Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

Enhancements of Major Aerosol Components Due to Additional HONO Sources in the North China Plain and Implications for Visibility and Haze

The Weather Research and Forecasting/Chemistry model(WRF-Chem) was updated by including photoexcited nitrogen dioxide(NO2) molecules,heterogeneous reactions on aerosol surfaces,and direct emissions of nitrous acid(HONO) in the Carbon-Bond Mechanism Z(CBM-Z).Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components.We calculated percentage changes of major aerosol components and concentration ratios of gas NO y(NOyg) to NO y and particulate nitrates(NO-3) to NO y due to the three additional HONO sources in the North China Plain in August of 2007.Our results indicate that when the three additional HONO sources are included,WRF-Chem can reasonably reproduce the HONO observations.Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO,nitrates(NO 3),ammonium(NH + 4),and PM 2.5(concentration of particulate matter of 2.5 μm in the ambient air) across the North China Plain.The three additional HONO sources produced a～5%-20% increase in monthly mean daytime concentration ratios of NO-3 /NO y,a ～15%-52% increase in maximum hourly mean concentration ratios of NO-3 /NO y,and a ～10%-50% increase in monthly mean concentrations of NO-3 and NH+4 across large areas of the North China Plain.For the Bohai Bay,the largest hourly increases of NO-3 exceeded 90%,of NH+4 exceeded 80%,and of PM 2.5 exceeded 40%,due to the three additional HONO sources.This implies that the three additional HONO sources can aggravate regional air pollution,further impair visibility,and enhance the incidence of haze in some industrialized regions with high emissions of NO x and particulate matter under favorable meteorological conditions.     

Atmospheric Measurements of HONO by Tunable Diode Laser Absorption Spectroscopy

Ambient gas phase nitrous acid (HONO) has been measured by Tunable Diode Laser Absorption Spectroscopy with sub-ppbv detection limits. An R-branch line in the 1263.4 cm^–1 ₃ band was found tobe free of interference and suitable for ambient HONO measurements. Nitrous acid was measured during the night and early morning at an urban site in Toronto, Canada, during the summer of 1998. Average mixing ratios, integrated over 30 minutes, ranged from below the minimum detection limit of 300 pptv to 1.9 ppbv, with the highest concentrations observed during the early morning hours. During the night of 19 June 1998, the concentration of HONO increased by as much as 0.5 ppbv/hr. The usual decrease in HONO after sunrise was delayed by a few hours, possibly due to a combination of an increase in the production rate of HONO with rush hour, and attenuation of the early morning light by high NO₂ within the aerosol fog/haze.     

Characteristics of reactive nitrogen compounds and other relevant trace gases in the atmosphere at urban and rural areas of Korea during May–June, 2004

This study examines the general characteristics of reactive nitrogen oxides (NO_y) at urban and rural sites in terms of measurement- and modeling-based analyses. In this field study, NO_x at urban and rural sites were 92 and 89% of NO_y on average, respectively. HONO levels (e.g., 1.8 ppbv) at the urban site were significantly higher than those at the rural site by a factor of 4.5. HONO concentrations at the urban site during the night were clearly higher than those during the day, which were likely to result from heterogeneous reactions on the surfaces of airborne aerosols and/or grounds. In contrast, there were no significant differences of PAN concentrations in either the temporal or spatial distributions. The significantly low ratios of NO_z/NO_y at both sampling sites indicated a more limited chemical aging process in air mass. O₃ levels were weakly related to NO_x oxidation at both sites, especially at the rural site.     

Measurements of the HONO photodissociation constant

Measurements of the photodissociation constant for nitrous acid (j _HONO) were made at an urban site in Toronto, Canada, during the months of May–July 2005, using an optically thin actinometer. Operating details of the j _HONO monitor are reported, along with laboratory tests. Measurements of j _HONO were obtained for solar zenith angles ranging from 20–75^∘, under clear and cloudy skies. Maximum error estimates on j _HONO under clear skies range from 11% at sunrise, to 4% at solar noon, with a minimum detection limit of 5.7 × 10⁻⁴/sec for our actinometer. Measured clear-sky values of j _HONO were compared with values calculated by a four-stream discrete ordinate radiative transfer (RT) model (ACD TUV version 4.1), and were found to be within better than 10% agreement for solar zenith angles < 65^∘. For conditions of scattered cloud, enhancement and suppression of the j _HONO values occurred by as much as 16%–70%, and 59%–80%, respectively. The integrated band area of the nπ^∗ transition for gas-phase nitrous acid yields an oscillator strength, f = (1.06 ± 0.044)×10⁻³ (based on clear-sky data), 19.1% higher than the value reported by Bongartz et al. (1991).     

Effects of additional HONO sources on visibility over the North China Plain

The objective of the present study was to better understand the impacts of the additional sources of nitrous acid （HONO） on visibility, which is an aspect not considered in current air quality models. Simulations of HONO contributions to visibility over the North China Plain （NCP） during August 2007 using the fully coupled Weather Research and Forecasting/Chemistry （WRF/Chem） model were performed, including three additional HONO sources： （1） the reaction of photo-excited nitrogen dioxide （NO~） with water vapor; （2） the NO2 heterogeneous reaction on aerosol surfaces; and （3） HONO emissions. The model generally reproduced the spatial patterns and diurnal variations of visibility over the NCP well. When the additional HONO sources were included in the simulations, the visibility was occasionally decreased by 20%-30% （3-4 km） in local urban areas of the NCP. Monthly-mean concentrations of NO3, NH＋, SO]- and PM2.5 were increased by 20%-52% （3-11μg m-3）, 10%-38%, 6%-10%, and 6%-11% （9-17 μg m-3）, respectively; and in urban areas, monthly-mean accumulation- mode number concentrations （AMNC） and surface concentrations of aerosols were enhanced by 15%-20% and 10%-20%, respectively. Overall, the results suggest that increases in concentrations of PM2.5, its hydrophilic components, and AMNC, are key factors for visibility degradation. A proposed conceptual model for the impacts of additional HONO sources on visibility also suggests that visibility estimation should consider the heterogeneous reaction on aerosol surfaces and the enhanced atmospheric oxidation capacity due to additional HONO sources, especially in areas with high mass concentrations of NOx and aerosols.