Chemical ionization mass spectrum of peroxyacetylnitrate

Pate, C. T.; Sprung, J.L.; Pitts, James N.

doi:10.1002/oms.1210110514

Cited by 15 publications

(15 citation statements)

References 19 publications

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“…decomposition to alkyl nitrate, alkaline decomposition to carboxylic acid, and identification of the carbonyl product(s) of the gas-phase decomposition in the presence of NO, are compound-specific. These tests represent a simple, cost-effective alternative to structure elucidation using conventional methods such as infrared spectroscopy and mass spectrometry, which are suitable for the identification of peroxyacyl nitrates as a group but have limited applicability to structure confirmation for individual compounds (1,14,32,33).…”

Section: Resultsmentioning

confidence: 99%

Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2

Grosjean¹,

Grosjean²,

Williams³

1994

Environ. Sci. Technol.

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Section: Resultsmentioning

confidence: 99%

Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2

Grosjean¹,

Grosjean²,

Williams³

1994

Environ. Sci. Technol.

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“…Spicer et al [1998] and Srinivasan et al [1998] reported ambient air measurements and laboratory investigation of P AN using negative ion chemical ionization mass spectrometry, respectively. Measurements of PAN by mass spectrometry using other ionization methods (i.e., electron impact ionization [e.g., Bertman andRoberts, 1991], photoionization [Kacmarek et al, 1978], and positive ion chemical ionization [Pate et al, 1976]) have been reported previously; however, these techniques have been used in laboratory experiments to investigate the structure and chemical properties of PANs but have not been used forambient air measurements, probably because of in-sufficientsensitivity. Somestudies using GC/NiCI MShave reported trace gas measurements other than PAN in ambient air.…”

Section: Introductionmentioning

confidence: 99%

A new measurement technique of peroxyacetyl nitrate at parts per trillion by volume levels: Gas chromatography/negative ion chemical ionization mass spectrometry

Tanimoto¹,

Hirokawa²,

Kajii³

et al. 1999

J. Geophys. Res.

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Abstract. A new technique for measuring peroxyacetyl nitrate (PAN) at parts per trillion by volume (pptv) levels has been developed using gas chromatography with negative ion chemical ionization mass spectrometry (GC/NICI MS). Four fi'agment ions, CH3C(O)O-(mass-to-charge ratios (rn/z)=59), NO 3-(rn/z=62), CH3C(O)OO-(rn/z=75), and NO2-(rn/z=46), were identified by NICI mass spectra. NO 3-(rn/z=62) was used in selected ion monitoring (SIM) mode among these fi'agment ions, since it gave the best signal-to-noise (S/N) ratio, and a potential interference from isopropyl nitrate (IPN) was excluded. Optimization of mass spectrometry and use of capillary gas chromatography enabled us to detect PAN at a retention time of 2.6 + 0.1 min in ambient air mixing ratio range. The present detection limit is 15 + 4 pptv (S/N=3), which is comparable to those of previously published GC/ECD methods, with good linearity at pptv levels. The instrumental accuracy and precision are estimated to be +20% and + 15%, respectively. Other PAN analogs (i.e., peroxypropionyl nitrate and peroxymethacryloyl nitrate) were also measured within 10 min. Exploratory ambient air measurements were made at our laboratory in a suburban area of Tokyo, Japan. These results demonstrated the performance of GC/NICI MS for ambient air measurements.

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“…61 The chemical ionization mass spectrum of PAN was obtained in 1976. 62 Being an energetic molecule, the parent peak of PAN was not observed in the positive ion mass spectrum. However, since PAN has a high ECD cross section, the negative ion mass spectrum of PAN can be detected with high sensitivity.…”

Section: Propertiesmentioning

confidence: 95%

“…The mass spectrum of PAN was first determined using electron impact ionization in 1969 as part of a study showing the release of singlet molecular oxygen (O 2 1 Δ g ) occurring during the base decomposition of PAN . The chemical ionization mass spectrum of PAN was obtained in 1976 . Being an energetic molecule, the parent peak of PAN was not observed in the positive ion mass spectrum.…”

Section: Measurement Methodsmentioning

confidence: 99%

The Impacts of Peroxyacetyl Nitrate in the Atmosphere of Megacities and Large Urban Areas: A Historical Perspective

Gaffney

Marley

2021

ACS Earth Space Chem.

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This paper is an overview of the history, discovery, and measurement of peroxyacetyl nitrate (PAN) and its analogs, the peroxyacyl nitrates (PANs), in highly populated urban areas and their downwind environments. The PANs are known to be strong lachrymators and highly phytotoxic. The discovery and characterization of PAN and its analogs helped to confirm that photochemical smog chemistry involved the oxidation of organics by the OH radical to produce organoperoxy radicals, which rapidly convert nitric oxide to nitrogen dioxide and lead to enhanced ozone formation. Advances in the knowledge of the chemistry of PAN and the PANs are reviewed including synthetic procedures, measurement techniques, field and satellite measurements, and important properties (rates of reaction, ultraviolet photolysis, and aqueous solubilities). Ground based measurements obtained in urban centers are highlighted, and the role of these large population centers is examined as sources of the PANs that impact downwind concentrations of tropospheric ozone. The phytotoxicity of PAN is discussed briefly along with its connections to other key trace species including the organic peracids, peroxides, and nitrates. The future potential of increasing wildfires due to climate change that are likely leading to large scale formation of the PANs is discussed along with the need to address the reactions of the PANs with polycyclic hydrocarbons on the surfaces of oily carbonaceous aerosols emitted from these fires. The work summarized here has led to the determination that PAN and its analogs play key roles in urban, regional, and global tropospheric chemistry.

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Chemical ionization mass spectrum of peroxyacetylnitrate

Cited by 15 publications

References 19 publications

Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2

Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2

A new measurement technique of peroxyacetyl nitrate at parts per trillion by volume levels: Gas chromatography/negative ion chemical ionization mass spectrometry

The Impacts of Peroxyacetyl Nitrate in the Atmosphere of Megacities and Large Urban Areas: A Historical Perspective

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