A boron dipyrromethene (BODIPY) based probe for selective passive sampling of atmospheric nitrous acid (HONO) indoors.

People spend up to 90% of their time indoors, and yet our understanding of indoor air quality and the chemical processes driving it are poorly understood, despite levels of key pollutants typically being higher indoors compared to outdoors. Nitrous acid (HONO) is a species that drives these indoor chemical processes, with potentially detrimental health effects. In this work, a BODIPY-based probe was synthesized with the aim of developing the first selective passive sampler for atmospheric HONO. Our probe and its products are easily detected by UV-Vis spectroscopy with molar extinct coefficients of 37 863 and 33 787 M-1 cm-1, respectively, and a detection limit of 14.8 ng mL-1. When protonated, the probe fluoresces with a quantum yield of 33%, which is turned off upon reaction. The synthesized BODIPY probe was characterized using NMR and UV-Vis spectroscopy. Products were characterized by UV-Vis and ultra high-resolution mass spectrometry. The reaction kinetics of the probe with nitrite was studied using UV-Vis spectroscopy, which had a pseudo-first-order rate of k = 7.7 × 10-4 s-1. The rapid reaction makes this probe suitable for targeted ambient sampling of HONO. This was investigated through a proof-of-concept experiment with gaseous HONO produced by a custom high-purity calibration source delivering the sample to the BODIPY probe in an acidic aqueous solution in clean air and a real indoor air matrix. The probe showed quantitative uptake of HONO in both cases to form the same products observed from reaction with nitrite, with no indication of interferences from ambient NO or NO2. The chemical and physical characteristics of the probe therefore make it ideal for use in passive samplers for selective sampling of HONO from the atmosphere.

Emerging investigator series: ozone uptake by urban road dust and first evidence for chlorine activation during ozone uptake by agro-based anti-icer: implications for wintertime air quality in high-latitude urban environments.

High-latitude urban regions provide a unique and complex range of environmental surfaces for uptake of trace pollutant gases, including winter road maintenance materials (e.g., gravel, rock salts, and anti-icer, a saline solution applied to roads during winter). In an effort to reduce the negative environmental and economic impacts of road salts, many municipalities have turned to agro-based anti-icing materials that are rich in organic material. To date, the reactivity of both anti-icer and saline road dust with pollutant gases remain unexplored, which limits our ability to assess the potential impacts of these materials on air quality in high-latitude regions. Here, we used a coated-wall flow tube to investigate the uptake of ozone, an important air pollutant, by road dust collected in Edmonton, Canada. At 25% relative humidity (RH) and 50 ppb ozone, γBET for ozone uptake by this sample is (8.0 ± 0.7) × 10-8 under dark conditions and (2.1 ± 0.1) × 10-7 under illuminated conditions. These values are 2-4× higher than those previously obtained by our group for natural mineral dusts, but are not large enough for suspended road dust to influence local ozone mixing ratios. In a separate set of experiments, we also investigated the uptake of ozone by calcium chloride (i.e., road salt) and commercial anti-icer solution. Although ozone uptake by pure calcium chloride was negligible, ozone uptake by anti-icer was significant, which implies that the reactivity of anti-icer is conferred by its organic content. Importantly, ozone uptake by anti-icer-and, to a lesser extent, road dust doped with anti-icer-leads to the release of inorganic chlorine gas, which we collected using inline reductive trapping and quantified using ion chromatography. To explain these results, we propose a novel pathway for chlorine activation: here, ozone oxidation of the anti-icer organic fraction (in this case, molasses) yields reactive OH radicals that can oxidize chloride. In summary, this study demonstrates the ability of road dust and anti-icer to influence atmospheric oxidant mixing ratios in cold-climate urban areas, and highlights previously unidentified air quality impacts of winter road maintenance decisions.