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Desorption atmospheric pressure photoionization-high resolution mass spectrometry: A
complementary approach for the chemical analysis of atmospheric aerosols
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Jevgeni Parshintseva*, Anu Vaikkinenb, Katriina Lipponena, Vladimir Vrkoslavc, Josef Cvačkac,
Risto Kostiainenb, Tapio Kotiahoa,b, Kari Hartonena, Marja-Liisa Riekkolaa, Tiina J. Kauppilab*
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a
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b
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c
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166 10 Prague 6, Czech Republic
Laboratory of Analytical Chemistry, Department of Chemistry, P.O.Box 55, FI-00014
University of Helsinki, Finland
Division of Pharmaceutical Chemistry and Technology, Faculty of Pharmacy, P.O.Box 56, FI00014 University of Helsinki, Finland
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,
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* Corresponding Authors
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E-mail:
evgeny.parshintsev@helsinki.fi
(+358504480733)
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Supporting Information
(+358503028326),
tiina.kauppila@helsinki.fi
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Figure S1. DAPPI-LRMS spectra of Teflon background and adipic, azelaic, caprylic, maleic,
malic, malonic, mandelic, cis-pinonic, sebacic, tartaric and vanillic acid standards. 1 µL of 10
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(azelaic and sebacic acids) or 100 µM (all others) sample solution was analyzed from Teflon
surface. Dopant was toluene at 10 µL/min flow rate.
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Figure S2. LC/MS total ion chromatogram of the sample collected at 6th of August 2012 (upper),
extracted ion chromatogram of m/z 185 (middle, pinic acid) and of m/z 183 (lower, pinonic acid).
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Concentration of acids, ng m-3 / particle number
concentration, cm-3
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16
particles
14
malic
12
tartaric
malonic
10
adipic
8
pinic
benzoic
6
azelaic
4
sebacic
2
0
8/2/2012
caprylic
pinonic
8/6/2012
8/10/2012
8/14/2012
8/18/2012
Sampling date
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35
36
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Figure S3. Aerosol particle number concentration (*103 cm-3) during the sampling period and the
concentrations of studied acids in ng/m3. Note, off-line sampling dates correspond to earlier
sampling times with CPC.
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Table S1. DAPPI-HRMS results for selected target ions. S/N = m/z value observed in sample, but I(sample)≤3*I(blank). Note that the
RSD:s were 9-129 % and the RSD was inversely related to average intensity (I, n=6, Pearson’s r for the linear fit between RSD and
log 1/I was 0.7).
103.0035,malonic
145.0504, adipic
185.0816, pinic
Sample, August 2012
I/m3
I
I/m3
I
I/m3
2nd, 17:00
0
0
0
0
3rd, 9:00
0
0
0
0
3rd 15:20
0
0
S/N
S/N
6th, 9:30
4741
33190
11125
6th, 16:35
0
0
7th, 8:30
0
7th, 16:00
121.0293, benzoic
187.0972, azelaic
201.1130, sebacic
183.1024, cis -pinonic
I
I/m3
I
I/m3
I
I/m3
I
I/m3
0
0
S/N
S/N
0
0
0
0
S/N
S/N
3678
23174
S/N
S/N
0
0
0
0
18406
115961
2261
149028
S/N
S/N
563
37084
169
11121
2286
150675
77873
9638
67466
S/N
S/N
S/N
S/N
0
0
4222
29555
S/N
S/N
3993
63884
S/N
S/N
S/N
S/N
0
0
6677
106829
0
S/N
S/N
13558
101681
S/N
S/N
S/N
S/N
762
5713
21605
162037
0
0
S/N
S/N
8720
130807
S/N
S/N
3154
47312
583
8750
6130
91955
8th, 7:05
0
0
0
0
0
0
S/N
S/N
0
0
0
0
7341
62400
8th, 15:40
0
0
0
0
2390
39909
S/N
S/N
S/N
S/N
0
0
5661
94534
9th, 8:00
0
0
S/N
S/N
26763
222132
S/N
S/N
7090
58846
2182
18108
35395
293777
9th, 16:20
0
0
S/N
S/N
5947
95156
21374
341991
2326
37210
0
0
15077
241229
10th, 8:30
0
0
S/N
S/N
27312
218493
51530
412236
5823
46587
2654
21229
39023
312183
14th, 8:30
1428
12854
12640
113762
44359
399228
39424
354819
11401
102612
3593
32334
27439
246950
15th, 8:40
1037
7259
13600
95201
68862
482034
S/N
S/N
15370
107590
4261
29825
49682
347775
15th, 15:30
0
0
S/N
S/N
12477
212108
S/N
S/N
3071
52211
1234
20982
20030
340502
16th, 8:25
3638
30922
19464
165444
54637
464414
47220
401368
15513
131861
4086
34733
30371
258151
16th, 16:55
293
4682
5772
92346
34515
552241
23290
372638
8300
132806
3192
51064
25378
406049
17th, 8:50
385
30442
2468
194991
8935
705880
7150
564883
2201
173867
785
62050
4844
382692
20th, 16:05
0
0
0
0
2184
34936
S/N
S/N
S/N
S/N
0
0
5547
88750
21th, 8:10
0
0
S/N
S/N
12194
195105
29082
465313
3480
55676
1116
17856
22957
367319
I
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Table S2. Absolute and relative concentration of studied acids determined by LC/MS. nd- not determined.
Sample,
August 2012
2nd, 17:00
3rd, 9:00
3rd 15:20
6th, 9:30
6th, 16:35
7th, 8:30
7th, 16:00
8th, 7:05
8th, 15:40
9th, 8:00
9th, 16:20
10th, 8:30
14th, 8:30
15th, 8:40
15th, 15:30
16th, 8:25
16th, 16:55
17th, 8:50
20th, 16:05
21th, 8:10
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malic
tartaric
malonic
adipic
ng/ ng/filt ng/ ng/filt ng/ ng/filt ng/ ng/filt
m3
er
m3
er
m3
er
m3
er
0.3
5.1 <0.1 0.4
0.2
3.5
0.4
5.9
1.5
9.7
0.5
3.2
1.4
8.7
1.3
8.2
0.1
7.8 <0.1 1.5
nd
nd
0.1
6.5
2.2 15.6 0.3
1.8
1.3
9.1
1.3
9.0
1.0 15.8 0.6
9.1
1.3 20.9 1.4 22.1
0.8
5.7
0.1
0.4
1.3
9.6
0.8
6.0
0.9 13.7 0.1
2.2
2.4 35.3 1.0 15.0
1.4 11.9 0.4
3.1
4.1 35.1 1.3 10.8
0.5
8.4
0.5
8.0
1.2 20.2 1.1 18.9
0.2
1.9
0.1
0.9
0.2
1.5
0.5
3.9
0.5
7.9
0.3
4.3
2.1 33.4 1.0 15.3
0.5
4.0
0.1
1.1
1.0
8.1
0.7
5.7
0.2
1.5
0.1
0.6
nd
nd
<0.1 4.9
2.9 20.1 0.7
4.6 10.2 71.1 3.0 21.0
0.5
9.3
0.2
4.2
2.3 39.7 0.8 13.3
3.3 28.3 1.4 12.1 9.6 82.0 3.4 28.6
0.5
7.9
0.2
3.2
2.0 31.6 0.7 11.5
0.2 12.7 0.1
4.6
0.8 63.0 0.2 18.8
1.2 18.8 0.5
8.7
2.3 36.2 1.2 18.7
0.5
8.0
0.2
3.0
2.0 32.4 0.7 11.4
Acids
pinic
ng/ ng/filt
m3
er
0.7 11.3
1.8 11.6
0.5 34.1
1.6 11.5
3.1 49.5
1.5 11.0
1.3 18.8
1.7 14.6
2.4 39.7
nd
nd
1.4 23.1
1.4 11.6
4.0 36.0
3.6 25.0
1.6 28.0
3.7 31.0
1.1 18.4
0.3 20.0
2.3 36.5
1.0 16.5
benzoic
azelaic
ng/ ng/filt ng/ ng/filt
m3
er
m3
er
0.1
0.8
0.1
1.6
0.2
1.2
0.3
1.8
0.1
5.0
0.1
7.5
0.2
1.2
0.3
2.0
0.2
2.5
0.3
4.3
0.1
0.9
0.2
1.4
0.1
2.2
0.2
2.3
0.3
2.8
0.3
2.2
0.2
3.0
0.2
3.8
nd
nd
0.1
0.9
0.3
5.1
0.2
2.6
0.1
0.9
0.2
1.6
0.5
4.5
0.6
5.5
0.3
1.9
0.5
3.3
0.2
3.9
0.2
3.1
0.2
2.0
0.4
3.7
0.2
2.4
0.2
2.8
0.0
2.2 <0.1 2.4
0.4
6.5
0.2
3.4
0.2
2.4
0.1
1.9
sebacic
ng/ ng/filt
m3
er
nd
0.5
0.1
0.7
<0.1 2.1
0.1
0.6
0.1
1.7
0.1
0.5
0.1
0.9
0.1
0.6
0.1
1.4
<0.1 0.3
<0.1 0.8
0.1
0.5
0.2
1.6
0.2
1.1
0.1
1.2
0.1
1.0
<0.1 0.8
<0.1 0.9
0.1
1.4
<0.1 0.6
caprylic
ng/ ng/filt
m3
er
0.5
7.2
1.0
6.0
0.5 34.7
1.5 10.2
2.9 46.4
1.5 11.4
2.8 41.6
5.1 43.7
3.5 58.6
0.5
4.1
1.9 30.0
1.0
8.0
3.8 34.1
5.9 41.0
3.3 56.2
3.3 27.9
2.3 36.6
0.4 33.7
1.6 25.3
1.1 17.2
pinonic
ng/ ng/filt
m3
er
0.2
3.2
0.6
4.1
0.1
8.3
0.6
4.1
0.7 11.1
0.5
3.4
0.4
5.3
0.5
4.4
0.5
9.1
0.3
2.9
0.4
6.6
0.5
3.6
0.8
7.3
1.1
7.8
0.5
8.3
1.1
9.1
0.4
5.9
0.1
5.9
0.6
8.9
0.3
5.1