Formation of secondary inorganic aerosol in a frigid urban atmosphere

Highlights

•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.

Abstract

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

References

[1] Akagi S K, Craven J S, Taylor J W, McMeeking G R, Yokelson R J, Burling I R, Urbanski S P, Wold C E, Seinfeld J H, Coe H, Alvarado M J, Weise D R (2012). Evolution of trace gases and particles emitted by a chaparral fire in California. Atmospheric Chemistry and Physics, 12(3): 1397–1421

[2] Cao J J, Xu H M, Xu Q, Chen B H, Kan H D (2012). Fine particulate matter constituents and cardiopulmonary mortality in a heavily polluted Chinese city. Environmental Health Perspectives, 120(3): 373–378

[3] Chen X R, Wang H C, Lu K D, Li C M, Zhai T Y, Tan Z F, Ma X F, Yang X P, Liu Y H, Chen S Y, Dong H B, Li X, Wu Z J, Hu M, Zeng L M, Zhang Y H (2020). Field determination of nitrate formation pathway in winter Beijing. Environmental Science & Technology, 54(15): 9243–9253

[4] Cheng Y, Yu Q Q, Liu J M, Du Z Y, Liang L L, Geng G N, Ma W L, Qi H, Zhang Q, He K B (2020). Secondary inorganic aerosol during heating season in a megacity in Northeast China: Evidence for heterogeneous chemistry in severe cold climate region. Chemosphere, 261: 127769

[5] Cheng Y F, Zheng G J, Wei C, Mu Q, Zheng B, Wang Z B, Gao M, Zhang Q, He K B, Carmichael G, Pöschl U, Su H (2016). Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China. Science Advances, 2(12): e1601530

[6] Chu B W, Ma Q X, Duan F K, Ma J Z, Jiang J K, He K B, He H (2020). Atmospheric “haze chemistry”: Concept and research prospects. Progress in Chemistry, 32(1): 1–4

[7] Collier S, Zhou S, Onasch T B, Jaffe D A, Kleinman L, Sedlacek A J III, Briggs N L, Hee J, Fortner E, Shilling J E, Worsnop D, Yokelson R J, Parworth C, Ge X L, Xu J Z, Butterfield Z, Chand D, Dubey M K, Pekour M S, Springston S, Zhang Q (2016). Regional influence of aerosol emissions from wildfires driven by combustion efficiency: insights from the BBOP campaign. Environmental Science & Technology, 50(16): 8613–8622

[8] Dao X, Lin Y C, Cao F, Di S Y, Hong Y H, Xing G H, Li J J, Fu P Q, Zhang Y L (2019). Introduction to the national aerosol chemical composition monitoring network of China: Objectives, current status, and outlook. Bulletin of the American Meteorological Society, 100(12): ES337–ES351

[9] Du Z Y, He K B, Cheng Y, Duan F K, Ma Y L, Liu J M, Zhang X L, Zheng M, Weber R J (2014). A yearlong study of water-soluble organic carbon in Beijing I: Sources and its primary vs. secondary nature. Atmospheric Environment, 92: 514–521

[10] Gen M S, Zhang R F, Huang D D, Li Y J, Chan C K (2019). Heterogeneous oxidation of SO₂ in sulfate production during nitrate photolysis at 300 nm: Effect of pH, relative humidity, irradiation intensity, and the presence of organic compounds. Environmental Science & Technology, 53(15): 8757–8766

[11] Li H Y, Cheng J, Zhang Q, Zheng B, Zhang Y X, Zheng G J, He K B (2019a). Rapid transition in winter aerosol composition in Beijing from 2014 to 2017: Response to clean air actions. Atmospheric Chemistry and Physics, 19(17): 11485–11499

[12] Li Y C, Liu J, Han H, Zhao T L, Zhang X, Zhuang B L, Wang T J, Chen H M, Wu Y, Li M M (2019b). Collective impacts of biomass burning and synoptic weather on surface PM_2.5 and CO in Northeast China. Atmospheric Environment, 213: 64–80

[13] Liu J M, Wang P F, Zhang H L, Du Z Y, Zheng B, Yu Q Q, Zheng G J, Ma Y L, Zheng M, Cheng Y, Zhang Q, He K B (2020a). Integration of field observation and air quality modeling to characterize Beijing aerosol in different seasons. Chemosphere, 242: 125195

[14] Liu M X, Song Y, Zhou T, Xu Z Y, Yan C Q, Zheng M, Wu Z J, Hu M, Wu Y S, Zhu T (2017). Fine particle pH during severe haze episodes in northern China. Geophysical Research Letters, 44(10): 5213–5221

[15] Liu P F, Ye C, Xue C Y, Zhang C L, Mu Y J, Sun X (2020b). Formation mechanisms of atmospheric nitrate and sulfate during the winter haze pollution periods in Beijing: Gas-phase, heterogeneous and aqueous-phase chemistry. Atmospheric Chemistry and Physics, 20(7): 4153–4165

[16] Liu X X, Zhang Y, Huey L G, Yokelson R J, Wang Y, Jimenez J L, Campuzano-Jost P, Beyersdorf A J, Blake D R, Choi Y, St Clair J M, Crounse J D, Day D A, Diskin G S, Fried A, Hall S R, Hanisco T F, King L E, Meinardi S, Mikoviny T, Palm B B, Peischl J, Perring A E, Pollack I B, Ryerson T B, Sachse G, Schwarz J P, Simpson I J, Tanner D J, Thornhill K L, Ullmann K, Weber R J, Wennberg P O, Wisthaler A, Wolfe G M, Ziemba L D (2016). Agricultural fires in the southeastern U.S. during SEAC⁴RS: Emissions of trace gases and particles and evolution of ozone, reactive nitrogen, and organic aerosol. Journal of Geophysical Research: Atmospheres, 121(12): 7383–7414

[17] Ming L L, Jin L, Li J, Fu P Q, Yang W Y, Liu D, Zhang G, Wang Z F, Li X D (2017). PM_2.5 in the Yangtze River Delta, China: Chemical compositions, seasonal variations, and regional pollution events. Environmental Pollution, 223: 200–212

[18] Morgan W T, Allan J D, Bauguitte S, Darbyshire E, Flynn M J, Lee J, Liu D T, Johnson B, Haywood J, Longo K M, Artaxo P E, Coe H (2020). Transformation and aging of biomass burning carbonaceous aerosol over tropical South America from aircraft in-situ measurements during SAMBBA. Atmospheric Chemistry and Physics, 20(9): 5309–5326

[19] Myhre G, Samset B H, Schulz M, Balkanski Y, Bauer S, Berntsen T K, Bian H, Bellouin N, Chin M, Diehl T, Easter R C, Feichter J, Ghan S J, Hauglustaine D, Iversen T, Kinne S, Kirkevåg A, Lamarque J F, Lin G, Liu X, Lund M T, Luo G, Ma X, van Noije T, Penner J E, Rasch P J, Ruiz A, Seland Ø, Skeie R B, Stier P, Takemura T, Tsigaridis K, Wang P, Wang Z, Xu L, Yu H, Yu F, Yoon J H, Zhang K, Zhang H, Zhou C (2013). Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations. Atmospheric Chemistry and Physics, 13(4): 1853–1877

[20] National Bureau of Statistics of China (2019). China Statistical Yearbook. Beijing: China Statistics Press

[21] Orlando J J, Tyndall G S (2012). Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance. Chemical Society Reviews, 41(19): 6294–6317

[22] Sun Y L, Wang Z F, Fu P Q, Jiang Q, Yang T, Li J, Ge X L (2013). The impact of relative humidity on aerosol composition and evolution processes during wintertime in Beijing, China. Atmospheric Environment, 77: 927–934

[23] Wang G H, Zhang R Y, Gomez M E, Yang L X, Zamora M L, Hu M, Lin Y, Peng J F, Guo S, Meng J J, Li J J, Cheng C L, Hu T F, Ren Y Q, Wang Y S, Gao J, Cao J J, An Z S, Zhou W J, Li G H, Wang J Y, Tian P F, Marrero-Ortiz W, Secrest J, Du Z F, Zheng J, Shang D J, Zeng L M, Shao M, Wang W G, Huang Y, Wang Y, Zhu Y J, Li Y X, Hu J X, Pan B W, Cai L, Cheng Y T, Ji Y M, Zhang F, Rosenfeld D, Liss P S, Duce R A, Kolb C E, Molina M J (2016). Persistent sulfate formation from London Fog to Chinese haze. Proceedings of the National Academy of Sciences of the United States of America, 113(48): 13630–13635

[24] Wang J F, Li J Y, Ye J H, Zhao J, Wu Y Z, Hu J L, Liu D T, Nie D Y, Shen F Z, Huang X P, Huang D D, Ji D S, Sun X, Xu W Q, Guo J P, Song S J, Qin Y M, Liu P F, Turner J R, Lee H C, Hwang S, Liao H, Martin S T, Zhang Q, Chen M D, Sun Y L, Ge X L, Jacob D J (2020a). Fast sulfate formation from oxidation of SO₂ by NO₂ and HONO observed in Beijing haze. Nature Communications, 11(1): 2844

[25] Wang X K, Gemayel R, Hayeck N, Perrier S, Charbonnel N, Xu C H, Chen H, Zhu C, Zhang L W, Wang L, Nizkorodov S A, Wang X M, Wang Z, Wang T, Mellouki A, Riva M, Chen J M, George C (2020b). Atmospheric photosensitization: A new pathway for sulfate formation. Environmental Science & Technology, 54(6): 3114–3120

[26] Weber R J, Guo H Y, Russell A G, Nenes A (2016). High aerosol acidity despite declining atmospheric sulfate concentrations over the past 15 years. Nature Geoscience, 9(4): 282–285

[27] Ye C, Liu P F, Ma Z B, Xue C Y, Zhang C L, Zhang Y Y, Liu J F, Liu C T, Sun X, Mu Y J (2018). High H₂O₂ concentrations observed during haze periods during the winter in Beijing: importance of H₂O₂ oxidation in sulfate formation. Environmental Science & Technology Letters, 5(12): 757–763

[28] Yin S, Wang X F, Zhang X R, Zhang Z X, Xiao Y, Tani H, Sun Z Y (2019). Exploring the effects of crop residue burning on local haze pollution in Northeast China using ground and satellite data. Atmospheric Environment, 199: 189–201

[29] Yokelson R J, Crounse J D, DeCarlo P F, Karl T, Urbanski S, Atlas E, Campos T, Shinozuka Y, Kapustin V, Clarke A D, Weinheimer A, Knapp D J, Montzka D D, Holloway J, Weibring P, Flocke F, Zheng W, Toohey D, Wennberg P O, Wiedinmyer C, Mauldin L, Fried A, Richter D, Walega J, Jimenez J L, Adachi K, Buseck P R, Hall S R, Shetter R (2009). Emissions from biomass burning in the Yucatan. Atmospheric Chemistry and Physics, 9(15): 5785–5812

[30] Zhang Q, Jimenez J L, Canagaratna M R, Allan J D, Coe H, Ulbrich I, Alfarra M R, Takami A, Middlebrook A M, Sun Y L, Dzepina K, Dunlea E, Docherty K, DeCarlo P F, Salcedo D, Onasch T, Jayne J T, Miyoshi T, Shimono A, Hatakeyama S, Takegawa N, Kondo Y, Schneider J, Drewnick F, Borrmann S, Weimer S, Demerjian K, Williams P, Bower K, Bahreini R, Cottrell L, Griffin R J, Rautiainen J, Sun J Y, Zhang Y M, Worsnop D R (2007). Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes. Geophysical Research Letters, 34(13): L13801

[31] Zhang R, Sun X S, Shi A J, Huang Y H, Yan J, Nie T, Yan X, Li X (2018). Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing, China. Atmospheric Environment, 177: 275–282

[32] Zheng B, Tong D, Li M, Liu F, Hong C P, Geng G N, Li H Y, Li X, Peng L Q, Qi J, Yan L, Zhang Y X, Zhao H Y, Zheng Y X, He K B, Zhang Q (2018). Trends in China’s anthropogenic emissions since 2010 as the consequence of clean air actions. Atmospheric Chemistry and Physics, 18(19): 14095–14111

[33] Zheng G J, Duan F K, Su H, Ma Y L, Cheng Y, Zheng B, Zhang Q, Huang T, Kimoto T, Chang D, Pöschl U, Cheng Y F, He K B (2015). Exploring the severe winter haze in Beijing: The impact of synoptic weather, regional transport and heterogeneous reactions. Atmospheric Chemistry and Physics, 15(6): 2969–2983

[34] Zheng G J, Su H, Wang S W, Andreae M O, Pöschl U, Cheng Y F (2020). Multiphase buffer theory explains contrasts in atmospheric aerosol acidity. Science, 369(6509): 1374–1377

[35] Zhou S, Collier S, Jaffe D A, Briggs N L, Hee J, Sedlacek A J III, Kleinman L, Onasch T B, Zhang Q (2017). Regional influence of wildfires on aerosol chemistry in the western US and insights into atmospheric aging of biomass burning organic aerosol. Atmospheric Chemistry and Physics, 17(3): 2477–2493

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 41805097), the Natural Science Foundation of Heilongjiang Province (No. YQ2019D004), the State Key Laboratory of Urban Water Resource and Environment (No. ES202006), the State Key Joint Laboratory of Environment Simulation and Pollution Control (No. 19K02ESPCT), the State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex (No. SCAPC202002) and Heilongjiang Touyan Team. The authors would like to thank Laura E. King for proofreading the paper.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-021-1452-0 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2022 Higher Education Press