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Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint

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Abstract

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.

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References

  • Akimoto H, Takagi H, Sakamaki F (1987) Photoenhancement of the nitrous acid formation in the surface reaction of nitrogen dioxide and water vapour: extra radical source in smog chamber experiments. Int J Chem Kinet 19:539–551

    Article  CAS  Google Scholar 

  • Alfassi ZB, Huie RE, Neta P (1986) Substituent effects on rates of one-electron oxidation of phenols by the radicals chlorine dioxide, nitrogen dioxide, and trioxosulfate(1-). J Phys Chem 90:4156–4158

    CAS  Google Scholar 

  • Arens F, Gutzwiller L, Gäggeler HW, Ammann M (2002) The reaction of NO2 with solid anthrarobin (1,2,10-trihydroxy-anthracene). Phys Chem Chem Phys 4:3684–3690

    Article  CAS  Google Scholar 

  • Atkinson R, Baulch DL, Cox RA, Crowley JN, Hampson RF, Hynes RG, Jenkin ME, Rossi MJ, Troe J (2004) Evaluated kinetic and photochemical data for atmospheric chemistry: volume I—gas phase reactions of Ox, HOx, NOx and SOx species. Atmos Chem Phys 4:1461–1738

    CAS  Google Scholar 

  • Auvinen J, Wirtanen L (2008) The influence of photocatalytic interior paints on indoor air quality. Atmos Environ 42:4101–4112

    Article  CAS  Google Scholar 

  • Bartels-Rausch T, Brigante M, Elshorbany YF, Ammann M, D’Anna B, George C, Stemmler C, Ndour M, Kleffmann J (2010) Humic acid in ice: photo-enhanced conversion of nitrogen dioxide into nitrous acid. Atmos Environ 44:5443–5450

    Article  CAS  Google Scholar 

  • Behnke W, George C, Scheer V, Zetzsch C (1997) Production and decay of ClONO2 from the reaction of gaseous N2O5 with NaCl solution: bulk and aerosol experiments. J Geophys Res 102(D3):3795–3804

    Article  CAS  Google Scholar 

  • Brigante M, Cazoir D, D’Anna B, George C, Donaldson DJ (2008) Photoenhanced uptake of NO2 by pyrene solid films. J Phys Chem A 112:9503–9508

    CAS  Google Scholar 

  • Carslaw N (2007) A new detailed chemical model for indoor air pollution. Atmos Environ 41:1164–1179

    Article  CAS  Google Scholar 

  • Febo A, Perrino C (1991) Prediction and experimental evidence for high air concentration of nitrous acid in indoor environments. Atmos Environ 25A:1055–1061

    Article  CAS  Google Scholar 

  • Febo A, Perrino C (1995) Measurement of high concentration of nitrous acid inside automobiles. Atmos Environ 29:345–351

    Article  CAS  Google Scholar 

  • Finlayson-Pitts BJ, Pitts JN Jr (2000) Chemistry of the upper and lower atmosphere. Theory, experiments, and applications. Academic, San Diego

    Google Scholar 

  • Finlayson-Pitts BJ, Wingen LM, Sumner AL, Syomin D, Ramazan KA (2003) The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: an integrated mechanism. Phys Chem Chem Phys 5:223–242

    Article  CAS  Google Scholar 

  • George C, Strekowski RS, Kleffmann J, Stemmler K, Ammann M (2005) Photoenhanced uptake of gaseous NO2 on solid organic compounds: a photochemical source of HONO? Faraday Discuss 130:195–210

    Article  CAS  Google Scholar 

  • Gligorovski S, Weschler CJ (2013) The oxidative capacity of indoor atmospheres. Environ Sci Technol 47(24):13905–13906

    Article  CAS  Google Scholar 

  • Gómez Alvarez E, Wortham H, Strekowski R, Zetzsch C, Gligorovski S (2012) Atmospheric photosensitized heterogeneous and multiphase reactions: from outdoors to indoors. Environ Sci Technol 46:1955–1963

    Article  Google Scholar 

  • Gómez Alvarez E, Amedro D, Afif C, Gligorovski S, Schoemacker C, Fittschen C, Doussin J-F, Wortham H (2013) Photolysis of nitrous acid as a primary source of OH radicals indoors. Proc Natl Acad Sci US A 110(33):13294–13299

    Article  Google Scholar 

  • Harwood EA, Hopkins PB, Sigurdsson ST (2000) Chemical synthesis of cross-link lesions found in nitrous acid treated DNA: a general method for the preparation of N2-substituted 2-deoxyguanosines. J Org Chem 65:2959–2964

    Article  CAS  Google Scholar 

  • Jenkin ME, Cox RA, Williams DJ (1988) Laboratory studies of the kinetics of formation of nitrous acid from the thermal reaction of nitrogen dioxide and water vapour. Atmos Environ 22:487–498

    Article  CAS  Google Scholar 

  • Kleffmann J, Wiesen P (2008) Technical note: quantification of interferences of wet chemical HONO LOPAP measurements under simulated polar conditions. Atmos Chem Phys 8:6813–6822

    CAS  Google Scholar 

  • Kleffmann J, Heland J, Kurtenbach R, Lörzer JC, Wiesen P (2002) A new instrument (LOPAP) for the detection of nitrous acid (HONO). Environ Sci Pollut Res 9(4):48–54

    Google Scholar 

  • Laufs S, Burgeth G, Duttlinger W, Kurtenbach R, Maban M, Thomas C, Wiesen P, Kleffmann J (2010) Conversion of nitrogen oxides on commercial photocatalytic dispersion paints. Atmos Environ 44:2341–2349

    Article  CAS  Google Scholar 

  • Leaderer BP, Naeher L, Jankun T, Balenger K, Holford TR, Toth C, Sullivan J, Wolfson JM, Koutrakis P (1999) Indoor, outdoor, and regional summer and winter concentrations of PM10, PM2.5, SO4 2−, H+, NH4 +, NO3 −, NH3, and nitrous acid in homes with and without kerosene space heaters. Environ Health Perspect 107:223–231

    CAS  Google Scholar 

  • Lee K, Xue J, Geyh AS, Özkaynak H, Leaderer BP, Weschler CJ, Spengler JD (2002) Nitrous acid, nitrogen dioxide, and ozone concentrations in residential environments. Environ Health Perspect 110:145–149

    Article  CAS  Google Scholar 

  • Monn C (2001) Exposure assessment of air pollutants: a review on spatial heterogeneity and indoor/outdoor/personal exposure to suspended particulate matter, nitrogen dioxide and ozone. Atmos Environ 35:1–32

    Article  CAS  Google Scholar 

  • Perraudin E, Budzinski H, Villenace E (2005) Kinetic study of the reactions of NO2 with polycyclic aromatic hydrocarbons adsorbed on silica particles. Atmos Environ 39:6557–6567

    Article  CAS  Google Scholar 

  • Pitts JN Jr, Grosjean D, Van Cauwenbergge K, Schmid JP, Fitz DR (1978) Photooxidation of aliphatic amines under simulated atmospheric conditions: formation of nitrosamines, nitramines, amides and photochemical oxidant. Environ Sci Technol 12:946–953

    Article  CAS  Google Scholar 

  • Pitts JN Jr, Sanhueza E, Atkinson R, Carter WPL, Winer AM, Harris GW, Plum CN (1984) An investigation of the dark formation of nitrous acid in environmental chambers. Int J Chem Kinet 16:919–939

    Article  CAS  Google Scholar 

  • Pitts JN Jr, Biermann HW, Tuazon EC, Green M, Long WD, Winer AM (1989) Time-resolved identification and measurement of indoor air pollutants by spectroscopic techniques: gaseous nitrous acid, methanol, formaldehyde and formic acid. J Air Pollut Control Assoc 39:1344–1347

    CAS  Google Scholar 

  • Sakamaki F, Hatakeyama S, Akimoto H (1983) Formation of nitrous Acid and nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and water vapor in a smog chamber. Int J Chem Kinet 15:1013–1029

    Article  CAS  Google Scholar 

  • Salthammer T, Fuhrmann F (2007) Photocatalytic surface reactions on indoor wall paint. Environ Sci Technol 41(18):6573–6578

    Article  CAS  Google Scholar 

  • Sarwar G, Corsi R, Kimura Y, Allen D, Weschler JC (2002) Hydroxyl radicals in indoor environments. Atmos Environ 36:3973–3988

    Article  CAS  Google Scholar 

  • Sleiman M, Gundel LA, Pankow JF, Jacob P III, Singer BC, Destaillats H (2010) Formation of carcinogens indoors by surface-mediated reactions of nicotine with nitrous acid, leading to potential third-hand smoke hazards. Proc Natl Acad Sci US A 107:6576–6581

    Article  CAS  Google Scholar 

  • Sosedova Y, Rouvière A, Bartels-Rausch T, Ammann M (2011) UVA/Vis-induced nitrous acid formation on polyphenolic films exposed to gaseous NO2. Photochem Photobiol Sci 10:1680–1690

    CAS  Google Scholar 

  • Spengler JD, Brauer M, Samet JM, Lambert WE (1993) Nitrous acid in Albuquerque, New Mexico, homes. Environ Sci Technol 27:841–845

    Article  CAS  Google Scholar 

  • Stemmler K, Ammann M, Donders C, Kleffmann J, George C (2006) Photosensitized reduction of nitrogen dioxide on humic acid as a source of nitrous acid. Nature 440:195–198

    Article  CAS  Google Scholar 

  • Stemmler K, Ndour M, Elshorbany Y, Kleffmann J, D’Anna B, George C, Bohn B, Ammann M (2007) Light induced conversion of nitrogen dioxide into nitrous acid on submicron humic acid aerosol. Atmos Chem Phys 7:4237–4248

    CAS  Google Scholar 

  • Stutz J, Kim ES, Platt U, Bruno P, Perrino C, Febo A (2000) UV-visible absorption cross section of nitrous acid. J Geophys Res 105(D11):14585–14592

    Article  CAS  Google Scholar 

  • Večeřa Z, Dasgupta PK (1994) Indoor nitrous acid levels. Production of nitrous acid from open-flame sources. Int J Environ Anal Chem 56:311–316

    Article  Google Scholar 

  • Wainman T, Weschler CJ, Lioy PJ, Zhang J (2001) Effects of surface type and relative humidity on the production and concentration of nitrous acid in a model indoor environment. Environ Sci Technol 35:2200–2206

    Article  CAS  Google Scholar 

  • Wallace LA, Emmerich SJ, Howard-Reed C (2002) Continuous measurements of air change rates in an occupied house for 1 year: the effect of temperature, wind, fans, and windows. J Expo Anal Environ Epidemiol 12:296–306

    Article  CAS  Google Scholar 

  • Weschler CJ (2004) Chemical reactions among indoor pollutants: what we’ve learned in the new millennium. Indoor Air 14:184–194

    Article  Google Scholar 

  • Weschler CJ (2009) Changes in indoor pollutants since the 1950s. Atmos Environ 43:153–169

    Article  CAS  Google Scholar 

  • Weschler CJ, Shields HC (1997) Potential reactions among indoor pollutants. Atmos Environ 31:3487–3495

    Article  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the project “Les surfaces internes à l'habitat, une source probable d'acide nitreux” and the French program PRIMEQUAL.

This work is also a contribution to the LABEX SERENADE (no. ANR-11-LABX-0064) funded by the “Investissements d’Avenir,” French Government program of the French National Research Agency (ANR) through the A*Midex project (no. ANR-11-IDEX-0001-02). Financial support by the German Science foundation (DFG project HE5214/4-1) is gratefully acknowledged.

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  1. Matthias Sörgel

    Present address: Biogeochemistry Department, Max Planck Institute for Chemistry, P.O. Box 3060, 55020, Mainz, Germany

Authors and Affiliations

  1. Aix Marseille University, CNRS, FRE 3416, Case 29, 3 place Victor Hugo, 13331, Marseille Cedex 3, France

    Vincent Bartolomei, Sasho Gligorovski, Elena Gómez Alvarez, Adrien Gandolfo, Rafal Strekowski, Etienne Quivet & Henri Wortham

  2. Forschungsstelle für Atmosphärische Chemie, Universität Bayreuth, Dr.-Hans-Frisch-Str. 1-3, 95448, Bayreuth, Germany

    Matthias Sörgel, Andreas Held & Cornelius Zetzsch

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  1. Vincent Bartolomei
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Correspondence to Sasho Gligorovski.

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Bartolomei, V., Sörgel, M., Gligorovski, S. et al. Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint. Environ Sci Pollut Res 21, 9259–9269 (2014). https://doi.org/10.1007/s11356-014-2836-5

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