Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Spectroscopic study of organic coatings on fine particles,exposed to ozone and simulated sunlight

This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C^?1 O₃ ppm^?1 in the region 290–358 nm and by 1.0 absorption units ng-C^?1 O₃ ppm^?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.     

Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

The heterogeneous ozonolysis of naphthalene adsorbed on XAD-4 resin was studied using an annular denuder technique. The experiments involved depositing a known quantity of naphthalene on the XAD-4 resin and then measuring the quantity of the solid naphthalene that reacted away under a constant flow of gaseous ozone (0.064 to 4.9 ppm) for a defined amount of time. All experiments were performed at room temperature (26 to 30 °C) and atmospheric pressure. The kinetic rate coefficient for the ozonolysis reaction of naphthalene adsorbed on XAD-4 resin is reported to be (10.1?±?0.4)?×?10^?19 cm³ molecule^?1 s^?1 (error is 2σ, precision only). This value is five times greater than the currently recommended literature value for the homogeneous gas phase reaction of naphthalene with ozone. The obtained rate coefficient is used to evaluate reaction artifacts from field concentration measurements of naphthalene, acenaphthene, and phenanthrene. The observed uncertainties associated with field concentration measurements of naphthalene, acenaphthene, and phenanthrene are reported to be much higher than the uncertainties associated with the artifact reactions. Consequently, ozone reaction artifact appears to be negligible compared to the observed field measurement uncertainty results.     

Heterogeneous light-induced ozone processing on the organic coatings in the atmosphere

Many of the more recent studies concerning heterogeneous reactions of atmospheric interest, carry, in some cases, much more details but still follow the basic philosophy of the first pioneering studies. Therefore, in this study the accent is put on the additional complexities that arise when the aerosols of interest have more complex compositions. Hence, it is attempted to identify the products following the simultaneous ozone processing and light irradiation on particles coated with 4-phenoxyphenol in the presence of 4-carboxybenzophenone as a photosensitizer. In order to reveal a more complete picture on the fate of these aromatic compounds under controlled experimental conditions, different analytical tools such as gas chromatography coupled to mass spectrometry (GC–MS) and proton transfer reaction-mass spectrometry (PTR-MS) have been applied.Several surface bound products were identified via GC–MS and some of them (phenol, hydroquinone, catechol, 4-hydroxybenzoic acid, benzoic acid, fumaric acid, terephthalic acid, maleic acid, 1,2,4-trihydroxybenzene and 4,4′-oxydiphenol) confirmed with standards. The main volatile secondary products as identified by PTR-MS in this study were formic acid, phenol and p-benzoquinone.A reaction mechanism was proposed and density functional theory calculations were performed in order to elucidate the initial steps of the ozonolysis reaction on 4-phenoxyphenol in the presence of 4-carboxybenzophenone.     

Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

For the first time we investigated the effect of solar irradiation upon the heterogeneous ozonation of adsorbed 3,4,5-trimethoxybenzaldehyde on solid surface. Light-induced heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde adsorbed on silica particles were performed and the consecutive reaction products were identified. At an ozone mixing ratio of 250 ppb, the loss of 3,4,5-trimethoxybenzaldehyde ranged from 1.0 · 10^?6 s^?1 in the dark to 2.9 · 10^?5 s^?1 under light irradiation. Such large enhancement of 29 times clearly shows the importance of light (λ > 300 nm) during the heterogeneous ozonolysis on organic coated particles.The reaction products identified in this study (3,4,5-trimethoxybenzoic acid, syringic acid, methyl 3,4,5-trimethoxybenzoate) absorb light in the spectral window (λ > 300 nm) which implies that light-induced heterogeneous ozone processing can have an influence on the aerosol surfaces by changing their physico-chemical properties.The main identified product of the heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde under dark conditions and in presence of light was 3,4,5-trimethoxybenzoic acid. For this reason we estimated the carbon yield of 3,4,5-trimethoxybenzoic acid. Carbon yields of 3,4,5-trimethoxybenzoic acid decreased with increasing ozone mixing ratio; from 40% at 250 ppb to 15% at ≥2.5 ppm under dark conditions. At ozone mixing ratio (250 ppb–1 ppm), carbon yields of 3,4,5-trimethoxybenzaldehyde are relatively higher in the experiment under dark condition than under simulated solar light.