title: Uptake of gas phase nitrous acid onto boundary layer soil surfaces.
abstract: Nitrous acid (HONO) is an important OH radical source that is formed on both ground and aerosol surfaces in the well-mixed boundary layer. Large uncertainties remain in quantifying HONO sinks and determining the mechanism of HONO uptake onto surfaces. We report here the first laboratory determination of HONO uptake coefficients onto actual soil under atmospheric conditions using a coated-wall flow tube coupled to a highly sensitive chemical ionization mass spectrometer (CIMS). Uptake coefficients for HONO decrease with increasing RH from (2.5 ± 0.4) × 10(-4) at 0% RH to (1.1 ± 0.4) × 10(-5) at 80% RH. A kinetics model of competitive adsorption of HONO and water onto the particle surfaces fits the dependence of the HONO uptake coefficients on the initial HONO concentration and relative humidity. However, a multiphase resistor model based on the physical and chemical processes affecting HONO uptake is more flexible as it accounts for the pH dependence of HONO uptake and bulk diffusion in the soil matrix. Fourier transform infrared (FTIR) spectrometry and cavity-enhanced absorption spectroscopy (CEAS) studies indicate that NO and N2O (16% and 13% yield, respectively) rather than NO2 are the predominant gas phase products, while NO2(-) and NO3(-) were detected on the surface post-exposure. Results are compared to uptake coefficients inferred from models and field measurements, and the atmospheric implications are discussed.
authors: School of Public and Environmental Affairs and Department of Chemistry, Indiana University , Bloomington, Indiana 47405-2204, United States.
authors: Melissa A
authors: MA
authors: Donaldson
authors: Andrew E
authors: AE
authors: Berke
authors: Jonathan D
authors: JD
authors: Raff
mesh_terms: D000327:Adsorption; D005740:Gases / Q000737:chemistry; D007700:Kinetics; D009566:Nitrates / Q000737:chemistry; D009569:Nitric Oxide / Q000737:chemistry; D009573:Nitrites / Q000737:chemistry; D009608:Nitrous Acid / Q000737:chemistry*; D012987:Soil / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D005740:Gases; D009566:Nitrates; D009573:Nitrites; D012987:Soil; D014867:Water; D009569:Nitric Oxide; D009608:Nitrous Acid