Formation of secondary inorganic aerosol in a frigid urban atmosphere

Abstract

•Harbin showed relatively high threshold RH (80%) for apparent increase of SOR.

•The observed SOR were at the lower end of the ratios from Beijing’s winter.

•Temperature-dependent increase of NOR was sharper than that of SOR.

• NOR increased with stronger biomass burning impact but SOR was largely unchanged.

Formation of secondary inorganic aerosol (SIA) was investigated during a six-month long heating season in Harbin, China. Enhanced sulfate formation was observed at high relative humidity (RH), with the same threshold RH (80%) for both colder and warmer measurement periods. Compared to wintertime results from Beijing, the threshold RH was considerably higher in Harbin, whereas the RH-dependent enhancement of sulfur oxidation ratio (SOR) was less significant. In addition, the high RH events were rarely encountered, and for other periods, the SOR were typically as low as ~0.1. Therefore, the sulfate formation was considered inefficient in this study. After excluding the several cases with high RH, both SOR and the nitrogen oxidation ratio (NOR) exhibited increasing trends as the temperature increased, with the increase of NOR being sharper. The nitrate to sulfate ratio tended to increase with increasing temperature as well. Based on a semi-quantitative approach, this trend was attributed primarily to the temperature-dependent variations of precursors including SO₂ and NO₂. The influence of biomass burning emissions on SIA formation was also evident. With stronger impact of biomass burning, an enhancement in NOR was observed whereas SOR was largely unchanged. The different patterns were identified as the dominant driver of the larger nitrate to sulfate ratios measured at higher concentrations of fine particulate matter.

Graphical abstract

Keywords

Haze / Sulfate / Nitrate / Heterogeneous chemistry / Biomass burning / Northeast China

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