An investigation of the dark formation of nitrous acid in environmental chambers

Pitts, James N.; Sanhueza, Eugenio; Atkinson, Roger; Carter, William; Winer, Arthur M.; Harris, G. W.; Plum, Christopher N.

doi:10.1002/kin.550160712

Cited by 176 publications

(203 citation statements)

References 21 publications

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“…At the relative humidity of !40% observed during the measurement intensive, there should be at least several monolayers of water on the glass manifold wall surfaces [Svensson et al, 1987;Saliba et al, 2001]. Thus the produced NO 2(ads) may react rapidly with adsorbed H 2 O to produce HONO, which is then released from the surface into the air [Pitts et al, 1984] This mechanism is consistent with the recent observations of photochemical production of HONO [Zhou et al, 2001] and NO x [Honrath et al, 1999[Honrath et al, , 2000 in snowpack from nitrate/HNO 3 photolysis. These observations are also supportive of a recent hypothesis that the photolysis of adsorbed HNO 3 /nitrate on ground surfaces is a major daytime source of HONO and thus is responsible for the observed elevated HONO concentrations in the rural atmospheric boundary layer .…”

Section: Resultssupporting

confidence: 87%

Photochemical production of nitrous acid on glass sample manifold surface

Zhou

Huang

et al. 2002

Geophysical Research Letters

124

134

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[1] Significant production of HONO was observed on glass sample manifold wall surface when exposed to sunlight during the PROPHET 2000 summer measurement intensive. It is hypothesized that the artifact HONO was produced by photolysis of adsorbed nitric acid/nitrate on the manifold wall surfaces followed by the subsequent reaction of produced NO 2 and adsorbed H 2 O on surface. This observation suggests against the use of an unshielded glass manifold as a sampling inlet for the measurement of atmospheric HONO. It may also have some implications in interpreting field NO x data measured using similar glass inlet manifolds, especially from the clean remote environments where NO x is low and HNO 3 is a major fraction of NO y .

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Section: Resultssupporting

confidence: 87%

Photochemical production of nitrous acid on glass sample manifold surface

Zhou

Huang

et al. 2002

Geophysical Research Letters

124

134

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“…The observation of increasing yields of NO with decreasing HONO yields at intermediate to high relative humidities in such studies of reaction (1) 10,14,15,17,23,24,73 is consistent with the formation of HONO followed by its conversion to NO on the '' unconditioned '' walls of the reactor as illustrated, for example, by the data in Fig. 2e.…”

supporting

confidence: 76%

“…12,13 However, the yield of HONO measured in laboratory studies is generally less than expected from reaction (1), particularly in reactors with large surface-to-volume (S/V) ratios. 10,[14][15][16][17][18][19][20][21][22][23][24] This suggests either that some of the HONO reacts on the surface before it is released to the gas phase, or that it is released and subsequently reacts on the chamber walls.…”

Section: Introductionmentioning

confidence: 99%

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

Syomin

Finlayson-Pitts

2003

Phys. Chem. Chem. Phys.

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Nitrous acid (HONO) is the major source of OH in polluted urban atmospheres, so an understanding of its formation and loss processes both in urban atmospheres and in laboratory systems is important. Earlier studies over a limited range of conditions showed that HONO is taken up and undergoes reaction on surfaces. We report here a comprehensive set of studies of the decay of HONO and the formation of gas phase products over a range of initial HONO concentrations (0.1-11 ppm) at 1 atm pressure in N 2 at 296 K and 0, 20 and 50% relative humidity (RH), respectively. The loss of HONO and increase in gas phase products were measured over time using long path FTIR spectroscopy. Studies were carried out in an unconditioned borosilicate glass cell and in the same cell after pretreatment with dry gaseous nitric acid. In the HNO 3 -conditioned cell, the loss of HONO was first order at all values of relative humidity (RH), and NO 2 was the only significant gas phase product. For the unconditioned cell, the reaction order increased from first order at 0% RH to second order at 50% RH. The gas phase products at 0% RH were equal amounts of NO and NO 2 . The yield of NO increased to > 90% at 50% RH while the yield of NO 2 decreased to 10%. For both the unconditioned and the HNO 3 -treated cell, the rate of loss of HONO decreased with increasing RH. These results suggest that there is a competition between water, HONO and HNO 3 for surface sites. Displacement of HONO from the cell walls by water was observed in separate experiments. Possible mechanisms, and the implications for HONO formation in environmental chambers and in air, are discussed.

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“…Reaction (R3a) is the overall stoichiometry of the wellknown surface reaction for the hydrolysis of NO 2 (FinlaysonPitts et al, 2003;Pitts Jr et al, 1984) that generates both gas phase nitrous acid (HONO) and nitric acid (Finlayson-Pitts et al, 2003). This entire reaction sequence could occur on either the surface of the particle and/or on the surface of the deposited particulate matter on the vaporization coil.…”

Section: Perci Ams Ionmentioning

confidence: 99%

The ozonolysis of primary aliphatic amines in fine particles

2008

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Abstract. The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO − 2 and NO − 3 ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO − 3 (HNO 3 ). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with p O 3 ≥3×10 −7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10 −3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g. NO 2 , NO 3 ), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

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An investigation of the dark formation of nitrous acid in environmental chambers

Cited by 176 publications

References 21 publications

Photochemical production of nitrous acid on glass sample manifold surface

Photochemical production of nitrous acid on glass sample manifold surface

HONO decomposition on borosilicate glass surfaces: implications for environmental chamber studies and field experiments

The ozonolysis of primary aliphatic amines in fine particles

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