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. 2015 Apr:106:382-391.
doi: 10.1016/j.atmosenv.2014.06.062.

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Michael S Waring  1 , J Raymond Wells  2
Affiliations

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

Michael S Waring et al. Atmos Environ (1994). 2015 Apr.

Abstract

Indoor chemistry may be initiated by reactions of ozone (O3), the hydroxyl radical (OH), or the nitrate radical (NO3) with volatile organic compounds (VOC). The principal indoor source of O3 is air exchange, while OH and NO3 formation are considered as primarily from O3 reactions with alkenes and nitrogen dioxide (NO2), respectively. Herein, we used time-averaged models for residences to predict O3, OH, and NO3 concentrations and their impacts on conversion of typical residential VOC profiles, within a Monte Carlo framework that varied inputs probabilistically. We accounted for established oxidant sources, as well as explored the importance of two newly realized indoor sources: (i) the photolysis of nitrous acid (HONO) indoors to generate OH and (ii) the reaction of stabilized Criegee intermediates (SCI) with NO2 to generate NO3. We found total VOC conversion to be dominated by reactions both with O3, which almost solely reacted with d-limonene, and also with OH, which reacted with d-limonene, other terpenes, alcohols, aldehydes, and aromatics. VOC oxidation rates increased with air exchange, outdoor O3, NO2 and d-limonene sources, and indoor photolysis rates; and they decreased with O3 deposition and nitric oxide (NO) sources. Photolysis was a strong OH formation mechanism for high NO, NO2, and HONO settings, but SCI/NO2 reactions weakly generated NO3 except for only a few cases.

Keywords: Indoor chemistry; Monte Carlo modeling; Photolysis; Terpenes; VOC oxidation.

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Figures

Fig. 1
Fig. 1
Box plots of (a) CO3, COH, and CNO3 for the different Monte Carlo sets R1–R4; (b) VOC oxidation rate by each oxidant for all cases within each set; (c) VOC oxidation rate by each oxidant for high outdoor O3 and low outdoor NOx cases only; (d) VOC oxidation rate by each oxidant for low outdoor O3 and high outdoor NOx cases only. See text for more details.
Fig. 2
Fig. 2
Box plots of fractions contribution of various OH and NO3 sources considered in the modeling, for the residential R1–R4 settings. For OH, source ‘O3’ is O3/alkene reactions; ‘JHONO’ is HONO photolysis. For NO3, source ‘O3’ is O3/NO2 reactions; ‘Dis’ is dissociation of N2O5; ‘SCI’ is SCI/NO2 reactions.
Fig. 3
Fig. 3
Scatter plots of the VOC oxidation by O3, OH, and NO3 versus CO3, CNO, and CNO2, over the R2 and R4 Monte Carlo sets (showing the first 100 cases only for plot clarity).
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