Supplement of Atmos. Chem. Phys., 16, 11001–11018, 2016
http://www.atmos-chem-phys.net/16/11001/2016/
doi:10.5194/acp-16-11001-2016-supplement
© Author(s) 2016. CC Attribution 3.0 License.
Supplement of
Chemical characterization of organosulfates in secondary organic aerosol
derived from the photooxidation of alkanes
Matthieu Riva et al.
Correspondence to: J. D. Surratt ([email protected])
The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence.
Table S1. Proposed structures, retention times, formulas and accurate masses of organosulfates (OSs) identified in dodecane, decalin and
cyclodecane SOA.
[M - H]- ion (m/z)
VOC
Retention
time (min)
Measured
mass
Error
(ppm)
Q-TOFMS
suggested
formula
DBE
Proposed structure
195
Decalin
7.93
195.0697
3.03
C7H15O4S−
0
Not Identified
209
Dodecane
6.75
209.0472
5.62
C7H13O5S−
1
Not Identified
237
Dodecane
9.12
237.0786
4.67
C9H17O5S−
1
Not Identified
8.51
249.0807
2.84
249
251
255
C10H17O5S−
Cyclodecane
9.31
249.0797
1.5
8.51
251.0950
1.28
Cyclodecane
Dodecane
O
9.31
251.0953
0.10
8.87
255.0914
4.56
OSO3
2
OH
C10H19O5S−
1
C9H19O6S−
1
OSO3
Not Identified
S2 HO
265
Cyclodecane
6.40
265.0747
1.41
C10H17O6S−
O
2
OSO3
265
267
Decalin
Decalin
4.40
265.0749
1.18
5.80
265.0757
4.19
6.75
265.0742
1.45
8.10
265.0754
3.06
6.38
267.0553
0.02
7.20
267.0550
2.55
O
C10H17O6S−
2
OSO3
OH
O
C9H15O7S
−
2
OOH
OSO3
OH
8.98
267
269
279
267.0914
2.16
C10H19O6S−
Cyclodecane
Decalin
Cyclodecane
9.61
267.0903
1.70
8.04
269.0696
0.73
5.77
279.0554
2.05
6.76
279.0551
5.40
1
C9H17O7S−
1
C10H15O7S−
3
OH
OSO3
OOH
OH
OSO3
Not Identified
S3 279
Dodecane
11.73
279.1256
3.66
12.04
279.1254
4.37
12.44
279.1265
0.43
C12H23O5S−
1
O
OSO3
OH
6.98
281.0698
0.64
7.27
281.0705
2.00
O
Cyclodecane
281
OH
C10H17O7S−
OSO3
2
O
Decalin
8.01
281.0702
OH
1.20
OH
OSO3
6.22
285
285.0651
C9H17O8S−
Decalin
6.51
285.0648
OH
OH
0.95
OSO3
1
0.58
OOH
295
Decalin
6.84
295.0495
1.19
7.10
295.0505
4.44
7.62
295.0506
5.16
O
C10H15O8S−
3
O
OH
OSO3
HO
S4 297
299
307
311
326
Decalin
6.84
297.0657
4.31
7.62
297.0645
0.27
8.30
297.0652
2.63
7.65
299.0805
2.05
Decalin
Dodecane
7.88
299.0801
1.26
7.93
307.0833
4.49
6.57
311.0444
0.23
Decalin
Decalin
O
C10H17O8S−
311.0450
1.98
7.26
326.0551
1.59
8.14
326.0550
1.28
9.38
326.0554
2.51
9.95
326.0557
3.43
OSO3
HOO
OH
C10H19O8S−
1
Not Identified
C12H19O7S−
3
Not Identified
O
C10H15O9S
7.00
2
−
OOH
OSO3
3
O
ONO2
C10H16NO9S−
HO
OH
OSO3
3
O
S5 Table S2. Concentrations (ng m-3) of OSs quantified (using methanol) in dodecane chamber
experiments in presence of ammonium sulfate aerosol. Ratios of OS quantified using
acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are
also reported.
No-Ac
Dry
Ac-Dry
No-Ac
Wet
Ac-Wet
C7H13O5S−
0.58
0.57
0.93
0.92
0.75
0.78
0.99 ± 0.11
C9H17O5S−
2.87
2.80
1.97
2.48
3.16
3.54
0.82 ± 0.20
C9H19O5S−
2.65
3.10
3.10
3.33
3.66
4.19
0.95 ± 0.20
C12H23O5S−
1.98
7.76
1.45
2.65
1.75
8.20
1.81 ± 0.37
C12H19O7S−
0.82
1.18
0.47
0.71
1.41
1.76
1.67 ± 0.43
Sum
8.92
15.41
7.92
10.11
10.74
18.45
1.28 ± 0.12
[M - H] −
(209.0472)a,b
(237.0786)a,b
(255.0914)a,b
(279.1254)c,d
(307.0040)a,b
a
Ac-Wet Ac-Dry
ACNTol/Methanol
−
Quantified using 3-pinanol-2-hydrogen sulfate (C9H13O6S ) as a surrogate standard, b OSs belonging
to Group−2, c quantified using octyl sulfate as a surrogate standard,
d
OSs belonging to Group−1.
Different isomers for one ion have been summed; Ac. and No Ac. correspond to acidified and noacidified sulfate seed aerosol, respectively.
S6 Table S3. Concentrations (ng m-3) of OSs quantified (using methanol) in decalin chamber
experiments in presence of ammonium sulfate aerosol. Ratios of OS quantified using
acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are
also reported.
No-Ac
Dry
Ac-Dry
No-Ac
Wet
Ac-Wet
C7H15O4S−
26.9
47.4
19.6
29.7
33.1
33.0
0.84 ± 0.23
C10H17O6S−
12.1
54.3
23.2
49.7
25.5
37.8
1.66 ± 0.45
C9H15O7S−
17.3
78.6
23.1
41.3
36.1
70.5
1.81 ± 0.42
C9H17O7S−
58.4
72.5
36.5
49.7
61.4
63.0
1.07 ± 0.20
C10H17O7S−
16.7
61.4
21.0
43.4
22.5
48.1
2.04 ± 0.26
C9H17O8S−
48.4
349.6
96.1
279.1
129.4
114.5
1.88 ± 0.55
C10H15O8S−
41.0
90.3
27.7
46.0
40.7
82.0
2.11 ± 0.75
C10H17O8S−
16.3
51.5
20.4
37.5
19.1
28.7
2.07 ± 0.38
C10H19O8S−
6.7
41.7
5.1
8.8
5.2
20.3
1.72 ± 0.37
C10H15O9S−
20.3
40.2
22.9
36.3
17.5
40.7
2.13 ± 0.26
C10H16NO9S−
7.9
54.0
38.8
104.4
27.1
71.6
3.03 ± 0.62
Sum
272.0
941.9
334.4
726.0
417.7
610.1
1.78 ± 0.16
[M - H] −
(195.0697)a,b
(265.0749)a,c
(267.0553)a,c
(269.0696)a,b
(281.0702)a,c
(285.0651)a,c
(295.0495)a,c
(297.0657)a,b
(299.0805)a,c
(311.0444)a,c
(326.0551)a,c
a
Ac-Wet Ac-Dry
ACNTol/Methanol
Quantified using 3-pinanol-2-hydrogen sulfate (C9H13O6S−) as a surrogate standard, b OSs belonging
to Group−2, c OSs belonging to Group−1. Different isomers for one ion have been summed; Ac. and No
Ac. correspond to acidified and no-acidified sulfate seed aerosol, respectively.
S7 Table S4. Concentrations (ng m-3) of OSs quantified (using methanol) in cyclodecane chamber
experiments in presence of ammonium sulfate aerosol. Ratios of OS quantified using
acetonitrile/toluene (ACN-Tol) divided by OS quantified using methanol as solvent mixture are
also reported.
[M - H] −
C10H17O5S−
(249.0807)a,b
C10H19O5S−
(251.0950)a,b
C10H17O6S−
(265.0747)a,b
C10H19O6S−
(267.0914)a,b
C10H15O7S−
(279.0554)a
C10H17O7S−
(281.0698)a,b
Sum
a
No-Ac
Dry
Ac-Dry
No-Ac
Wet
2.5
48.1
3.9
4.6
3.2
26.5
2.30 ± 0.33
3.2
39.2
3.8
4.6
4.1
24.4
1.92 ± 0.10
10.4
40.8
7.4
9.4
5.5
44.0
1.52 ± 0.30
4.6
39.4
5.0
5.7
9.4
22.9
1.36 ± 0.10
N.d.
6.4
N.d.
N.d.
N.d.
2.5
5.8
28.3
3.9
4.4
4.5
19.3
1.64 ± 0.28
26.5
202.3
23.9
28.8
26.7
139.6
1.74 ± 0.15
Ac-Wet Ac-Wet Ac-Dry
ACNTol/Methanol
−
Quantified using 3-pinanol-2-hydrogen sulfate (C9H13O6S ) as a surrogate standard, b OSs belonging
to Group−1. Different isomers for one ion have been summed; N.d.: not detected; Ac. and No Ac.
correspond to acidified and no-acidified sulfate seed aerosol, respectively.
S8 Relative Abundance
100
96.9615
HSO4−
80
279.1265
C12H23O5S−
60
40
20
199.1708
C12H23O2−
0
80
Figure S1.
120
160
200
m/z
240
280
MS2 spectrum obtained for dodecane-derived OS-279 (m/z 279.1274).
Fragmentation scheme is proposed in Figure 1.
S9 O
O
− SO3
O
OH
185.1218
C10H17O3−
a
OSO3
OH
265.0752
C10H17O6S−
− HSO4−
O
O
b
OOH
OOH
OOH
O
OSO3
− HSO4−
O
− SO3
HO
HO
− H2O
OOH
189.1110
C9H17O4−
269.0696
C9H17O7S− − SO3Ÿ/−
OOH
OSO3
251.0573
C9H15O6S−
O
HO
S10 O
O
c
O
O
OH
O
O
O
OH
295.0494
C10H15O8S−
OH
OH
−SO3
HO
−HSO3−
O
O
OSO3
−HSO4−
HO
215.0934
C10H15O5−
O
− CO2
OSO3
O
O
HO
−SO3
OH
HO
O
251.0583
C9H15O6S−
O
171.1051
C9H15O3−
OH
OSO3
O
263.0572
C10H15O6S−
− HNO3
ONO2
ONO2
OH
O
OSO3
d
O
326.0554
C10H16NO9S−
− HSO4−
−SO3Ÿ/−
O
ONO2
OH
O
O
Figure S2. Fragmentation schemes for selected decalin-derived OSs: a) m/z 265.0752
(C10H17O6S–), (b) m/z 269.0696 (C9H17O7S–), (c) m/z 295.0494 (C10H15O8S–) and (d) m/z
326.0554 (C10H16NO9S–). MS2 spectra are reported in Figure 2.
S11 Relative Abundance
100
96.9618
HSO4−
80
187.0947
C9H15O4−
60
267.0552
C9H15O7S−
40
20
0
80
120
160
200
240
280
m/z
O
O
− SO3
OOH
O
187.0947
C9H15O4−
OOH
OSO3
267.0552
C9H15O7S−
− HSO4−
O
OOH
Figure S3. MS2 spectrum and fragmentation scheme of ion at m/z 267.0552 identified in SOA
formed from decalin oxidation.
S12 Relative Abundance
100
96.9601
HSO4−
80
60
40
281.0702
C10H17O7S−
201.1132
C10H17O4−
20
0
80
120
160
200
m/z
240
O
280
OH
OH
O
−SO3
OH
OH
OSO3
281.0702
C10H17O7S−
O
201.1132
C10H17O4−
O
−HSO4−
O
OH
Figure S4. MS2 spectrum and fragmentation scheme of the parent ion at m/z 281.0702
identified in SOA formed from decalin oxidation.
S13 285.0654
C9H17O8S−
Relative Abundance
100
80
60
96.9612
HSO4−
205.1081
C9H17O5−
40
20 80.9150
HSO3−
0
80
120
160
200
240
280
m/z
OH
O
OOH
−HSO4−
OH
OH
OSO3
OOH
285.0654
C9H17O8S−
OH
OH
−HSO3−
O
OOH
−SO3
OH
OH
O
OOH
205.1081
C9H17O5−
Figure S5. MS2 spectrum and fragmentation scheme of the parent ion at m/z 285.0654
identified in SOA formed from decalin oxidation.
S14 96.9608
HSO4−
Relative Abundance
100
80
60
297.0657
C10H17O8S−
217.1065
C10H17O5−
40
279.0515
C10H15O7S−
20
0
80
120
160
200
m/z
240
280
O
−HSO4−
HOO
O
O
OSO3
HOO
O
OH
297.0657
C10H17O8S−
OSO3
−H2O
O
−SO3
O
OH
279.0515
C10H15O7S−
O
HOO
OH
217.1065
C10H17O5−
Figure S6. MS2 spectrum and fragmentation scheme of the parent ion at m/z 297.0669
identified in SOA formed from decalin oxidation.
S15 Relative Abundance
100
96.9609
HSO4−
80
60
311.0447
C10H15O9S−
40
20
0
80
O
120
160
200
m/z
240
280
O
OOH
OOH
OSO3
O
HO
320
O
−HSO4−
O
311.0427
C10H15O9S−
Figure S7. MS2 spectrum and fragmentation scheme of the parent ion at m/z 311.0427
identified in SOA formed from decalin oxidation.
S16 OH/O2
O2
RO2/HO2
O
−H2O
O2
O
OO
HO2
RO2/HO2
O
a
1,6-H
O
O
OOH
C10H18O3
OOH
O
b
c
1,5-H/O2
OH − H2O
O
O
O
OH
OOH
OOH
OO
OO
HO2
− OH
O
HO2
O
OH
O
OOH
C10H18O4
H+
Gas Phase
1,5-H − OH
OH
Particle Phase
O
− H2O/
OH
OOH
OSO3
O
OOH
OOH
C10H18O5
O
OH
O
O
OH
H+
OS-265
C10H17O6S−
O
Gas Phase
Particle Phase
O
O
OH
OSO3
OH
OSO3
OS-281
C10H17O7S−
HOO
OH
OS-297
C10H17O8S−
Figure S8. Tentatively proposed formation pathways of OS-265 (265.0752), OS-281
(281.0702) and OS-295 (295.0494) from the oxidation of decalin in the presence of ammonium
sulfate aerosol.
S17 249.0807
C10H17O5S−
Relative Abundance
100
80
60
96.9601
HSO4−
40
20
0
80
120
160
m/z
200
O
240
O
OSO3
− HSO4−
249.0807
C10H17O5S−
Figure S9. MS2 spectrum and fragmentation scheme of the parent ion at m/z 249.0807
identified in SOA formed from cyclodecane oxidation.
S18 Relative Abundance
100
96.9592
HSO4−
251.0953
C10H19O5S−
80
60
40
20
80
120
160
m/z
OH
200
240
O
OSO3
− HSO4−
251.0953
C10H19O5S−
Figure S10. MS2 spectrum and fragmentation scheme of the parent ion at m/z 251.0953
identified in SOA formed from cyclodecane oxidation.
S19 Relative Abundance
100
96.9588
HSO4−
265.0747
C10H17O6S−
80
60
40
20
0
80
120
HO
160
m/z
O
200
240
O
O
− HSO4−
OSO3
265.0747
C10H17O6S−
Figure S11. MS2 spectrum and fragmentation scheme of the parent ion at m/z 265.0747
identified in SOA formed from cyclodecane oxidation.
S20 Relative Abundance
100
96.9589
HSO4−
80
267.0914
C10H19O6S−
60
40
20
0
80
120
160
m/z
OH
200
240
OH
OSO3
O
− HSO4−
OH
267.0914
C10H19O6S−
OH
Figure S12. MS2 spectrum and fragmentation scheme of the parent ion at m/z 267.0914
identified in SOA formed from cyclodecane oxidation.
S21 Relative Abundance
100
96.9602
HSO4−
281.0698
C10H17O7S−
80
60
40
20
80
120
160
200
240
280
m/z
OH
OH
O
OH
O
− HSO4−
O
OSO3
281.0698
C10H17O7S−
Figure S13. MS2 spectrum and fragmentation scheme of the parent ion at m/z 281.0698
identified in SOA formed from cyclodecane oxidation.
S22 OO
OOH
OH/O2
HO2
OOH
OH
− H2O
− H2O
C10H20O2
RO2/HO2
− OH
O
O
O
1,5-H/O2
− HO2
− HO2
OH
H+
Gas Phase
Particle Phase
O
OH
O
C10H18O
OSO3
OO
HO2
OH/
O2
− H2O
OH
O
OO
− H2O
OO
OH/O2
OS-251
C10H19O5S−
− H2O
O
OO
O
OOH
H+
C10H20O3
OH − H2O
RO2/HO2
1,8-H
HO2
O
OOH
OH
HOO
O
O
O
OH
C10H18O3
OSO3
OS-251
C10H19O5S−
OOH
OH
O
− OH
1,5-H/
O2/HO2
− OH
H+
Gas Phase
Particle Phase
O
O
OSO3
C10H18O4
O
OH
H+
OS-249
C10H17O5S−
O
Gas Phase H+
Particle Phase
HO
OH
OOH
− H2O/OH
OH
O
O
OH
O
OSO3
OH
OSO3
OS-265
C10H17O6S−
Gas Phase
Particle Phase
H+
OH
O
OS-267
C10H19O6S−
OH
OSO3
OS-281
C10H17O7S−
Figure S14. Tentatively proposed formation pathways of OSs formed from the oxidation of
cyclodecane in presence of sulfate aerosol.
S23 Figure S15. Extracted ion chromatograms (EICs) for alkane-derived OSs identified in aerosol
collected from both smog chamber experiments (in red) and field studies (in green).
S24