Kinetics of hypochlorous acid reactions with organic and chloride-containing tropospheric aerosol.

Chlorine plays an important role in tropospheric oxidation processes, in both marine and continental environments. Although modeling studies have explored the importance of halogen chemistry, uncertainty remains in associated chemical mechanisms and fundamental kinetics parameters. Prior kinetics measurements of multiphase halogen recycling reactions have been largely performed with dilute, bulk solutions, leaving unexplored more realistic chemical systems which have high solute concentrations and are internally mixed with both halide and organic components. Here, we address the multiphase kinetics of gaseous HOCl using an aerosol flow tube and aerosol mass spectrometer to study its reactions with particulate chloride, using atmospherically relevant particle acidity, solute concentrations, and ionic strength. We also investigate the chemistry that results when biomass burning (BB) aerosol components and chloride are internally mixed. Using pH-buffered deliquesced particles, we show that the rate constant for reaction of dissolved HOCl with H+ and Cl- at high relative humidity (RH) (80-85%) is within a factor of two of the literature value for bulk phase conditions. However, at lower RH values (60-70%) where the particles are considerably more concentrated, the rate constant for chloride loss from the particles is an order of magnitude higher. For pure organic compounds commonly found in biomass burning (BB) aerosol, such as coniferaldehyde, salicylic acid and furfural, an increase in the aerosol chlorine content occurs with HOCl exposure, indicating the formation of organochlorine species. Together, these independent findings explain results for internally mixed aerosol particles with both chloride and BB components present where we observed behavior consistent with both chloride loss and organochlorine formation occurring simultaneously upon HOCl exposure. Our results indicate that chlorine recycling via HOCl uptake by chloride-containing particles will occur in the atmosphere efficiently over a wide range of RH conditions, even when reactive organic compounds are present in the same particles as chloride. Simultaneously, formation of organochlorine compounds, which are commonly toxic, is likely occurring when reactive organic components are present.

Reaction of HOCl with Wood Smoke Aerosol: Impacts on Indoor Air Quality and Outdoor Reactive Chlorine.

High loadings of biomass burning (BB) aerosol particles from wildfire or residential heating sources can be present in both outdoor and indoor environments, where they deposit onto surfaces such as walls and furniture. These pollutants can interact with oxidants in both the aerosol and deposited forms. Hypochlorous acid (HOCl), a strong oxidant emitted during cleaning with chlorine-cleaning agents such as bleach, can attain mixing ratios of hundreds of ppbv indoors; moreover, lower mixing ratios are naturally present outdoors. Here, we report the heterogeneous reactivity of HOCl with wood smoke aerosol particles. After exposure to gas-phase HOCl, the particle chlorine content increased reaching chlorine-to-organic mass ratios of 0.07 with the chlorine covalently bound as organochlorine species, many of which are aromatic. Investigating individual potential BB components, we observed that unsaturated species such as coniferaldehyde and furfural react efficiently with HOCl. These observations indicate that organochlorine pollutants will form indoors when bleach cleaning a wildfire impacted space. The chlorine component of particles internally mixed with BB material and chloride initially increased, upon HOCl exposure, indicating that active chlorine recycling in the outdoor environment will be suppressed in the presence of BB emissions.

Measurement of Formation Rates of Secondary Aerosol in the Ambient Urban Atmosphere Using a Dual Smog Chamber System.

A dual smog chamber system was used to quantify the formation rates of secondary organic and inorganic aerosol in an urban environment (Pittsburgh, US). Ambient air was introduced in both chambers, and HONO photolysis was used to produce hydroxyl radicals (OH) in the perturbed chamber. The second chamber was used as a reference. The production rate of secondary organic aerosol (SOA) under typical noon-time OH concentrations ranged from 0.2 to 0.8 µg m-3 h-1. The production rate of sulfate was approximately five times less than that of the SOA. Nucleation and growth of new particles were observed in the perturbation chamber. The produced SOA had a similar composition with the preexisting oxygenated ambient OA. The reacted amounts of the measured VOCs were able to explain 5-50% of the formed SOA in the perturbed chamber. Intermediate volatility organic compounds could be responsible for the rest. The oxygen to carbon ratio (O:C) in the perturbed chamber remained approximately the same during SOA production, while an increase was observed in the control chamber. A possible explanation could be the loss of less oxidized species to the chamber walls. After 2 h, the OA increased by 70% on average and the sulfate by 40%.