New insight into the spatiotemporal variability and source apportionments of C1–C4 alkyl nitrates in Hong Kong

Alkyl nitrates (RONO2) were measured concurrently at a mountain site (TMS) and an urban site (TW) at the foot of the same mountain in Hong Kong from September to November 2010, when high O3 mixing ratios were frequently observed. The abundance and temporal patterns of five C1–C4 RONO2 and their parent hydrocarbons (RH), the RONO2/RH ratios and photochemical age of air masses at TMS differed from those at TW, reflecting different contributions of direct emissions and secondary formation of RONO2 at the two sites. Relative to 2-BuONO2/n-butane, the measured ratios of C1–C2 RONO2/RH at the two sites exhibited significant positive deviations from pure photochemical (PP) curves and background initial ratio (BIR) curves obtained from laboratory kinetic data, suggesting that background mixing ratios had a significant influence on the RONO2 and RH distributions. In contrast to the C1–C2 RONO2/RH ratios, the evolution for the measured ratios of C3 RONO2/RH to 2-BuONO2/n-butane agreed well with the ratio distributions in the PP and BIR curves at the two sites. Furthermore, the ratios of 1-/2-PrONO2 and yields of 1- and 2-PrONO2 suggested that the C3 RONO2 were mainly from secondary formation at TMS, whereas secondary formation and other additional sources had a significant influence on C3 RONO2 mixing ratios at TW. The source apportionment results confirmed that secondary formation was the dominant contributor to all the RONO2 at TMS, while most of the RONO2 at TW were from secondary formation and biomass burning. The findings of the source apportionments and photochemical evolution of RONO2 are helpful to evaluate photochemical processing in Hong Kong using RONO2 as an indicator.