Alkyl and aromatic nitrates in atmospheric particles determined by gas chromatography tandem mass spectrometry
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J. Am. Soc. Mass Spectrom. (2019) DOI: 10.1007/s13361-019-02347-8
RESEARCH ARTICLE
Alkyl and aromatic nitrates in atmospheric particles determined by gas chromatography tandem mass spectrometry Xinhao Yang,1 Feixian Luo,1 Junqi Li,1 Deyang Chen,1 Ye E.,1 Weili Lin,1 Jun Jin1,2 1
College of Life and Environmental Sciences, Minzu University of China, Room 1316, Li Gong Building, Beijing, 100081, China Engineering Research Center of Food Environment and Public Health, Beijing, 100081, China
2
Abstract. Organic nitrates in the atmosphere are associated with photochemical pollution and are Synthesis the main components of secondary organic aerosols, which are related to haze. An efficient method for determining organic nitrates in atmospheric Ultrasonic Centrifugation fine particles (PM2.5) was established using synthesized standards. Four alkyl (C7–C10) nitrates and three aromatic nitrates (tolyl nitrate, phenethyl nitrate, and p-xylyl nitrate) were synSampling Instrumental Identification analysis thesized and characterized by 1H and 13C nuclear magnetic resonance spectroscopy. The optimal ions for quantifying and confirming the identities of the analytes were identified by analyzing the standards by gas chromatography tandem mass spectrometry. The tandem mass spectrometer was a triple quadrupole instrument. This method can obtain more accurate information of organic nitrates than on-line methods. Spiked recovery tests were performed using three spike concentrations, and the recoveries were 61.0–111.4 %, and the relative standard deviations were < 8.2% for all of the analytes. Limits of detection and quantification were determined, and the linearity of the method for each analyte was assessed. The applicability of the method was demonstrated by analyzing six PM2.5 samples. Overall, 87% of the analytes were detected in the samples. Phenethyl nitrate, heptyl nitrate, and octyl nitrate were detected in every sample. Phenethyl nitrate was found at a higher mean concentration (3.23 ng/m3) than the other analytes. Keywords: Organic nitrates, PM2.5, Synthesis, GC-MS/MS 57.13 57.13
100 100 95 90 85
69.12
80
Relat ive Abundance
75 70 65
43.15 55.13 55.13
60
43.15
55
41.13 41.13
50 50 45 40
76.07 76.07
35 30 25 20
71.12
46.07
32.08
46.07
78.07
15 10 5
00
30 30
67.13
39.18
54.18
38.10
40
50 50
83.19
58.07 65.08 60
85.12 89.07
70 70
80
90 90
96.14
107.14 111.15 117.08 110 110
100
120
128.10 135.06 130 130
146.06 152.06
140
150 150
161.05 164.33 160
170 170
178.04 183.22 180
m/z
Received: 28 July 2019/Revised: 6 September 2019/Accepted: 8 October 2019
O
rganic nitrates (ONs) are esters and derivatives containing nitrate groups. ONs are active nitrogen oxides that have important effects in the atmosphere. ONs can be divided into anthropogenic ONs and biogenic ONs. Many studies of biogenic ONs have been performed because they play important roles in the atmospheric nitrogen cycle [1, 2]. Anthropogenic ONs may, however, be the dominant ONs in the atmosphere in densely populated urba
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