Supplement of Atmos. Chem. Phys., 16, 14527–14543, 2016
http://www.atmos-chem-phys.net/16/14527/2016/
doi:10.5194/acp-16-14527-2016-supplement
© Author(s) 2016. CC Attribution 3.0 License.
Supplement of
Detection of atmospheric gaseous amines and amides by a high-resolution
time-of-flight chemical ionization mass spectrometer with protonated ethanol
reagent ions
Lei Yao et al.
Correspondence to: Lin Wang ([email protected])
The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence.
Table S1 Tentative formula assignment of MS peaks with m/z values less than 163 Th.
ID
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Ion formula
NH3·H+
H2O·H+
HCN·H+
C2H4·H+
CH3N·H+
CH2O·H+
O2+
CH5N·H+
CH4O·H+
NH3·H2O·H+
(H2O)2·H+
C2H3N·H+
C2H2O·H+
C2H5N·H+
C2H4O·H+
NO2+
CH3NO·H+
C2H7N·H+
C2N2·H+
(H2O)3·H+
C3H4O·H+
C4H8·H+
C3H7N·H+
C3H6O·H+
C2H3O2·H+
C2H5NO·H+
C3H9N·H+
CH4N2O·H+
C2H7NO·H+
C2H6O2·H+
(C2H5OH)·NH3·H+
(C2H5OH)·H2O·H+
C4H5N·H+
C4H4O·H+
C5H8·H+
C3H3NO·H+
C4H7N·H+
C3H2O2·H+
C4H6O·H+
C3H5NO·H+
C4H9N·H+
C3H4O2·H+
C4H8O·H+
C3H7NO·H+
Molecular weight
18.0338
19.0178
28.0182
29.0386
30.0338
31.0178
31.9893
32.0495
33.0335
36.0444
37.0284
42.0338
43.0178
44.0495
45.0335
45.9924
46.0287
46.0651
53.0134
55.0389
57.0335
57.0699
58.0651
59.0491
60.0206
60.0444
60.0808
61.0396
62.0600
63.0441
64.0757
65.0597
68.0495
69.0335
69.0699
70.0287
70.0651
71.0128
71.0491
72.0444
72.0808
73.0284
73.0648
74.0600
Potential identity
Hydrogen cyanide
Methylamine
Acetonitrile
Formamide
C2-Amine
Cyanogen
C2-Amide
C3-Amine
2-Aminoethanol
Pyrrole
3-Pyrroline
Pyrrolidine
C3-Amide
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
C4H11N·H+
C4H10O·H+
C2H5NO2·H+
C3H8O2·H+
C2H7NO2·H+
CH3NH2·(C2H5OH)·H+
C2H6OS·H+
C6H6·H+
C3H8O·H2O·H+
C5H5N·H+
C4H4N2·H+
C2H6O2·H2O·H+
C6H8·H+
C5H7N·H+
C2H6O·(H2O)2·H+
C4H5NO·H+
C4H4O2·H+
C5H8O·H+
C4H7NO·H+
C4H6O2·H+
C5H10O·H+
C3H5NO2·H+
C4H9NO·H+
C5H13N·H+
C3H4O3·H+
C4H8O2·H+
C5H12O·H+
C2H7N3O·H+
C4H10O2·H+
CH4NO·(C2H5OH)·H+
C2H7N·(C2H5OH)·H+
C5H5NO·H+
C5H4O2·H+
C6H8O·H+
C5H7NO·H+
C6H11N·H+
C5H6O2·H+
C6H10O·H+
C5H9NO·H+
C5H8O2·H+
C6H12O·H+
C4H7NO2·H+
C5H11NO·H+
C6H15N·H+
C5H10O2·H+
C6H14O·H+
C4H9NO2·H+
C5H12O2·H+
74.0964
75.0804
76.0393
77.0597
78.0549
78.0913
79.0212
79.0542
79.0753
80.0495
81.0447
81.0546
81.0699
82.0651
83.0703
84.0444
85.0284
85.0648
86.0600
87.0441
87.0804
88.0393
88.0757
88.1121
89.0233
89.0597
89.0961
90.0662
91.0754
92.0706
92.1070
96.0444
97.0284
97.0648
98.0600
98.0964
99.0441
99.0804
100.0757
101.0597
101.0961
102.0550
102.0913
102.1277
103.0754
103.1117
104.0706
105.0910
C4-Amine
Glycine
Pyridine
Pyrimidine
N-Methylpyrrole
C3-Oxoamide
C4-Amide
C5-Amine
2,5-Dimethyl-3-pyrroline
C4-Oxoamide
C5-Amide
C6-Amine
4-Aminobutyric acid
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
C2H6NO·(C2H5OH)·H+
C3H9N·(C2H5OH)·H+
C6H5NO·H+
C8H12·H+
C6H7NO·H+
C6H6O2·H+
C6H8O2·H+
C6H11NO·H+
C5H6O3·H+
C6H10O2·H+
C6H14N2·H+
C4H5NOS·H+
C5H9NO2·H+
C6H13NO·H+
C5H8O3·H+
C6H12O2·H+
C5H12N2O·H+
C5H11NO2·H+
C4H10N2O2·H+
C6H14O2·H+
C5H11OS·H+
C3H7NO·(C2H5OH)·H+
C4H12N·(C2H5OH)·H+
C8H8O·H+
C6H14O·H2O·H+
C4H11NOS·H+
C8H11N·H+
C4H10O2S·H+
C8H10O·H+
C9H14·H+
C3H9NO2S·H+
C7H8O2·H+
C8H12O·H+
C6H6O3·H+
C7H10O2·H+
C8H14O·H+
C5H5NO3·H+
C6H9NO2·H+
C7H13NO·H+
C7H12O2·H+
C9H7N·H+
C6H10O3·H+
C7H14O2·H+
C6H13NO2·H+
C6H12O3·H+
C3H5NO2·(C2H5OH)·H+
C4H9NO·(C2H5OH)·H+
C5H13N·(C2H5OH)·H+
106.0863
106.1226
108.0444
109.1012
110.0600
111.0441
113.0597
114.0913
115.0390
115.0754
115.1230
116.0165
116.0760
116.1070
117.0546
117.0910
117.1022
118.0863
119.0815
119.1067
120.0570
120.1019
120.1383
121.0648
121.1210
122.0634
122.0964
123.0474
123.0804
123.1168
124.0995
125.0597
125.0961
127.0390
127.0753
127.1117
128.0342
128.0706
128.1070
129.0910
130.0651
131.0702
131.1067
132.1019
133.0859
134.0812
134.1176
134.1539
2,5-Dimethylpiperazine
C5-Oxoamide
C6-Amide
L-Valine
Phenethylamine
Quinoline
L-Leucine
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
C8H6O2·H+
C4H10N2O3·H+
C6H14O3·H+
C7H5NS·H+
C4H9NO4·H+
C5H13NO3·H+
C7H8N2O·H+
C9H12O·H+
C6H14O2·H2O·H+
C4H11NO2S·H+
C7H8O3·H+
C8H12O2·H+
C9H16O·H+
C6H7NO3·H+
C8H15NO·H+
C7H10O3·H+
C8H14O2·H+
C8H18N2·H+
C5H9N3O2·H+
C7H13NO2·H+
C8H17NO·H+
C6H8O4·H+
C7H12O3·H+
C8H16O2·H+
C6H11NO3·H+
C7H15NO2·H+
C6H10O4·H+
C7H14O3·H+
C8H18O2·H+
C4H7NO2·(C2H5OH)·H+
C5H11NO·(C2H5OH)·H+
C6H15N·(C2H5OH)·H+
C5H8O3S·H+
C9H8O2·H+
C6H12O4·H+
C8H7NS·H+
C5H11NO4·H+
C5H15N3O2·H+
C5H14N2OS·H+
C10H14O·H+
C7H5NOS·H+
C10H15O·H+
C6H14O3·H2O·H+
C9H14O2·H+
C9H18N2·H+
C8H12O3·H+
C9H16O2·H+
C9H20N2·H+
135.0441
135.0764
135.1016
136.0215
136.0604
136.0968
137.0709
137.0961
137.1172
138.1039
141.0546
141.0910
141.1308
142.0499
142.1226
143.0703
143.1067
143.1542
144.0768
144.1019
144.1383
145.0495
145.0859
145.1223
146.0811
146.1176
147.0652
147.1016
147.1379
148.0968
148.1332
148.1696
149.0267
149.0597
149.0808
150.0372
150.0761
150.1237
151.0899
151.1117
152.0165
152.1196
153.1121
155.1067
155.1543
157.0859
157.1223
157.1699
1-Butylpiperazine
7-Aminoheptanoic acid
4-Pyrrolidinopiperidine
Triacetonediamine
189
190
191
192
193
194
195
196
197
198
199
200
201
202
C11H11N·H+
C9H19NO·H+
C7H10O4·H+
C8H14O3·H+
C10H9NO·H+
C11H13N·H+
C8H17NO2·H+
C7H12O4·H+
C8H16O3·H+
C9H20O2·H+
C4H5NO3·(C2H5OH)·H+
C5H9NO2·(C2H5OH)·H+
C6H13NO·(C2H5OH)·H+
C8H18O3·H+
158.0964
158.1539
159.0652
159.1016
160.0757
160.1121
160.1332
161.0808
161.1172
161.1536
162.0761
162.1125
162.1489
163.1329
2,8-Dimethylquinoline
2,3,3-Trimethylindolenine
8-Aminooctanoic acid
Figure S1. A typical mass spectrum with RH ＜ 20%. The dominant reagent ions are
protonated ethanol dimer ((C2H5OH)2·H+), monomer ((C2H5OH)·H+), and trimer
((C2H5OH)3·H+). The ratio of the clusters of protonated ethanol with water (C2H5OH·H2O·H+)
to the sum of (C2H5OH)·H+, (C2H5OH)2·H+, and (C2H5OH)3·H+ is ~0.026.
Figure S2. Schematics for laboratory tests of effects of (A) RH and (B) organics. All sampling
lines are made of PFA or PTFE material.
Figure S3. Schematic of CIMS setup during the field measurements.
Figure S4. Background check for amines and amides during a 3 h ambient sampling period.
Figure S5. Inlet memory of TMA and PA by inlet spike tests. The red and pink curves are
fittings by the sum of two decaying exponentials. The characteristic decaying times of two
exponentials, which are displacement of amines and amides inside the inlet by pumping and
removing amines and amides adsorbed on the inlet surface, were 1.1 s and 8.5 s for TMA, and
1.4 s and 1.4 s for PA, respectively.
Figure S6. Changes in pH values of HNO3 solution as titration by diethylamine proceeds.
Note that pH values in this plot are 2-h averages
Figure S7. Changes in NH4+ concentration as hydrolysis of formamide and propanamide
proceeds.
Figure S8. Calibration curves of C1- to C4-amines (MA, DMA, TMA, and DEA) and C1- to
C3-amides (FA, AA, and PA). The red solid lines are linear fittings to guide the eye and the
slopes are sensitivities for detection.
Figure S9. Diurnal variations of amines and amides with less variations.
Figure S10. Three-day backward retroplumes (100 m above the ground level) from the
sampling location at (A) 07:00, 27 July 2015; (B) 07:00, 28 July 2015; (C) 07:00, 30 July
2015; (D) 07:00, 31 July 2015; and (E) 07:00, 4 August 2015. The embedded boxes show 12h
backward trajectories.