Seasonal variations of C-1-C-4 alkyl nitrates at a coastal site in Hong Kong: Influence of photochemical formation and oceanic emissions

Five C-1-C-4 alkyl nitrates (RONO2) were measured at a coastal site in Hong Kong in four selected months of 2011 and 2012. The total mixing ratios of C-1-C-4 RONO2 (Sigma 5RONO2) ranged from 15.4 to 143.7 pptv with an average of 65.9 +/- 33.0 pptv. C-3-C-4 RONO2 (2-butyl nitrate and 2-propyl nitrate) were the most abundant RONO2 during the entire sampling period. The mixing ratios of C-3-C-4 RONO2 were higher in winter than those in summer, while the ones of methyl nitrate (MeONO2) were higher in summer than those in winter. Source analysis suggests that C-2-C-4 RONO2 were mainly derived from photochemical formation along with biomass burning (58.3-71.6%), while ocean was a major contributor to MeONO2 (53.8%) during the whole sampling period. The photochemical evolution of C-2-C-4 RONO2 was investigated, and found to be dominantly produced by the parent hydrocarbon oxidation. The notable enrichment of MeONO2 over C-3-C-4 RONO2 was observed in a summer episode when the air masses originating from the South China Sea (SCS) and MeONO2 was dominantly derived from oceanic emissions. In order to improve the accuracy of ozone (O-3) prediction in coastal environment, the relative contribution of RONO2 from oceanic emissions versus photochemical formation and their coupling effects on O-3 production should be taken into account in future studies. (C) 2017 Elsevier Ltd. All rights reserved