Yee Jun Tham

Observations of Nitryl Chloride and Modeling its Source and Effect on Ozone in the Planetary Boundary Layer of Southern China

Nitryl chloride (ClNO2) plays potentially important roles in atmospheric chemistry, but its abundance and effect are not fully understood due to the small number of ambient observations of ClNO2 to date. In late autumn 2013, ClNO2 was measured with a chemical ionization mass spectrometer (CIMS) at a mountain top (957 m above sea level) in Hong Kong. During 12 nights with continuous CIMS data, elevated mixing ratios of ClNO2 (>400 parts per trillion by volume) or its precursor N2O5 (>1000 pptv) were observed on six nights, with the highest ever reported ClNO2 (4.7 ppbv, 1 min average) and N2O5 (7.7 ppbv, 1 min average) in one case. Backward particle dispersion calculations driven by winds simulated with a mesoscale meteorological model show that the ClNO2/N2O5-laden air at the high-elevation site was due to transport of urban/industrial pollution north of the site. The highest ClNO2/N2O5 case was observed in a later period of the night and was characterized with extensively processed air and with the presence of nonoceanic chloride. A chemical box model with detailed chlorine chemistry was used to assess the possible impact of the ClNO2 in the well-processed regional plume on next day ozone, as the air mass continued to downwind locations. The results show that the ClNO2 could enhance ozone by 5–16% at the ozone peak or 11–41% daytime ozone production in the following day. This study highlights varying importance of the ClNO2 chemistry in polluted environments and the need to consider this process in photochemical models for prediction of ground-level ozone and haze.

Nighttime chemistry at a high altitude site above Hong Kong

Nighttime reactions of nitrogen oxides influence ozone, volatile organic compounds, and aerosol and are thus important to the understanding of regional air quality. Despite large emissions and rapid recent growth of nitrogen oxide concentrations, there are few studies of nighttime chemistry in China. Here we present measurements of nighttime nitrogen oxides, NO3 and N2O5, from a coastal mountaintop site in Hong Kong adjacent to the megacities of the Pearl River Delta region. This is the first study of nighttime chemistry from a site within the residual layer in China. Key findings include the following. First, highly concentrated urban NOx outflow from the Pearl River Delta region was sampled infrequently at night, with N2O5 mixing ratios up to 8 ppbv (1 min average) or 12 ppbv (1 s average) in nighttime aged air masses. Second, the average N2O5 uptake coefficient was determined from a best fit to the available steady state lifetime data as γ(N2O5) = 0.014 ± 0.007. Although this determination is uncertain due to the difficulty of separating N2O5 losses from those of NO3, this value is in the range of previous residual layer determinations of N2O5 uptake coefficients in polluted air in North America. Third, there was a significant contribution of biogenic hydrocarbons to NO3 loss inferred from canister samples taken during daytime. Finally, daytime N2O5 mixing ratios were in accord with their predicted photochemical steady state. Heterogeneous uptake of N2O5 in fog is determined to be an important production mechanism for soluble nitrate, even during daytime.

Oxidizing capacity of the rural atmosphere in Hong Kong, Southern China

Atmospheric oxidizing capacity (AOC), dominated by the hydroxyl radical (OH), is an important index of the self-cleaning capacity of atmosphere and plays a vital role in the tropospheric chemistry. To better understand the key processes governing the chemistry of rural atmosphere of southern China, we analyzed the oxidation capacity and radical chemistry at a regional background site in Hong Kong from 23 August to 22 December 2012, which covered the summer, autumn and winter seasons. A chemical box model built on the latest Master Chemical Mechanism (v3.3) was used to elucidate the OH reactivity and sources of ROX radicals (ROX=OH+HO2+RO2). The AOC showed a clear seasonal pattern with stronger intensity in late summer compared to autumn and winter. Reactions with NO2 (30%) and oxygenated volatile organic compounds (OVOCs) (31%) together dominated the OH loss in summer, while reactions with CO (38% in autumn and 39% in winter) and OVOCs (34% in autumn and 25% in winter) made larger contributions in autumn and winter. Photolysis of O3 (36%-47%) presented the major ROX source during all three seasons. The second largest ROx source was HONO photolysis (25%) in summer compared to HCHO photolysis in autumn (20%) and winter (21%). Besides, photolysis of other OVOCs was another important primary source of ROx radicals with average contributions of 14%, 13% and 20% for the summer, autumn and winter cases, respectively. Overall, the present study evaluates the oxidizing capacity of the rural atmosphere of South China and elucidates the varying characteristics of photochemical processes in different air masses.

Nighttime NO x loss and ClNO 2 formation in the residual layer of a polluted region: Insights from field measurements and an iterative box model

The heterogeneous reaction of dinitrogen pentoxide (N2O5) on aerosols is an important sink of nitrogen oxides (NOx) in the polluted boundary layer, and the production of nitryl chloride (ClNO2) can have significant effects on the atmospheric oxidative capacity. However, the heterogeneous loss of N2O5 and the formation of ClNO2 are still not well quantified, especially in China. In a previous study, we measured ClNO2 and N2O5 concentrations in several air masses at a high-elevation site in Hong Kong, and found the highest levels ever reported at one night. The present study employed an iterative box model to investigate five N2O5/ClNO2-laden nights. We first estimated the N2O5 uptake coefficient and ClNO2 yield and then calculated the relative importance of N2O5 heterogeneous reactions to NOx loss and the accumulated ClNO2 production over the entire night. The average uptake coefficient was 0.004±0.003, and the average yield was 0.42±0.26. As the air masses aged, the accumulated ClNO2 reached up to 6.0ppbv, indicating significant production of ClNO2 in the polluted air from the Pearl River Delta. ClNO2 formation (N2O5+Cl-), N2O5 hydrolysis (N2O5+H2O), and NO3 reactions with volatile organic compounds (NO3+VOCs) consumed 23%, 27%, and 47% of the produced NO3, respectively, as the average for five nights. A significant portion of the NOx in the air masses (70%±10%) was removed during the night via NO3 reactions with VOCs (~40%) and N2O5 heterogeneous loss (~60%).

Heterogeneous N 2 O 5 uptake coefficient and production yield of ClNO 2 in polluted northern China: Roles of aerosol water content and chemical composition

Heterogeneous uptake of dinitrogen pentoxide (N2O5) and production of nitryl chloride (ClNO2) are important nocturnal atmospheric processes that have significant implications for the production of secondary pollutants. However, the understanding of N2O5 uptake processes and ClNO2 production remains limited, especially in China. This study presents a field investigation of the N2O5 heterogeneous uptake coefficient (γ (N2O5)) and ClNO2 production yield (φ) in a polluted area of northern China during the summer of 2014. The N2O5 uptake coefficient and ClNO2 yield were estimated by using the simultaneously measured ClNO2 and total nitrate in 10 selected cases, which have concurrent increases in the ClNO2 and nitrate concentrations and relatively stable environmental conditions. The determined γ (N2O5) and φ values varied greatly, with an average of 0.022 for γ (N2O5) (±0.012, standard deviation) and 0.34 for φ (±0.28, standard deviation). The variations in γ (N2O5) could not be fully explained by the previously derived parameterizations of N2O5 uptake that consider nitrate, chloride, and the organic coating. Heterogeneous uptake of N2O5 was found to have a strong positive dependence on the relative humidity and aerosol water content. This result suggests that the heterogeneous uptake of N2O5 in Wangdu is governed mainly by the amount of water in the aerosol, and is strongly water limited, which is different from most of the field observations in the US and Europe. The ClNO2 yield estimated from the parameterization was also overestimated comparing to that derived from the observation. The observation-derived φ showed a decreasing trend with an increasing ratio of acetonitrile to carbon monoxide, an indicator of biomass burning emissions, which suggests a possible suppressive effect on the production yield of ClNO2 in the plumes influenced by biomass burning in this region. The findings of this study illustrate the need to improve our understanding and to parameterize the key factors for γ (N2O5) and φ to accurately assess photochemical and haze pollution.