Impacts of heterogeneous reactions of sea salt and nitrogen-containing gases on ozone in Shandong coastal area
HUANG Lei1, XUE Di1, WANG Jiao1, CHEN Chun-qiang1, ZHANG Jie1, ZHANG Yi-sheng4, LIU Xiao-huan1,2,3
1. College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China; 2. Key Laboratory of Marine Environment and Ecology, Ministry of Education, Ocean University of China, Qingdao 266100, China; 3. Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China; 4. School of Environment and Municipal Engineering, Qingdao University of Technology Qingdao, Qingdao 266033, China
Abstract：The heterogeneous reactions of nitrogen-containing gases with sea salt and the subsequent production of highly reactive chlorine radicals (Cl·) could contribute to the formation of ozone (O3). The heterogeneous reactions of NO2, HNO3 and N2O5 with sea salt in the Community Multiscale Air Quality (CMAQ) model wao incorporated to simulate their impact on O3 concentration over coastal areas of Shandong in summer and winter of 2017. The simulation results indicated that the heterogeneous reactions substantially enhanced O3 concentrations up to 0.2×10-9~6.6×10-9(0.5%~15.5%) in summer and 0.8×10-9~15.3×10-9 (1.7%~27.4%) in winter, with the nighttime ClNO2 concentrations increased by 100×10-12~250×10-12 in summer and 300×10-12~650×10-12 in winter. The enhancement of O3 in summer was mainly concentrated in eastern Shandong, while in winter it covered most areas of Shandong, implicative of stronger and wider impact of heterogeneous reactions on O3 in winter in comparison to summer. The ozone enhancement triggered by the heterogeneous reactions was mainly taken effect during daytime, especially during 8:00~16:00. The influence also covered areas including Bohai Sea and South Yellow Sea, and the enhanced ozone concentration could be transported inland through four pathways, resulting in an increase of 0.2×10-9~15.3×10-9 of O3 concentration in the eastern coastal areas of Shandong, and 0.3×10-9~6.2×10-9 in the central and western areas like Jinan and Heze city, about 350km away from the eastern coastline of Shandong.
Lewis E R, Schwartz S E. Sea salt aerosol production:Mechanisms, methods, measurements and models-A critical review[J]. Geophysical Monograph Series, 2004,152:3719.
[2]
De Haan D O, Brauers T, Oum K, et al. Heterogeneous chemistry in the troposphere:Experimental approaches and applications to the chemistry of sea salt particles[J]. International Reviews in Physical Chemistry, 1999,18(3):343-385.
[3]
Finlayson-Pitts B J. Chlorine atoms as a potential tropospheric oxidant in the marine boundary layer[J]. Research on Chemical Intermediates, 1993,19(3):235-249.
[4]
Knipping E M, Dabdub D. Impact of chlorine emissions from sea-salt aerosol on coastal urban ozone[J]. Environmental Science & Technology, 2003,37(2):275-284.
[5]
Dai J, Liu Y, Wang P, et al. The impact of sea-salt chloride on ozone through heterogeneous reaction with N2O5in a coastal region of south China[J]. Atmospheric Environment, 2020,236:117604.
[6]
Robbins R C, Cadle R D, Eckhardt D L. The conversion of sodium chloride to hydrogen chloride in the atmosphere[J]. Journal of the Atmospheric Sciences, 1959,16(1):53-56.
[7]
Finlayson-Pitts B J. Reaction of NO2 with NaCl and atmospheric implications of NOCl formation[J]. Nature, 1983,306(5944):676-677.
[8]
Livingston F E, Finlayson-Pitts B J. The reaction of gaseous N2O5 with solid NaCl at 298K:Estimated lower limit to the reaction probability and its potential role in tropospheric and stratospheric chemistry[J]. Geophysical Research Letters, 1991,18(1):17-20.
[9]
De Haan D O, Finlayson-Pitts B J. Knudsen cell studies of the reaction of gaseous nitric acid with synthetic sea salt at 298K[J]. The Journal of Physical Chemistry A, 1997,101(51):9993-9999.
[10]
Langer S, Pemberton R S, Finlayson-Pitts B J. Diffuse reflectance infrared studies of the reaction of synthetic sea salt mixtures with NO2:A key role for hydrates in the kinetics and mechanism[J]. The Journal of Physical Chemistry A, 2000,101(7):1277-1286.
[11]
George C, Ponche J L, Mirabel P, et al. Study of the uptake of N2O5 by water and NaCl Solutions[J]. Journal of Physical Chemistry, 1994,98(35):8780-8784.
[12]
Behnke W, Krüger H U, Scheer V, et al. Formation of atomic ci from sea spray via photolysis ofnitryl chloride:determination of the sticking coefficient of N2O5 on NaCl aerosol[J]. Journal of Aerosol Science, 1991,22(22):S609-S612.
[13]
叶春翔,李宏军,朱彤,等.海盐颗粒物表面的NO2非均相反应[J]. 中国科学:化学, 2010,40(12):1765-1771.Ye C X, Li H J, Zhu T, et al. Heterogeneous reaction of NO2 with sea salt particles[J]. Scientia Sinica Chimica, 2010,40(12):1765-1771.
[14]
Bertram T H, Thornton J A. Toward a general parameterization of N2O5 reactivity on aqueous particles:the competing effects of particle liquid water, nitrate and chloride[J]. Atmospheric Chemistry and Physics, 2009,9(4):8351-8363.
[15]
Haskins J D, Lee B H, Lopez-Hilifiker F D, et al. Observational constraints on the formation of Cl2 from the reactive uptake of ClNO2 on aerosols in the polluted marine boundary layer[J]. Journal of Geophysical Research:Atmospheres, 2019,124(15):8851-8869.
[16]
Wang T, Tham Y J, Xue L, et al. Observations of nitryl chloride and modeling its source and effect on ozone in the planetary boundary layer of southern China[J]. Journal of Geophysical Research:Atmospheres, 2016,121(5):2476-2489.
[17]
Yan C, Tham Y J, Zha Q, et al.Fast heterogeneous loss of N2O5 leads to significant nighttime NOx removal and nitrate aerosol formation at a coastal background environment of southern China[J]. Science of The Total Environment, 2019,677:637-647.
[18]
McLaren R, Wojtal P, Majonis D, et al. NO3 radical measurements in a polluted marine environment:links to ozone formation[J]. Atmospheric Chemistry and Physics, 2010,10(9):4187-4206.
[19]
Simon H, Kimura Y, McGaughey G, et al. Modeling the impact of ClNO2 on ozone formation in the Houston area[J]. Journal of Geophysical Research:Atmospheres, 2009,114(D7).
[20]
Simon H, Kimura Y, Mcgaughey G, et al. Modeling heterogeneous ClNO2 formation, chloride availability, and chlorine cycling in Southeast Texas[J]. Atmospheric Environment, 2010,44(40):5476-5488.
[21]
Sarwar G, Simon H, Bhave P, et al. Examining the impact of heterogeneous nitryl chloride production on air quality across the United States[J]. Atmospheric Chemistry and Physics, 2012,12(14):6455-6473.
[22]
Sarwar G, Simon H, Xing J, et al. Importance of tropospheric ClNO2 chemistry across the Northern Hemisphere[J]. Geophysical Research Letters, 2014,41(11):4050-4058.
[23]
Li Q, Zhang L, Tham Y J, et al. Impacts of heterogeneous uptake of dinitrogen pentoxide and chlorine activation on ozone and reactive nitrogen partitioning:improvement and application of the WRF-Chem model in southern China[J]. Atmospheric Chemistry and Physics, 2016,16(23):14875-14890.
[24]
吴虹,张彩艳,王静,等.青岛环境空气PM10和PM2.5污染特征与来源比较[J]. 环境科学研究, 2013,26(6):583-589.Wu H, Zhang C Y, Wang J, et al. Comparative study on pollution characteristics and source apportionment of PM10 and PM2.5 in Qingdao[J]. Research of Environmental Sciences, 2013,26(6):583-589.
[25]
王珉,胡敏.青岛沿海大气气溶胶中海盐源的贡献[J]. 环境科学, 2000,(5):83-85.Wang M, Hu M. Sea salt source contribution to the aerosol in Qingdao seashore Area[J]. Environmental Science, 2000,(5):83-85.
[26]
张颖,王体健,庄炳亮,等.东亚海盐气溶胶时空分布及其直接气候效应研究[J]. 高原气象, 2014,33(6):1551-1561.Zhang Y, Wang T J, Zhuang B L, et al. Study of spatial and temporal variations of sea salt aerosol and its direct climate effect over East Asia[J]. Plateau Meteorology, 2014,33(6):1551-1561.
[27]
张艳.滨海地区背景点和城区大气PM1和PM2.5的化学组成及对人体健康的影响[D]. 山东大学, 2020.Zhang Y. Chemical compositions and their effect on human health of atmospheric PM1 and PM2.5 in a background site and an urban site in coastal area[D]. Shandong University, 2020.
[28]
Miyazaki K, Eskes H J, Sudo K. Global NOx emission estimates derived from an assimilation of OMI tropospheric NO2 columns[J]. Atmospheric Chemistry and Physics, 2012,11(5):31523-31583.
[29]
Gong S L. A parameterization of sea-salt aerosol source function for sub- and super-micron particles[J]. Global biogeochemical cycles, 2003,17(4):1097-1014.
[30]
Abbatt J P D, Waschewsky G C G. Heterogeneous interactions of HOBr, HNO3, O3, and NO2 with deliquescent NaCl aerosols at room temperature[J]. Atmospheric Chemistry and Physics, 1998,102(21):3719-3725.
[31]
US-EPA. Guidance on the use of models and other analyses for demonstrating attainment of air quality goals for ozone, PM2.5, and regional haze[S]. US Environmental Protection Agency Office of Air Quality Planning and Standards, 2007.
[32]
沈劲,王雪松,李金凤,等.Models-3/CMAQ和CAMx对珠江三角洲臭氧污染模拟的比较分析[J]. 中国科学:化学, 2011,41(11):1750-1762.Shen J, Wang X S, Li J F, et al. Evaluation and intercomparison of ozone simulations by Models-3/CMAQ and CAMx over Pearl River Delta[J]. Scientia Sinica Chinica, 2011,41(11):1750-1762.
[33]
吴兑,吴晟,李海燕,等.穗港晴沙两重天-2010年3月17-23日珠三角典型灰霾过程分析[J]. 环境科学学报, 2011,31(4):695-703.Wu D, Wu S, Li H Y, et al.Dusty sky in Hong Kong and clear sky in the inland of the Pearl River Delta:Analysis of a typical haze episode during 17-23 March 2010[J]. Acta Scientiae Circumstantiae, 2011, 31(4):695-703.
[34]
高晋徽,朱彬,王言哲,等.2005~2013年中国地区对流层二氧化氮分布及变化趋势[J]. 中国环境科学, 2015,35(8):2307-2318.Gao J H, Zhu B, Wang Y Z, et al. Distribution and long-term variation of tropospheric NO2 over China during 2005 to 2013[J]. China Environmental Science, 2015,35(8):2307-2318.
[35]
Chang W L, Bhave P V, Brown S S, et al.Heterogeneous atmospheric Chemistry, Ambient Measurements, and Model Calculations of N2O5:A Review[J]. Aerosol Science and Technology, 2011,45(6):665-695.
[36]
Phillips G J, Tang M J, Thieser J, et al. Significant concentrations of nitryl chloride observed in rural continental Europe associated with the influence of sea salt chloride and anthropogenic emissions[J]. Geophysical research letters, 2012,39(10):L10811.
[37]
Priestley M, Le Breton M, Bannan T J, et al. Observations of organic and inorganic chlorinated compounds and their contribution to chlorine radical concentrations in an urban environment in northern Europe during the wintertime[J]. Atmospheric Chemistry and Physics, 2018,18(18):13481-13493.
[38]
Sommariva R, Hollis L D J, Tomás Sherwen, et al. Seasonal and geographical variability of nitryl chloride and its precursors in Northern Europe[J]. Atmospheric Science Letters, 2018,19(19):e844.
[39]
Jeong D, Seco R, Gu D, et al. Integration of airborne and ground observations of nitryl chloride in the Seoul metropolitan area and the implications on regional oxidation capacity during KORUS-AQ 2016[J]. Atmospheric Chemistry and Physics, 2019,19(19):12779-12795.
[40]
Eger P G, Friedrich N, Schuladen J, et al. Shipborne measurements of ClNO2 in the Mediterranean Sea and around the Arabian Peninsula during summer[J]. Atmospheric Chemistry and Physics, 2019,19(19):12121-12140.
[41]
Tham Y J, Yan C, Xue L, et al. Presence of high nitryl chloride in Asian coastal environment and its impact on atmospheric photochemistry[J]. Chinese Science Bulletin, 2014,59(4):356-359.
[42]
Yun H, Wang W, Wang T, et al. Nitrate formation from heterogeneous uptake of dinitrogen pentoxide during a severe winter haze in southern China[J]. Atmospheric Chemistry and Physics, 2018,18(23):17515-17527.
[43]
Xia M, Peng X, Wang W, et al. Significant production of ClNO2 and possible source of Cl2 from N2O5 uptake at a suburban site in eastern China[J]. Atmospheric Chemistry and Physics, 2020,20(10):6147-6158.
