1. State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China 2. Key Laboratory of Environmental Optics and Technology, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China 3. State Key Laboratory of Severe Weather & CMA Key Laboratory of Atmospheric Chemistry, Chinese Academy of Meteorological Sciences, Beijing 100081, China 4. National Research Center for Environmental Analysis and Measurement, Environmental Development Center of the Ministry of Ecology and Environment, Beijing 100029, China 5. State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China 6. Department of Earth System Science, Tsinghua University, Beijing 100084, China
•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.
S K Akagi, J S Craven, J W Taylor, G R McMeeking, R J Yokelson, I R Burling, S P Urbanski, C E Wold, J H Seinfeld, H Coe, M J Alvarado, D R Weise (2012). Evolution of trace gases and particles emitted by a chaparral fire in California. Atmospheric Chemistry and Physics, 12(3): 1397–1421 https://doi.org/10.5194/acp-12-1397-2012
2
J J Cao, H M Xu, Q Xu, B H Chen, H D Kan (2012). Fine particulate matter constituents and cardiopulmonary mortality in a heavily polluted Chinese city. Environmental Health Perspectives, 120(3): 373–378 https://doi.org/10.1289/ehp.1103671
3
X R Chen, H C Wang, K D Lu, C M Li, T Y Zhai, Z F Tan, X F Ma, X P Yang, Y H Liu, S Y Chen, H B Dong, X Li, Z J Wu, M Hu, L M Zeng, Y H Zhang (2020). Field determination of nitrate formation pathway in winter Beijing. Environmental Science & Technology, 54(15): 9243–9253 https://doi.org/10.1021/acs.est.0c00972
4
Y Cheng, Q Q Yu, J M Liu, Z Y Du, L L Liang, G N Geng, W L Ma, H Qi, Q Zhang, K B He (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 https://doi.org/10.1016/j.chemosphere.2020.127769
5
Y F Cheng, G J Zheng, C Wei, Q Mu, B Zheng, Z B Wang, M Gao, Q Zhang, K B He, G Carmichael, U Pöschl, H Su (2016). Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China. Science Advances, 2(12): e1601530 https://doi.org/10.1126/sciadv.1601530
6
B W Chu, Q X Ma, F K Duan, J Z Ma, J K Jiang, K B He, H He (2020). Atmospheric “haze chemistry”: Concept and research prospects. Progress in Chemistry, 32(1): 1–4
7
S Collier, S Zhou, T B Onasch, D A Jaffe, L Kleinman, A J Sedlacek III, N L Briggs, J Hee, E Fortner, J E Shilling, D Worsnop, R J Yokelson, C Parworth, X L Ge, J Z Xu, Z Butterfield, D Chand, M K Dubey, M S Pekour, S Springston, Q Zhang (2016). Regional influence of aerosol emissions from wildfires driven by combustion efficiency: insights from the BBOP campaign. Environmental Science & Technology, 50(16): 8613–8622 https://doi.org/10.1021/acs.est.6b01617
8
X Dao, Y C Lin, F Cao, S Y Di, Y H Hong, G H Xing, J J Li, P Q Fu, Y L Zhang (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 https://doi.org/10.1175/BAMS-D-18-0325.1
9
Z Y Du, K B He, Y Cheng, F K Duan, Y L Ma, J M Liu, X L Zhang, M Zheng, R J Weber (2014). A yearlong study of water-soluble organic carbon in Beijing I: Sources and its primary vs. secondary nature. Atmospheric Environment, 92: 514–521 https://doi.org/10.1016/j.atmosenv.2014.04.060
10
M S Gen, R F Zhang, D D Huang, Y J Li, C K Chan (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 https://doi.org/10.1021/acs.est.9b01623
11
H Y Li, J Cheng, Q Zhang, B Zheng, Y X Zhang, G J Zheng, K B He (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 https://doi.org/10.5194/acp-19-11485-2019
12
Y C Li, J Liu, H Han, T L Zhao, X Zhang, B L Zhuang, T J Wang, H M Chen, Y Wu, M M Li (2019b). Collective impacts of biomass burning and synoptic weather on surface PM2.5 and CO in Northeast China. Atmospheric Environment, 213: 64–80 https://doi.org/10.1016/j.atmosenv.2019.05.062
13
J M Liu, P F Wang, H L Zhang, Z Y Du, B Zheng, Q Q Yu, G J Zheng, Y L Ma, M Zheng, Y Cheng, Q Zhang, K B He (2020a). Integration of field observation and air quality modeling to characterize Beijing aerosol in different seasons. Chemosphere, 242: 125195 https://doi.org/10.1016/j.chemosphere.2019.125195
14
M X Liu, Y Song, T Zhou, Z Y Xu, C Q Yan, M Zheng, Z J Wu, M Hu, Y S Wu, T Zhu (2017). Fine particle pH during severe haze episodes in northern China. Geophysical Research Letters, 44(10): 5213–5221 https://doi.org/10.1002/2017GL073210
15
P F Liu, C Ye, C Y Xue, C L Zhang, Y J Mu, X Sun (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 https://doi.org/10.5194/acp-20-4153-2020
16
X X Liu, Y Zhang, L G Huey, R J Yokelson, Y Wang, J L Jimenez, P Campuzano-Jost, A J Beyersdorf, D R Blake, Y Choi, J M St Clair, J D Crounse, D A Day, G S Diskin, A Fried, S R Hall, T F Hanisco, L E King, S Meinardi, T Mikoviny, B B Palm, J Peischl, A E Perring, I B Pollack, T B Ryerson, G Sachse, J P Schwarz, I J Simpson, D J Tanner, K L Thornhill, K Ullmann, R J Weber, P O Wennberg, A Wisthaler, G M Wolfe, L D Ziemba (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 https://doi.org/10.1002/2016JD025040
17
L L Ming, L Jin, J Li, P Q Fu, W Y Yang, D Liu, G Zhang, Z F Wang, X D Li (2017). PM2.5 in the Yangtze River Delta, China: Chemical compositions, seasonal variations, and regional pollution events. Environmental Pollution, 223: 200–212 https://doi.org/10.1016/j.envpol.2017.01.013
18
W T Morgan, J D Allan, S Bauguitte, E Darbyshire, M J Flynn, J Lee, D T Liu, B Johnson, J Haywood, K M Longo, P E Artaxo, H Coe (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 https://doi.org/10.5194/acp-20-5309-2020
19
G Myhre, B H Samset, M Schulz, Y Balkanski, S Bauer, T K Berntsen, H Bian, N Bellouin, M Chin, T Diehl, R C Easter, J Feichter, S J Ghan, D Hauglustaine, T Iversen, S Kinne, A Kirkevåg, J F Lamarque, G Lin, X Liu, M T Lund, G Luo, X Ma, T van Noije, J E Penner, P J Rasch, A Ruiz, Ø Seland, R B Skeie, P Stier, T Takemura, K Tsigaridis, P Wang, Z Wang, L Xu, H Yu, F Yu, J H Yoon, K Zhang, H Zhang, C Zhou (2013). Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations. Atmospheric Chemistry and Physics, 13(4): 1853–1877 https://doi.org/10.5194/acp-13-1853-2013
20
National Bureau of Statistics of China (2019). China Statistical Yearbook. Beijing: China Statistics Press
21
J J Orlando, G S Tyndall (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 https://doi.org/10.1039/c2cs35166h
22
Y L Sun, Z F Wang, P Q Fu, Q Jiang, T Yang, J Li, X L Ge (2013). The impact of relative humidity on aerosol composition and evolution processes during wintertime in Beijing, China. Atmospheric Environment, 77: 927–934 https://doi.org/10.1016/j.atmosenv.2013.06.019
23
G H Wang, R Y Zhang, M E Gomez, L X Yang, M L Zamora, M Hu, Y Lin, J F Peng, S Guo, J J Meng, J J Li, C L Cheng, T F Hu, Y Q Ren, Y S Wang, J Gao, J J, Cao Z S An, W J Zhou, G H Li, J Y Wang, P F Tian, W Marrero-Ortiz, J Secrest, Z F Du, J Zheng, D J Shang, L M Zeng, M Shao, W G Wang, Y Huang, Y Wang, Y J Zhu, Y X Li, J X Hu, B W Pan, L Cai, Y T Cheng, Y M, Ji F Zhang, D Rosenfeld, P S Liss, R A Duce, C E Kolb, M J Molina (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
J F Wang, J Y Li, J H Ye, J Zhao, Y Z Wu, J L Hu, D T Liu, D Y Nie, F Z Shen, X P Huang, D D Huang, D S Ji, X Sun, W Q Xu, J P Guo, S J Song, Y M Qin, P F Liu, J R Turner, H C Lee, S Hwang, H Liao, S T Martin, Q Zhang, M D Chen, Y L Sun, X L Ge, D J Jacob (2020a). Fast sulfate formation from oxidation of SO2 by NO2 and HONO observed in Beijing haze. Nature Communications, 11(1): 2844 https://doi.org/10.1038/s41467-020-16683-x
25
X K Wang, R Gemayel, N Hayeck, S Perrier, N Charbonnel, C H Xu, H Chen, C Zhu, L W Zhang, L Wang, S A Nizkorodov, X M Wang, Z Wang, T Wang, A Mellouki, M Riva, J M Chen, C George (2020b). Atmospheric photosensitization: A new pathway for sulfate formation. Environmental Science & Technology, 54(6): 3114–3120 https://doi.org/10.1021/acs.est.9b06347
26
R J Weber, H Y Guo, A G Russell, A Nenes (2016). High aerosol acidity despite declining atmospheric sulfate concentrations over the past 15 years. Nature Geoscience, 9(4): 282–285 https://doi.org/10.1038/ngeo2665
27
C Ye, P F Liu, Z B Ma, C Y Xue, C L Zhang, Y Y Zhang, J F Liu, C T Liu, X Sun, Y J Mu (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 https://doi.org/10.1021/acs.estlett.8b00579
28
S Yin, X F Wang, X R Zhang, Z X Zhang, Y Xiao, H Tani, Z Y Sun (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 https://doi.org/10.1016/j.atmosenv.2018.11.033
29
R J Yokelson, J D Crounse, P F DeCarlo, T Karl, S Urbanski, E Atlas, T Campos, Y Shinozuka, V Kapustin, A D Clarke, A Weinheimer, D J Knapp, D D Montzka, J Holloway, P Weibring, F Flocke, W Zheng, D Toohey, P O Wennberg, C Wiedinmyer, L Mauldin, A Fried, D Richter, J Walega, J L Jimenez, K Adachi, P R Buseck, S R Hall, R Shetter (2009). Emissions from biomass burning in the Yucatan. Atmospheric Chemistry and Physics, 9(15): 5785–5812 https://doi.org/10.5194/acp-9-5785-2009
30
Q Zhang, J L Jimenez, M R Canagaratna, J D Allan, H Coe, I Ulbrich, M R Alfarra, A Takami, A M Middlebrook, Y L Sun, K Dzepina, E Dunlea, K Docherty, P F DeCarlo, D Salcedo, T Onasch, J T Jayne, T Miyoshi, A Shimono, S Hatakeyama, N Takegawa, Y Kondo, J Schneider, F Drewnick, S Borrmann, S Weimer, K Demerjian, P Williams, K Bower, R Bahreini, L Cottrell, R J Griffin, J Rautiainen, J Y Sun, Y M Zhang, D R Worsnop (2007). Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes. Geophysical Research Letters, 34(13): L13801 https://doi.org/10.1029/2007GL029979
31
R Zhang, X S Sun, A J Shi, Y H Huang, J Yan, T Nie, X Yan, X Li (2018). Secondary inorganic aerosols formation during haze episodes at an urban site in Beijing, China. Atmospheric Environment, 177: 275–282 https://doi.org/10.1016/j.atmosenv.2017.12.031
32
B Zheng, D Tong, M Li, F Liu, C P Hong, G N Geng, H Y Li, X Li, L Q Peng, J Qi, L Yan, Y X Zhang, H Y Zhao, Y X Zheng, K B He, Q Zhang (2018). Trends in China’s anthropogenic emissions since 2010 as the consequence of clean air actions. Atmospheric Chemistry and Physics, 18(19): 14095–14111 https://doi.org/10.5194/acp-18-14095-2018
33
G J Zheng, F K Duan, H Su, Y L Ma, Y Cheng, B Zheng, Q Zhang, T Huang, T Kimoto, D Chang, U Pöschl, Y F Cheng, K B He (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 https://doi.org/10.5194/acp-15-2969-2015
34
G J Zheng, H Su, S W Wang, M O Andreae, U Pöschl, Y F Cheng (2020). Multiphase buffer theory explains contrasts in atmospheric aerosol acidity. Science, 369(6509): 1374–1377 https://doi.org/10.1126/science.aba3719
35
S Zhou, S Collier, D A Jaffe, N L Briggs, J Hee, A J Sedlacek III, L Kleinman, T B Onasch, Q Zhang (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 https://doi.org/10.5194/acp-17-2477-2017
