Heterogeneous photochemistry of gaseous NO2 on solid fluoranthene films: A source of gaseous nitrous acid (HONO) in the urban environment

Cazoir, David; Brigante, Marcello; Ammar, Rachid; D’Anna, Barbara; George, Christian

doi:10.1016/j.jphotochem.2013.07.016

Cited by 35 publications

(53 citation statements)

References 41 publications

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“…To explain enhanced HONO formation, photosensitized conversion of HNO 3 /nitrate by adsorbed organic compounds was recently proposed. [69][70][71][72] In addition, increased HONO formation by scavenging of OH radicals formed via reaction (R2) by organic compounds was proposed for the liquid phase photolysis of nitrate. 66 To test the influence of organic compounds on the reaction system, in one experiment a GC calibration mixture of 29 VOCs (rC10, see Section 2.3. for details; each with a final mixing ratio of 3-4 ppbV) was continuously added to the humidified HNO 3 mixture, both, during surface saturation overnight and during the photolysis.…”

Section: Influence Of Vocsmentioning

confidence: 99%

Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces

Laufs

Kleffmann

2016

Phys. Chem. Chem. Phys.

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During the last few decades, nitrous acid (HONO) has attracted significant attention as a major source of the OH radical, the detergent of the atmosphere. However, the different daytime sources identified in the laboratory are still the subject of controversial discussion. In the present study, one of these postulated HONO sources, the heterogeneous photolysis of nitric acid (HNO3), was studied on quartz glass surfaces in a photo flow-reactor under atmospherically relevant conditions. In contrast to other investigations, a very low HNO3 photolysis frequency for HONO formation of J(HNO3→ HONO) = 2.4 × 10(-7) s(-1) (0° SZA, 50% r.h.) was determined. If these results can be translated to atmospheric surfaces, HNO3 photolysis cannot explain the significant HONO levels in the daytime atmosphere. In addition, it is demonstrated that even the small measured yields of HONO did not result from the direct photolysis of HNO3 but rather from the consecutive heterogeneous conversion of the primary photolysis product NO2 on the humid surfaces. The secondary NO2 conversion was not photo-enhanced on pure quartz glass surfaces in good agreement with former studies. A photolysis frequency for the primary reaction product NO2 of J(HNO3→ NO2) = 1.1 × 10(-6) s(-1) has been calculated (0° SZA, 50% r.h.), which indicates that renoxification by photolysis of adsorbed HNO3 on non-reactive surfaces is also a minor process in the atmosphere.

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Section: Influence Of Vocsmentioning

confidence: 99%

Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces

Laufs

Kleffmann

2016

Phys. Chem. Chem. Phys.

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“…Recently, Cazoir et al (2014) studied the heterogeneous loss kinetics of gaseous NO 2 on solid fluoranthene films deposited on a Pyrex substrate under UV-A (range 300-420 nm) radiation. The uptake coefficients decreased from 2 Â 10 À6 to 7.0 Â 10 À7 , for initial NO 2 concentrations of 20 and 150 ppb, respectively, and they were not affected by temperature and RH.…”

Section: Photolysis/photoenhanced Surface Reactionsmentioning

confidence: 99%

Sources of atmospheric nitrous acid: State of the science, current research needs, and future prospects

Spataro

Ianniello

2014

Journal of the Air & Waste Management Association

103

107

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Nitrous acid (HONO) plays a key role in tropospheric photochemistry, primarily due to its role as a source of hydroxyl (OH) radicals via its rapid photolysis. OH radicals are involved in photooxidation processes, such as the formation of tropospheric 03 and other secondary atmospheric pollutants (peroxyacetyl nitrate/PAN] and secondary particles). Recent field and modeling studies have postulated the occurrence of a strong and unknown daytime HONO source, but there are still many significant uncertainties concerning the identification and formation mechanisms of these unknown sources. Up to now, five HONO formation pathways are known: direct emission, homogeneous gas-phase reactions, heterogeneous reactions, surface photolysis; and biological processes. In this review paper the HONO sources proposed to explain the observed HONO budget, especially during daytime, are discussed, highlighting the knowledge gaps that need further investigation. In this framework it is crucial to have available accurate and reliable measurements of atmospheric HONO concentrations; thus, a short description ofHONO measurement techniques currently available is also reported. The techniquesare divided into three basic categories: spectroscopic techniques, wet chemical techniques, and off-line methods.

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“…Enhanced reactivity of NO2 was found when irradiation was involved in the heterogeneous process. For example, the photo-enhanced uptake of NO2 have been found on polycyclic aromatic hydrocarbons (PAHs) [7][8][9][10], humic acid (HA) [11][12][13], soot [14,15] and mineral dust [3,16]. The photoenhanced γ is usually within 10 -7 ~10 -6 , larger than those on inorganic particles at dark by one or two orders of magnitude.…”

Section: Introductionmentioning

confidence: 99%

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Wang

et al. 2021

Journal of Environmental Sciences

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Heterogeneous reactions of NO2 on different surfaces play an important role in atmospheric NOx removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO2 uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during daytime. However, the uptake behavior of NO2 varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO2 uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO2 uptake coefficient (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark condition, with the measured γ varied from <10 -8 to 3.2×10 -7 under different humidity.A photo-enhanced uptake of NO2 on urban grime were observed, with obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9×10 -6 to at 5% RH and 5.8×10 -6 at 70% RH on urban grime, showing a positive RH dependence for both NO2 uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO2-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.

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Heterogeneous photochemistry of gaseous NO2 on solid fluoranthene films: A source of gaseous nitrous acid (HONO) in the urban environment

Cited by 35 publications

References 41 publications

Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces

Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces

Sources of atmospheric nitrous acid: State of the science, current research needs, and future prospects

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

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Heterogeneous photochemistry of gaseous NO2 on solid fluoranthene films: A source of gaseous nitrous acid (HONO) in the urban environment

Cited by 35 publications

References 41 publications

Investigations on HONO formation from photolysis of adsorbed HNO3on quartz glass surfaces

Investigations on HONO formation from photolysis of adsorbed HNO3on quartz glass surfaces

Sources of atmospheric nitrous acid: State of the science, current research needs, and future prospects

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

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Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces

Investigations on HONO formation from photolysis of adsorbed HNO₃on quartz glass surfaces