The characterization of nocturnal dinitrogen pentoxide pollution in winter of Shenzhen
YUN Long1, NIU Ying-bo2, LUO Yao2, LU Jun-ming2, WANG Jun-rui2, LIN Chu-xiong1, GU Tian-fa1, QIU Zhi-cheng1, HUANG Xiao-feng2, HE Ling-yan2
1. Shenzhen Environmental Monitoring Center of Guangdong Province, Shenzhen 518049, China; 2. Laboratory of Atmospheric Observation Supersite, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, China
Abstract:The heterogeneous hydrolysis of N2O5 has a significant impact on nocturnal particulate nitrate formation, yet this process in highly polluted urban areas in winter remain poorly understood. Previous N2O5 observations in the Pearl River Delta are mainly concentrated in summer or warm conditions. At present, there is no report on the observation of N2O5 at night in winter in Shenzhen. Here we presented measurements of gas-phase N2O5 and HNO3 by high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) during winter in urban ShenZhen, China. In this season, N2O5 showed large day-to-day variations with average mixing ratios of (174.3 ±262.0)×10-12, with the maximum value of 4535.1×10-12. High reactivity of N2O5, with average τ(N2O5)-1 of 8.3×10-2s-1, suggested active nocturnal chemistry and a large nocturnal nitrate formation potential via N2O5 heterogeneous uptake. Coupled with simultaneous measurement of NO, NO2, O3 and pNO3-, the chemical behavior of active nitrogen in winter night of Shenzhen was quantitatively characterized. In addition, the analysis of odd oxygen budget showed that the measured concentrations of O3, NO2, HNO3 and pNO3- account for all of the Ox, the Ox budget closure occurs at a ratio of 1.5 (HNO3+ pNO3-) formed per Ox lost, indicating N2O5 hydrolysis as the mechanism in winter.
Brown S S, Ryerson T B, Wollny A G, et al. Variability in nocturnal nitrogen oxide processing and its role in regional air quality[J]. Science, 2006,311(5757):67-70.
[2]
Chameides W L. Photo-chemical role of tropospheric nitrogen-oxides[J]. Geophys Res Lett, 1978,5(1):17-20.
[3]
von Glasow R. Wider role for airborne chlorine[J]. Nature, 2010, 464(7286):168-169.
[4]
Dentener F J, Crutzen P J. Reaction of N2O5 on Tropospheric Aerosols-Impact on the Global Distributions of NOx, O3, and OH[J]. J Geophys Res-Atmos, 1993,98(D4):7149-7163.
[5]
Zheng B, Tong D, Li M, et al. Trends in China's anthropogenic emissions since 2010 as the consequence of clean air actions[J]. Atmospheric Chemistry and Physics, 2018,18(19):14095-14111.
[6]
Paulot F, Jacob D J, Pinder R W, et al. Ammonia emissions in the United States, European Union, and China derived by high-resolution inversion of ammonium wet deposition data:Interpretation with a new agricultural emissions inventory (MASAGE_NH3)[J]. J Geophys Res-Atmos, 2014,119(7):4343-4364.
[7]
Tian H, Melillo J, Lu C, et al.:Contributions from multiple global change factors[J]. Global Biogeochemical Cycles, 2011,25(1).
[8]
Zhu J, Wang Q, He N, et al. Effect of atmospheric nitrogen deposition and its components on carbon flux in terrestrial ecosystems in China[J]. Environmental Research, 2021,202:111787.
[9]
Huang X F, Zou B B, He L Y, et al. Exploration of PM2.5 sources on the regional scale in the Pearl River Delta based on ME-2 modeling[J]. Atmospheric Chemistry and Physics, 2018,18(16):11563-11580.
[10]
陈雪,黄晓锋,朱波,等.深圳市秋季VOCs空间分布特征与关键减排物种[J]. 中国环境科学, 2021,41(9):4069-4076. Chen X, Huang X F, Zhu B et al. Spatial distribution characteristics of VOCs and key emission reduction species in autumn Shenzhen[J]. China Environmental Science, 2021,41(9):4069-4076.
[11]
江家豪,彭杏,朱波,等.深圳大气PM2.5化学组成的长期变化特征[J]. 中国环境科学, 2021,41(2):574-579. Jiang J H, Peng X, Zhu B et al. Long-term variational characteristics of the chemical composition of PM2.5 in Shenzhen[J]. China Environmental Science, 2021,41(2):574-579.
[12]
韩煜,牛英博,夏士勇,等.深圳大学城园区典型OVOCs污染特征与来源解析[J]. 中国环境科学, 2018,38(11):4023-4030. Han Y, Niu Y B, Xia S Y et al. Pollution characteristics and source apportionment of typical OVOCs in Shenzhen University Town[J]. China Environmental Science, 2018,38(11):4023-4030.
[13]
陈瑶,云龙,罗遥,等.深圳冬季大气气态硝酸和颗粒态硝酸盐气粒分配特征[J]. 中国环境科学, 2021,41(9):4036-4042. Chen Y, Yun L, Luo Y, et al. Characteristics of gas-particle partitioning of gaseous nitric acid and particle nitrate in Shenzhen in winter[J]. China Environmental Science, 2021,41(9):4036-4042.
[14]
Le Breton M, McGillen M R, Muller J B A, et al. Airborne observations of formic acid using a chemical ionization mass spectrometer[J]. Atmospheric Measurement Techniques, 2012,5(12):3029-3039.
[15]
Kercher J P, Riedel T P, Thornton J A. Chlorine activation by N2O5:simultaneous, in situ detection of ClNO2 and N2O5 by chemical ionization mass spectrometry[J]. Atmospheric Measurement Techniques, 2009,2(1):193-204.
[16]
牛英博,黄晓锋,王海潮,等.珠江三角洲大气夜间非均相化学反应对二次气溶胶和臭氧的影响[J]. 科学通报, 2022,67(18):2060-2068. Niu Y B, Huang X F, Wang H C et al. Effects of nighttime heterogeneous reactions on the formation of secondary aerosols and ozone in the Pearl River Delta[J]. Chinese Science Bulletin, 2022, 67(18):2060-2068.
[17]
Brown S S, Dubé W P, Bahreini R, et al. Biogenic VOC oxidation and organic aerosol formation in an urban nocturnal boundary layer:Aircraft vertical profiles in Houston, TX[J]. Atmospheric Chemistry and Physics, 2013,13(22):11317-11337.
[18]
Brown S S, An H, Lee M, et al. Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene:Results from the Seoul tower during MAPS 2015[J]. Faraday Discussions, 2017,200:529-557.
[19]
Brown S S, Stutz J. Nighttime radical observations and chemistry[J]. Chemical Society Reviews, 2012,41(19):6405-6447.
[20]
Platt U, Alicke B, Dubois R, et al. Free radicals and fast photochemistry during BERLIOZ[J]. J. Atmos. Chem., 2002,42(1):359-394.
[21]
Brown S S, Stark H, Ravishankara A R. Applicability of the steady state approximation to the interpretation of atmospheric observations of NO3 and N2O5[J]. J. Geophys. Res-Atmos., 2003,108(D17):4539.
[22]
Wagner N L, Riedel T P, Young C J, et al. N2O5 uptake coefficients and nocturnal NO2 removal rates determined from ambient wintertime measurements[J]. J. Geophys Res.-Atmos., 2013,118(16):9331-9350.
[23]
Brown S S, Dubé W P, Tham Y J, et al. Nighttime chemistry at a high altitude site above Hong Kong[J]. Journal of Geophysical Research, 2016,121(5):2457-2475.
[24]
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, 2016, 121(5):2476-2489.
[25]
Brown S S, Dibb J E, Stark H, et al. Nighttime removal of NOx in the summer marine boundary layer[J]. Geophys Res Lett, 2004,31(7):L071081-5.
[26]
Wang X, Wang T, Yan C, et al. Large daytime signals of N2O5 and NO3 inferred at 62 amu in a TD-CIMS:chemical interference or a real atmospheric phenomenon?[J]. Atmospheric Measurement Techniques, 2014,7(1):1-12.
[27]
Wang X F, Wang H, Xue L K, et al. Observations of N2O5 and ClNO2 at a polluted urban surface site in North China:High N2O5 uptake coefficients and low ClNO2 product yields[J]. Atmos. Environ., 2017,156:125-134.
[28]
Osthoff H D, Roberts J M, Ravishankara A R, et al. High levels of nitryl chloride in the polluted subtropical marine boundary layer[J]. Nat Geosci, 2008,1(5):324-328.
[29]
Atkinson R, Baulch D L, Cox R A, et al. Evaluated kinetic and photochemical data for atmospheric chemistry:Volume I-gas phase reactions of Ox, HOx, NOx and SOx species[J]. Atmospheric Chemistry and Physics, 2004,4(6):1461-1738.
[30]
Brown S S, deGouw J A, Warneke C, et al. Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol[J]. Atmospheric Chemistry and Physics, 2009,9(9):3027-3042.
[31]
Huang X F, Cao L M, Tian X D, et al. Critical role of simultaneous reduction of atmospheric odd oxygen for winter haze mitigation[J]. Environ Sci Technol, 2021,55(17):11557-11567.
[32]
Brown S S, Neuman J A, Ryerson T B, et al. Nocturnal odd-oxygen budget and its implications for ozone loss in the lower troposphere[J]. Geophys Res Lett, 2006,33(8):801.
[33]
Womack C C, McDuffie E E, Edwards P M, et al. An Odd Oxygen Framework for Wintertime Ammonium Nitrate Aerosol Pollution in Urban Areas:NOx and VOC Control as Mitigation Strategies[J]. Geophys Res Lett, 2019,46(9):4971-4979.