Emerging investigator series: heterogeneous OH oxidation of primary brown carbon aerosol: effects of relative humidity and volatility.

The climate forcing of light-absorbing organic aerosol, or brown carbon (BrC), emitted from biomass burning may be significant but is currently poorly constrained, in part due to evolution during its residence time in the atmosphere. Here, the effects of ambient relative humidity (RH) and particle volatility on the heterogeneous OH oxidation of primary BrC were investigated in laboratory experiments. Particles were generated from smoldering pine wood, isolated from gaseous emissions, conditioned at 200 °C in a thermal denuder to remove the most volatile particulate organics, and injected into a smog chamber, where they were conditioned at either 15 or 60% RH and exposed to gas phase OH radicals. Changes in composition were monitored using an aerosol mass spectrometer (AMS), and changes in absorption at 405 nm were monitored using a photoacoustic spectrometer. Heterogeneous OH oxidation of nascent BrC at 60% RH resulted in steady increases in the AMS fraction of CO2+ (associated with carboxylic acids), the O : C ratio, and the carbon oxidation state, consistent with extensive functionalization. These composition changes corresponded first to very rapid absorption enhancement and then bleaching. Net bleaching was observed after the equivalent of 10 h residence time in the atmosphere. The evolution did not depend strongly on RH, consistent with homogeneously well-mixed primary BrC even at 15% RH at room temperature. In contrast, the evolution did depend strongly on the pre-treatment of the particles, such that only bleaching occurred for particles treated at 200 °C. This suggests that lower volatility constituents of ambient primary BrC have less capacity for absorption enhancement in the atmosphere upon heterogeneous oxidation, potentially as they are already more functionalized and/or oligomeric.

Sources of isocyanic acid (HNCO) indoors: a focus on cigarette smoke.

The sources and sinks of isocyanic acid (HNCO), a toxic gas, in indoor environments are largely uncharacterized. In particular, cigarette smoke has been identified as a significant source. In this study, controlled smoking of tobacco cigarettes was investigated in both an environmental chamber and a residence in Toronto, Canada using an acetate-CIMS. The HNCO emission ratio from side-stream cigarette smoke was determined to be 2.7 (±1.1) × 10-3 ppb HNCO/ppb CO. Side-stream smoke from a single cigarette introduced a large pulse of HNCO to the indoor environment, increasing the HNCO mixing ratio by up to a factor of ten from background conditions of 0.15 ppb. Although there was no evidence for photochemical production of HNCO from cigarette smoke in the residence, it was observed in the environmental chamber via oxidation by the hydroxyl radical (1.1 × 107 molecules per cm3), approximately doubling the HNCO mixing ratio after 30 minutes of oxidation. Oxidation of cigarette smoke by O3 (15 ppb = 4.0 × 1017 molecules per cm3) and photo-reaction with indoor fluorescent lights did not produce HNCO. By studying the temporal profiles of both HNCO and CO after smoking, it is inferred that gas-to-surface partitioning of HNCO acts as an indoor loss pathway. Even in the absence of smoking, the indoor HNCO mixing ratios in the Toronto residence were elevated compared to concurrent outdoor measurements by approximately a factor of two.

Evidence for Gas-Surface Equilibrium Control of Indoor Nitrous Acid.

Nitrous acid (HONO) is an important component of indoor air as a photolabile precursor to hydroxyl radicals and has direct health effects. HONO concentrations are typically higher indoors than outdoors, although indoor concentrations have proved challenging to predict using box models. In this study, time-resolved measurements of HONO and NO2 in a residence showed that [HONO] varied relatively weakly over contiguous periods of hours, while [NO2] fluctuated in association with changes in outdoor [NO2]. Perturbation experiments were performed in which indoor HONO was depleted or elevated and were interpreted using a two-compartment box model. To reproduce the measurements, [HONO] had to be predicted using persistent source and sink processes that do not directly involve NO2, suggesting that HONO was in equilibrium with indoor surfaces. Production of gas phase HONO directly from conversion of NO2 on surfaces had a weak influence on indoor [HONO] during the time of the perturbations. Highly similar temporal responses of HONO and semivolatile carboxylic acids to ventilation of the residence along with the detection of nitrite on indoor surfaces support the concept that indoor HONO mixing ratios are controlled strongly by gas-surface equilibrium.

Exploring Conditions for Ultrafine Particle Formation from Oxidation of Cigarette Smoke in Indoor Environments.

Cigarette smoke is an important source of particles and gases in the indoor environment. In this work, aging of side-stream cigarette smoke was studied in an environmental chamber via exposure to ozone (O3), hydroxyl radicals (OH) and indoor fluorescent lights. Aerosol mass concentrations increased by 13-18% upon exposure to 15 ppb O3 and by 8-42% upon exposure to 0.45 ppt OH. Ultrafine particle (UFP) formation was observed during all ozone experiments, regardless of the primary smoke aerosol concentration (185-1950 µg m-3). During OH oxidation, however, UFP formed only when the primary particle concentration was relatively low (<130 µg m-3) and the OH concentration was high (∼1.1 × 107 molecules cm-3). Online aerosol composition measurements show that oxygen- and nitrogen- containing species were formed during oxidation. Gas phase oxidation of NO to NO2 occurred during fluorescent light exposure, but neither primary particle growth nor UFP formation were observed. Overall, exposure of cigarette smoke to ozone will likely lead to UFP formation in indoor environments. On the other hand, UPF formation via OH oxidation will only occur when OH concentrations are high (∼107 molecules cm-3), and is therefore less likely to have an impact on indoor aerosol associated with cigarette smoke.