Photoenhanced uptakes of NO2 by indoor surfaces: A new HONO source

Nitrous acid (HONO) is a known household pollutant that can lead to human respiratory tract irritation. HONO acts as the nitrosating agent, e.g. by the formation of the so-called third-hand smoke after wall reactions of HONO with nicotine (1). HONO can be generated indoors directly during combustion processes or indirectly via heterogeneous NO2 reactions with adsorbed water on diverse surfaces (2). Recently a new source was identified as another path of HONO formation in the troposphere (3). Namely, the light-induced heterogeneous reaction of NO2 with adsorbed organics (known as photosensitizers) on various surfaces such as roads, buildings, rocks or plants leads to enhanced HONO production. The detected values of HONO indoors vary in the range between 2 and 25 parts per billion (ppb). However, like outdoors, the processes leading to HONO formation indoors are not completely understood (4). Indoor photolysis radiation sources include exterior sunlight (λ>350 nm) that enters typically through the windows and indoor illumination sources, i.e., rare gas/mercury fluorescent light bulbs and tungsten and tungsten/halogen light bulbs among others. The present work is showing the importance of indoor sources of HONO recently identified or postulated. We have tested a number of common household chemical agents commonly used for cleaning purposes or coatings of domestic surfaces to better identify different indoor HONO sources. We used a heterogeneous flow tube technique to test the HONO production potentials of these household chemical agents under different experimental conditions, namely with and without light and at different relative humidity levels and different NO2 concentrations. We report uptake kinetics measurements of the heterogeneous reaction of gas phase NO2 with lacquer and paint coated on the walls of the reactor. The flow tube was irradiated with four near-ultraviolet (UV) emitting lamps (range of wavelengths 300-420nm). We observed that the heterogeneous conversion of NO2 to HONO on lacquer surfaces and on white wall paints is substantially enhanced in the presence of light and at higher relative humidity (RH = 60%). In runs carried out applying experimental conditions typically found indoors, i.e., NO2 mixing ratios of 25 ppb and 60% RH%, the observed NO2 uptakes on a surface coated with lacquer and paint showed an enhancement of one order of magnitude in the presence of light as compared to the uptake observed in the dark. Our results indicate, contrary to other study that claimed that humidity does not influence the NO2 reactions with adsorbed organics, that actually both postulated HONO sources combined i.e. heterogeneous NO2 reactions with adsorbed organics (photosensitizers) in presence of elevated humidity leads to even more pronounced HONO production. Reference: 1. M., Sleiman, L. A., Gundel, J. F., Pankow, P., Jacob, B. C., Singer, H., Destaillats, P. Natl. Acad. Sci. USA, 107, 6576 (2010). 2. B. J. Finlayson-Pitts, L. M. Wingen, A. L. Sumner, D. Syomin, K. A. Ramazan, Phys. Chem. Chem. Phys. 5, 223 (2003). 3. K., Stemmler, M., Ammann, C., Donders, J., Kleffmann, C., George, Nature 440, 195 (2006). 4. E. Gomez Alvarez, H. Wortham, R. Strekowski, C. Zetzsch, S. Gligorovski, Environ. Sci. Technol., 46, 1955 (2012).