Four years of ground-based MAX-DOAS observations of HONO and NO₂ in the Beijing area

Abstract. Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO₂ (nitrogen dioxide) as well as aerosols have been performed daily in Beijing city centre (39.98° N, 116.38° E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75° N, 116.96° E) located ~60 km east of Beijing from March 2010 to December 2012. This extensive dataset allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO₂ near-surface concentrations (0–200 m layer) and total vertical column densities (VCDs) and also aerosol optical depths (AODs) and extinction coefficients retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (~0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (~0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO₂ appear to be highly correlated, with correlation coefficients in the 0.7–0.9 and 0.5–0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO₂ and also with aerosols observed in Beijing suggests possibly larger role of NO₂ conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1–0.4 ppb around local noon. The HONO / NO₂ ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ~0.01–0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely driven mainly by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O₃ photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that in the 0–200 m altitude range, HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O₃ dominates in summer from mid-morning until mid-afternoon.