Photochemical production of nitrous acid on glass sample manifold surface

Zhou, Xianliang; He, Yi; Huang, Gu; Thornberry, T. D.; Carroll, Mary Anne; Bertman, S. B.

doi:10.1029/2002gl015080

Cited by 124 publications

(142 citation statements)

References 23 publications

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“…It is also well known that N 2 O 5 is taken up on surfaces and hydrolyzed (54). Due to such uptake, there is a reservoir of strongly adsorbed reactive oxides of nitrogen on surfaces in both environmental chambers (14) and in the field (13).…”

Section: Nomentioning

confidence: 99%

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Raff

Njegic

Chang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

113

182

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Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO y ) are also globally distributed, because NO formed in combustion processes is oxidized to NO 2 , HNO 3 , N 2 O 5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NO y onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO 2 or N 2 O 5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO 2 ), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO 2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

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Section: Nomentioning

confidence: 99%

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Raff

Njegic

Chang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

113

182

View full text Add to dashboard Cite

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“…Thus, the mechanism proposed in the present study might explain a significant fraction of the observed HONO formation in the urban atmosphere, besides other postulated photolytic HONO sources. 38,47,49,[52][53][54] However, this estimate needs to be verified using data from further experiments performed under atmospheric conditions, and also investigations on the wavelength dependencies of the photolysis processes.…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

The photolysis of ortho-nitrophenols: a new gas phase source of HONO

Bejan

Aal

Barnes

et al. 2006

Phys. Chem. Chem. Phys.

250

291

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Formation of nitrous acid (HONO) in the gas phase has been observed for the first time in a flow tube photoreactor upon irradiation (l = 300-500 nm) of 2-nitrophenol and methyl substituted derivatives using a selective and sensitive instrument (LOPAP) for the detection of HONO. Formation of HONO by heterogeneous NO 2 photochemistry has been excluded, since production of NO 2 under the experimental conditions is negligible. Variation of the surface to volume ratio and the nitrophenol concentration showed that the photolysis occurred in the gas phase indicating that HONO formation is initiated by intramolecular hydrogen transfer from the phenolic OH group to the nitro group. From the measured linear dependence of the HONO formation rate on the reactant's concentration and photolysis light intensity, a non-negligible new HONO source is proposed for the urban atmosphere during the day. Unexpectedly high HONO mixing ratios have been observed recently in several field campaigns during the day. It is proposed that the photolysis of aromatic compounds containing the ortho-nitrophenol entity could help to explain, at least in part, this high contribution of HONO to the oxidation capacity of the urban atmosphere.

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“…As recent measurements of the photolysis of adsorbed HNO 3 (Zhu et al, 2010) found NO 2 * as the main photolysis product, Zhou et al (2011) assume that HONO formation by HNO 3 photolysis also follows the mechanism of NO 2 conversion provided by and Stemmler et al (2006). Adsorbed HNO 3 therefore acts as a reservoir or a source of NO x in rural environments (Zhou et al, 2002b(Zhou et al, , 2011. One might speculate if the reaction of NO 2 * formed by HNO 3 photolysis at the surface with adsorbed water is also enhanced with regard to the gas phase Reaction (R8), and thus can act as source of HONO from HNO 3 photolysis.…”

Section: Important Ground Sourcesmentioning

confidence: 99%

Quantification of the unknown HONO daytime source and its relation to NO<sub>2</sub>

et al. 2011

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Abstract. During the DOMINO (Diel Oxidant MechanismIn relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO 2 , j (NO 2 ) as a proxy for j (HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO 2 mixing ratios and expressed as a conversion frequency (% h −1 ), showed a clear dependence on j (NO 2 ) with values up to 43 % h −1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO 2 conversion on soot surfaces and the reaction of electronically excited NO 2 * with water vapour, with the result that these two reactions normally contributed less than 10 % (<1 % NO 2 + soot + hν; and <10 % NO 2 * + H 2 O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20 %) than the "classical" OH formation from ozone photolysis (O( 1 D)) integrated over the day.Correspondence to: M. Sörgel

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Photochemical production of nitrous acid on glass sample manifold surface

Cited by 124 publications

References 23 publications

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

The photolysis of ortho-nitrophenols: a new gas phase source of HONO

Quantification of the unknown HONO daytime source and its relation to NO<sub>2</sub>

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Photochemical production of nitrous acid on glass sample manifold surface

Cited by 124 publications

References 23 publications

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

The photolysis of ortho-nitrophenols: a new gas phase source of HONO

Quantification of the unknown HONO daytime source and its relation to NO&lt;sub&gt;2&lt;/sub&gt;

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Quantification of the unknown HONO daytime source and its relation to NO<sub>2</sub>