheric Sciences Research Center, State University of New York at Albany, Albany,
New York
4
School of Chemical and Biomolecular Engineering and School of Earth and
Atmospheric Sciences, Georgia Institute of Technology, Atlanta,
Georgia, USA
Correspondence to: Y. L. Sun ([email protected])
+
+
+
f(x) = 0.506x
a
f(x) = 0.962x
2
b
2
r = 1.00
r = 1.00
3
+
5
NO +NO2
4
3
2
+
+
+
SO +SO2 +SO3 +HSO3 +H2SO4
6
2
1
1
0
0
0
2
4
3.5
f(x) = 0.996x
3.0
r = 1.00
6
8
2HR SO4
10
12
0
c
0.20
2
1
f(x) = 0.758x
2
HR NO3
3
4
d
2
0.15
Cl +HCl
+
2.5
2.0
+
1.5
+
+
NH +NH2 +NH3
+
r = 1.00
1.0
0.10
0.05
0.5
0.0
0.00
0.0
1.0
2.0
+
HR NH4
3.0
0.00 0.05 0.10 0.15 0.20 0.25
HR Chl
Fig. S1. Correlations between the sum of selected fragmentation ions for PMF analysis
and the total mass concentrations of (a) sulfate, (b) nitrate, (c) ammonium, and (d)
chloride from high resolution (HR) analysis.
1.520
Q for FPEAK 0
Best Solution
Q/Qexpected
Q/Qexpected
(a)
8
6
4
2
0
1.500
1.490
0.6
0.4
0.2
FPEAK
1.0
0.8
0.6
0.4
0.2
0.0
R, Time Series
Residual
8 HOA
7 COA
4 NOA
6 LO-OOA
5 MO-OOA
3 LV-OOA
1 NO3-OA
2 SO4-OA
(d)
2_3
5_6
3_6
2_6
4_5
1_8
2_5
1_6
6_8 2_4
5_7
6_7
3_47_8
4_7
4_6
1_2
3_7
1_3
1_7
5_8
3_8
4_8
2_7 1_5
1_4
2_8
0.0
FPEAK
(e)
Scaled Residual
0
-0.2
-0.4
-0.6
Mass Frac.
1.0
0.8
0.6
0.4
0.2
0.0
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
Number of Factors
(c)
3_5
0.2
0.4
0.6
0.8
R, Mass Spectra
1.0
20
10
0
-10
Boxes are +/- 25% of points
-20
10
-3
Mass Conc. (µg m )
Q for P 8
Best Solution
1.510
1 2 3 4 5 6 7 8 9 10 11 12
20
30
40
50
60
70
80
90
100
110
120
m/z
(f)
30
Measured Total Mass
Reconstructed Total Mass
20
-3
 Residual (µg m )
10
0
0.4
0.2
0.0
-0.2
-0.4
2
2
 (Resid / )/Qexp
2
2
 (Resid / )/Qexp
(b)
15
10
5
0
(g)
Residual (= measured - reconstructed)
Q/Qexp contribution for each time step
(h)
7/14
7/16
7/18
7/20
7/22
7/24
(i)
12
8
4
0
10
7/26
7/28
7/30
8/1
8/3
Q/Qexp contribution for each fragment ion
20
30
40
50
60
70
m/z
80
90
100
110
120
Fig. S2. Summary of the evaluation of the PMF analysis of the unified organic and
inorganic aerosols dataset. (a) Q/Qexpected as a function of number of factors (p) selected
for PMF modeling; (b) Q/Qexpected as a function of fPeak; (c) mass fraction of each factor
vs. fPeak values for the 8-factor solution. The residual fraction for different fpeak values
is ~0.6%; (d) correlations of mass spectra and time series among PMF factors. The
numbers refer to the OA factors in (c); (e) the box and whiskers plot showing the
distributions of scaled residuals for each fragment ion; (f) time series of the measured
mass concentration and the reconstructed mass; (g) variations of the residual of the fit; (h)
the Q/Qexpected values for each point in time; and (i) the Q/Qexpected values for each
fragment ion.
8
6
4
2
0
12
8
4
0
2.5
2.0
1.5
1.0
0.5
0.0
O/C = 0.13, H/C = 1.71, N/C = 0.046, OM/OC = 1.37 NO -OA
3
HOA
O/C = 0.17, H/C = 1.59, N/C = 0.004, OM/OC = 1.36
COA
O/C = 0.35, H/C = 1.52, N/C = 0.044, OM/OC = 1.65
NOA
2.0
1.5
1.0
0.5
0.0
1.2
0.8
0.4
0.0
O/C = 0.34, H/C = 1.43, N/C = 0.002, OM/OC = 1.58 SV-OOA
12
8
4
0
12
10
8
6
4
2
0
-3
O/C = 0.05, H/C = 1.87, N/C = 0.003, OM/OC = 1.22
b
6
4
2
0
8
6
4
2
0
O/C = 0.61, H/C = 1.26, N/C = 0.007, OM/OC = 1.92 LV-OOA
6
4
2
0
CxHy CxHyO1 CxHyO2 CxHyNp
CxHyOzNp HyO1 SOx NOx NHx Clx
10
20
30
40
50
60
70
80
90
100
7/13
7/18
m/z (amu)
7/23
7/28
Date & Time
c
0.6
0.4
0.2
0.0
3
2
1
0
Mass Concentration (µg m )
8
6
4
2
0
O/C = 0.66, H/C = 1.30, N/C = 0.015, OM/OC = 2.00 SO -OA
4
-3
15
10
5
0
40
30
20
10
0
10
8
6
4
2
0
8
6
4
2
0
Concentration (µg m )
% of Total Signal
a
4
2
0
2
1
0
8
6
4
2
0
6
4
2
0
8/2
0 2 4 6 8 10 12 14 16 18 20 22 24
Hour of Day
Factor 8
Factor 7
Factor 6
Factor 5
Factor 4
Factor 3
Factor 2
Factor 1
CxHy CxHyO1 CxHyO2 CxHyNp
CxHyOzNp HyO1 SOx NOx NHx Clx
10
20
30
40
50
60
m/z (amu)
70
80
90
100
12
8
4
0
8
6
4
2
0
6
4
2
0
5
4
3
2
1
0
b
4
3
2
1
0
3.0
2.0
1.0
0.0
-3
Factor 9
Mass Concentration (µg m )
a
-3
10
8
6
4
2
0
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
15
10
5
0
12
8
4
0
8
6
4
2
0
20
15
10
5
0
40
30
20
10
0
Mass Concentration (µg m )
% of Total Signal
Fig. S3. (a) High resolution mass spectra of seven factors. The signals of OA in SO4-OA
and NO3-OA were enhanced by a factor of 3 and 10, respectively, for clarity. (b) Time
series of mass concentration of OA in each factor, and (c) Diurnal profile of OA in each
factor.
3
2
1
0
6
4
2
0
3.0
2.0
1.0
0.0
10
8
6
4
2
0
6
4
2
0
7/13
7/18
7/23
7/28
Date & Time (EST)
8/2
c
6
4
2
0
5
4
3
2
1
0
3
2
1
0
6
4
2
0
1.0
0.8
0.6
0.4
0.2
0.0
8
6
4
2
0
3.0
2.0
1.0
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hour of Day
Fig. S4. (a) High resolution mass spectra of nine factors. The signals of OA in factor 2
and factor 1 were enhanced by a factor of 3 and 10, respectively, for clarity. (b) Time
series of mass concentration of OA in each factor, and (c) Diurnal profile of OA in each
factor.
fPeak = -0.2
fPeak = 0
fPeak = 0.6
SO4-OA
b
NO3-OA
4
2
0
12
HOA
8
COA
NOA
LO-OOA
MO-OOA
4
2
0
LV-OOA
6
Fraction of Total Signal
-3
Mass Concentration (µg m )
4
0
10
8
6
4
2
0
5
4
3
2
1
0
8
6
4
2
0
6
fPeak = -0.2
fPeak = 0
fPeak = 0.6
SO4-OA
0.20
0.15
0.10
0.05
0.00
0.4
0.3
0.2
0.1
0.0
NO3-OA
80
60
40
20
0
0.10
0.08
0.06
0.04
0.02
0.00
0.10
0.08
0.06
0.04
0.02
0.00
0.10
0.08
0.06
0.04
0.02
0.00
HOA
-3
a
x10
10
8
6
4
2
0
6
COA
NOA
LO-OOA
MO-OOA
0.12
0.08
0.04
0.00
LV-OOA
0.12
4
0.08
2
0.04
dat
0
0.00
7/13
7/18
7/23
7/28
8/2
10
20
30
40
50
60
70
80
90
100
110
120
Fig. S5. Comparisons of (a) time series and (b) mass spectra profiles of PMF factors from
8-factor solution for three selected fPeak values (-0.2, 0, and 0.6).
0.64
0.62
HOA vs. NOx
0.590
0.580
2-
SO4-OA vs. SO4
0.7
0.8
0.6
0.5
SO4-OA vs. CO2
+
-
0.980
0.6
0.5
LV-OOA vs. CO2
+
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
0.50
0.4
0.2
0.0
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
0.7
0.4
0.6
NO3-OA vs. NO3
HOA vs. EC
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
Pearson R
Pearson R
0.985
0.500
0.9
0.4
1.000
0.990
0.510
0.8
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
0.995
0.520
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
Pearson R
Pearson R
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
1.00
0.95
0.90
0.85
0.80
0.75
0.70
HOA vs. Babs
Pearson R
0.63
0.600
Pearson R
0.65
0.530
Pearson R
0.610
0.66
Pearson R
Pearson R
0.67
MO-OOA vs. HCHO
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
0.45
0.40
0.35
0.30
0.25
LO-OOA vs. Chl
-0.6-0.4-0.2 0.0 0.2 0.4 0.6
Fig. S6. Correlations of selected PMF factors with external tracer species as a function of
fPeak. The blue circles refer to the best solution, i.e., fPeak = 0.
a
f(x) = 0.76x
2
2
r = 1.00
8
6
4
2
6
4
2
0
0
2
4
6
8
10
TSHOA, Sun et al. (2011)
c
0
f(x) = 1.10x
10
2
r = 0.90
8
6
4
2
0
0
2
4
6
8
10
TSCOA, Sun et al. (2011)
d
TSLV-OOA + SO4-OA, This study
0
TSLO-OOA+MO-OOA, This study
r = 0.98
8
TSCOA, This study
TSHOA, This study
b
f(x) = 0.97x
10
f(x) = 0.94x
8
2
r = 0.92
6
4
2
0
2
4
6
8
10
TSSV-OOA, Sun et al. (2011)
0
2
4
6
8
TSLV-OOA, Sun et al. (2011)
Fig. S7. Time series (TS) comparison of (a) HOA, (b) COA, (c) LO-OOA + MO-OOA vs.
SV-OOA, and (d) LV-OOA + SO4-OA vs. LV-OOA from 8-factor solution of PMF
analysis of the combined organic and inorganic aerosols in this study and 5-factor
solution of PMF analysis of OA in Sun et al. (2011).
MS (% of Total), PMFOA
LV-OOA
MO-OOA
15
10
5
LO-OOA
10
10
8
8
6
6
4
4
NOA
COA
8
6
6
6
4
4
2
S = 1.14
2
S = 0.87
2
r = 0.97
0
0
4
8
2
r = 0.97
0
0
4
8
S = 1.01
2
12
0
2
4
6
r = 0.95
0
8 10
0
2
4
2
S = 1.00
2
r = 0.98
0
4
2
S = 1.05
2
12
HOA
8
S = 0.98
2
0
6
2
r = 0.99
0
2
4
6
r = 1.00
0
8
0
2
4
6
8
3.5
5
8
6
4
4
2.0
2
1.5
S = 1.39
S = 1.22
2
r = 0.86
0
0
2
4
6
6
1
0
1
2
3
4
5
0
0
2
4
6
6
4
S = 0.85 0.5
2
r = 0.91
0.0
2
r = 0.73
0
8
4
1.0
2
2
10
2.5
3
12
8
3.0
4
6
-3
TS (µg m ), PMFOA
MS (% of Total), PMFOA+Inorg
S = 0.79
2
S = 0.96
2
r = 0.98
0
-3
1
2
3
4
S = 1.03
2
2
r = 0.99
0
0
2
4
6
8
2
r = 1.00
0
0
2
4
6
8
TS (µg m ), PMFOA+Inorg
Fig. S8. Mass spectra (MS) and time series (TS) comparison of six OA factors from PMF
analysis of the combined organic and inorganic aerosols, and OA only.
6 8
2
4
1.6
1.2
0.8
0.4
0.0
4
6 8
2
4
6 8
-3
0.08
0.2
0.04
0.0
0.00
4
1000
LO-OOA
6 8
2
4
6 8
100
Dva (nm)
MO-OOA
4
6 8
2
4
6 8
-3
100
Dva (nm)
6 8
2
4
100
Dva (nm)
2.5
2.0
1.5
1.0
0.5
0.0
1000
4
1000
6 8
1000
LV-OOA
2.5
2.0
1.5
1.0
0.5
0.0
4
1000
6 8
2
4
100
Dva (nm)
6 8
1000
-3
100
Dva (nm)
dM/dlogDva (µg m )
6 8
0.12
0.4
-3
-3
dM/dlogDva (µg m )
100
Dva (nm)
0.6
dM/dlogDva (µg m )
4
NOA
0.16
-3
0.0
COA
dM/dlogDva (µg m )
0.4
0.8
dM/dlogDva (µg m )
-3
6-Factor
8-Factor
0.8
dM/dlogDva (µg m )
HOA
dM/dlogDva (µg m )
-3
dM/dlogDva (µg m )
1.2
NO3-OA
0.16
0.12
0.08
0.04
0.00
0.8
0.6
0.4
0.2
0.0
-
NO3
4
6 8
2
4
100
Dva (nm)
6 8
1000
SO4-OA
0.6
5
4
3
2
1
0
2-
SO4
0.4
0.2
0.0
4
6 8
2
4
100
Dva (nm)
6 8
1000
Fig. S9. Comparisons of the size distributions of OA factors from multiple linear
regression analysis using six OA factors from PMF of only the OA (6-factor in the figure)
and eight OA factors from PMF of the combined organic and inorganic aerosol (8-factor
in the figure). The last two plots show the comparisons of the size distributions of
NO3-OA and SO4-OA with nitrate and sulfate, respectively.
-3
dM/dlogDva (µg m )
HOA
Linear regression method
Tracer-m/z method
5 2:00-3:00
5 3:00-4:00
5 4:00-5:00
4
4
4
3
3
3
2
2
2
1
1
1
0
0
0
a
5 0:00-1:00
4
3
2
1
0
5 1:00-2:00
4
3
2
1
0
5 6:00-7:00
4
3
2
1
0
5 12:00-13:00
4
3
2
1
0
5 7:00-8:00
4
3
2
1
0
5 13:00-14:00
4
3
2
1
0
5 8:00-9:00
4
3
2
1
0
5 14:00-15:00
4
3
2
1
0
5 9:00-10:00
4
3
2
1
0
5 15:00-16:00
4
3
2
1
0
5 10:00-11:00
4
3
2
1
0
5 16:00-17:00
4
3
2
1
0
5 11:00-12:00
4
3
2
1
0
5 17:00-18:00
4
3
2
1
0
5 18:00-19:00
4
3
2
1
0
5 19:00-20:00
4
3
2
1
0
5 20:00-21:00
4
3
2
1
0
5 21:00-22:00
4
3
2
1
0
5 22:00-23:00
4
3
2
1
0
5 23:00-24:00
4
3
2
1
0
6
2
4 6
100
6
1000
2
4 6
100
6
1000
2
100
4 6
6
1000
2
100
4 6
6
1000
2
5 5:00-6:00
4
3
2
1
0
4 6
100
6
1000
2
4 6
100
1000
Dva (nm)
-3
dM/dlogDva (µg m )
OOA
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
0:00-1:00
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
6:00-7:00
12:00-13:00
18:00-19:00
6
2
100
4 6
1000
Linear regression method
10 2:00-3:00
10
8
8
6
6
4
4
2
2
0
0
8:00-9:00
10
10
8
8
6
6
4
4
2
2
0
0
10 14:00-15:00
10
8
8
6
6
4
4
2
2
0
0
10 20:00-21:00
10
8
8
6
6
4
4
2
2
0
0
1:00-2:00
7:00-8:00
13:00-14:00
19:00-20:00
6
2
100
4 6
1000
6
2
100
4 6
Tracer-m/z method
10 4:00-5:00
8
6
4
2
0
9:00-10:00
10 10:00-11:00
8
6
4
2
0
15:00-16:00
10 16:00-17:00
8
6
4
2
0
21:00-22:00
10 22:00-23:00
8
6
4
2
0
3:00-4:00
6
1000
2
100
4 6
1000
6
2
100
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
10
8
6
4
2
0
4 6
1000
b
5:00-6:00
11:00-12:00
17:00-18:00
23:00-24:00
6
2
100
4 6
1000
Dva (nm)
Fig. S10. Comparisons of size distributions of (a) HOA and (b) OOA from linear
regression method and tracer-m/z method for each hour in the day.
RH (%)
WS (m/s)
Temp.
30
25
20
15
10
SO2
2.5
2.0
1.5
1.0
0.5
0.0
80
60
40
4
3
2
1
0
25
20
15
10
5
0
80
60
40
20
0
Temp. (ºC)
(b)
(c)
NO
NO2
SO2 (ppb)
O3, Ox (ppb) NO, NO2 (ppb)
RH
(a)
100
(d)
0
2
O3
4
6
8
Ox
10 12 14 16 18 20 22 24
Hour of Day
Fig. S10. Diurnal profiles of (a) relative humidity (RH) and temperature, (b) wind speed
(WS), (c) NO, NO2, and SO2, and (d) O3 and Ox for the entire study.
Temp. (°C)
100
80
60
40
20
0
25
20
15
6
80
60
40
20
0
HCHO O3
4
2
-3
0
4
3
2
1
O3 (ppb)
HCHO (ppb)
Temp. RH
RH (%)
Mass Conc. (µg m )
30
SO4-OA
NO3-OA
LV-OOA
MO-OOA
LO-OOA
HOA
COA
NOA
0
12:00 AM
7/22/2009
6:00 AM
12:00 PM
6:00 PM
12:00 AM
7/23/2009
Date/Time (EST)
Fig. S11. Time series of meteorology (temperature, relative humidity and solar radiation),
HCHO and O3, and OA concentrations in PMF factors of SO4-OA, NO3-OA, LV-OOA,
MO-OOA, LO-OOA, NOA, COA, and HOA.
Table S1. Summary of the contribution of OA in each factor to the total OA for different
fPeak values. Note only solutions that converged and generated realistic mass spectra are
included.
LV-OOA
MO-OOA
LO-OOA
NOA
COA
HOA
NO3-OA
SO4-OA
Average
17.1%
22.5%
21.1%
3.6%
11.7%
11.4%
2.7%
9.9%
Std Dev
2.0%
0.7%
3.2%
1.0%
0.4%
0.8%
0.8%
2.4%
Min
15.3%
21.8%
17.5%
2.6%
11.1%
10.8%
1.8%
7.8%
Max
19.0%
23.5%
23.9%
4.8%
12.0%
12.6%
3.7%
12.3%
References:
Sun, Y. L., Zhang, Q., Schwab, J. J., Demerjian, K. L., Chen, W. N., Bae, M. S., Hung, H.
M., Hogrefe, O., Frank, B., Rattigan, O. V., and Lin, Y. C.: Characterization of
the sources and processes of organic and inorganic aerosols in New York City
with a high-resolution time-of-flight aerosol mass spectrometer, Atmos. Chem.
Phys., 11, 1581-1602, 10.5194/acp-11-1581-2011, 2011.