Emerging investigator series: an instrument to measure and speciate the total reactive nitrogen budget indoors: description and field measurements

Abstract

Reactive nitrogen species (N_r), defined here as all N-containing compounds except N₂ and N₂O, have been shown to be important drivers for indoor air quality. Key N_r species include NO_x (NO + NO₂), HONO and NH₃, which are known to have detrimental health effects. In addition, other N_r species that are not traditionally measured may be important chemical actors for indoor transformations (e.g. amines). Cooking and cleaning are significant sources of N_r, whose emission will vary depending on the type of activity and materials used. Here we present a novel instrument that measures the total gas-phase reactive nitrogen (tN_r) budget and key species NO_x, HONO, and NH₃ to demonstrate its suitability for indoor air quality applications. The tN_r levels were measured using a custom-built heated platinum (Pt) catalytic furnace to convert all N_r species to NO_x, called the tN_r oven. The measurement approach was validated through a series of control experiments, such that quantitative measurement and speciation of the total N_r budget are demonstrated. The optimum operating conditions of the tN_r oven were found to be 800 °C with a sampling flow rate of 630 cubic centimetres per minute (ccm). Oxidized nitrogen species are known to be quantitatively converted under these conditions. Here, the efficiency of the tN_r oven to convert reduced N_r species to NO_x was found to reach a maximum at 800 °C, with 103 ± 13% conversion for NH₃ and 79–106% for selected relevant amines. The observed variability in the conversion efficiency of reduced N_r species demonstrates the importance of catalyst temperature characterization for the tN_r oven. The instrument was deployed successfully in a commercial kitchen, a complex indoor environment with periods of rapidly changing levels, and shown to be able to reliably measure the tN_r budget during periods of longer-lived oscillations (>20 min), typical of indoor spaces. The measured NO_x, HONO and basic N_r (NH₃ and amines) were unable to account for all the measured tN_r, pointing to a substantial missing fraction (on average 18%) in the kitchen. Overall, the tN_r instrument will allow for detailed survey(s) of the key gaseous N_r species across multiple locations and may also identify missing N_r fractions, making this platform capable of stimulating more in-depth analysis in indoor atmospheres.