基于I-CIMS的深圳大气中气态硝酸观测及污染特征分析

焦伯旸; 唐梦雪; 曹礼明; 杨胜奥; 黄晓锋; 何凌燕

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中国环境科学 ›› 2025, Vol. 45 ›› Issue (9) : 4807-4814.

大气污染与控制

基于I-CIMS的深圳大气中气态硝酸观测及污染特征分析

焦伯旸, 唐梦雪, 曹礼明, 杨胜奥, 黄晓锋, 何凌燕

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Gaseous nitric acid observation and contamination characteristic analysis in Shenzhen based on I-CIMS

JIAO Bo-yang, TANG Meng-xue, CAO Li-ming, YANG Sheng-ao, HUANG Xiao-feng, HE Ling-yan

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摘要

为探究深圳市大气气态硝酸(HNO₃)的污染特征及驱动机制,本研究基于碘离子化学电离飞行时间质谱(I-CIMS)技术,于2023年夏季和2024年冬季开展HNO₃观测,结合机器学习探讨其驱动机制.结果显示,冬季HNO₃浓度(0.72±0.19)×10^-9显著高于夏季(0.09±0.05)×10^-9,呈昼高夜低特征.模型拟合良好(R²=0.91),SHAP分析表明温度是首要影响因子,气粒分配主导HNO₃变化.温度在夏季影响更为明显,化学过程在冬季影响更显著.氯盐通过置换硝酸盐抑制HNO₃生成,揭示氯亏损对氮循环的复杂作用.建议优先控制NH₃排放,不仅抑制总硝酸生成也降低HNO₃向颗粒相转化,并关注氯亏损对沿海城市氮循环的复杂影响,为珠三角区域硝酸盐污染防控提供科学依据.

Abstract

To investigate the pollution characteristics and driving mechanisms of atmospheric gaseous nitric acid (HNO₃) in Shenzhen, this study conducted HNO₃ measurements during summer 2023 and winter 2024 using iodide ion chemical ionization time-of-flight mass spectrometry (I-CIMS), combined with machine learning for mechanism analysis. The results revealed significantly higher HNO₃ concentrations in winter (0.72±0.19×10^-9) compared to summer (0.09±0.05×10^-9), with distinct diurnal patterns showing daytime peaks. The model demonstrated good performance (R²=0.91), with SHAP analysis identifying temperature as the primary driver governing HNO₃ variation through gas-particle partitioning. Seasonal differences emerged: temperature dominated summer dynamics through thermodynamic control, while chemical processes prevailed in winter. Notably, chloride salts suppressed HNO₃ formation through nitrate displacement, revealing the complex role of chloride depletion in nitrogen cycling. Our findings highlight the priority of NH₃ emission control, which concurrently inhibits total nitrate formation and reduces HNO₃ particle-phase conversion. Special attention should be given to coastal urban nitrogen cycling complexities induced by chloride depletion, providing scientific basis for nitrate pollution mitigation in the Pearl River Delta region.

导出引用

焦伯旸, 唐梦雪, 曹礼明, 杨胜奥, 黄晓锋, 何凌燕. 基于I-CIMS的深圳大气中气态硝酸观测及污染特征分析[J]. 中国环境科学. 2025, 45(9): 4807-4814

JIAO Bo-yang, TANG Meng-xue, CAO Li-ming, YANG Sheng-ao, HUANG Xiao-feng, HE Ling-yan. Gaseous nitric acid observation and contamination characteristic analysis in Shenzhen based on I-CIMS[J]. China Environmental Science. 2025, 45(9): 4807-4814

中图分类号： X51

参考文献

[1] Goldan P D, Kuster W C, Albritton D L, et al. Calibration and tests of the filter-collection method for measuring clean-air, ambient levels of nitric acid [J]. Atmospheric Environment, 1983,17(7):1355-1364.
[2] Durham J L, Overton J H, Aneja V P. Influence of gaseous nitric acid on sulfate production and acidity in rain [J]. Atmospheric Environment, 1981,15(6):1059-1068.
[3] Ye C X, Zhou X L, Pu D, et al. Rapid cycling of reactive nitrogen in the marine boundary layer [J]. Nature, 2016,532:489-491.
[4] Stanier C, Singh A, Adamski W, et al. Overview of the LADCO Winter Nitrate Study: Hourly ammonia, nitric acid and PM_2.5 composition at an urban and rural site pair during PM_2.5 episodes in the US Great Lakes Region [J]. Atmospheric Chemistry and Physics, 2012,12(289):11037-11056.
[5] Arnold F, Hauck G. Lower stratosphere trace gas detection using aircraft-borne active chemical ionization mass spectrometry [J]. Nature, 1985,315(6017):307-309.
[6] Uno I, Wang Z, Itahashi S, et al. Paradigm shift in aerosol chemical composition over regions downwind of China [J]. Scientific Reports, 2020,10(1):63592.
[7] Dentener F J, Crutzen P J. Reaction of N₂O₅ on tropospheric aerosols: Impact on the global distributions of NO_x, O₃, and OH [J]. Journal of Geophysical Research: Atmospheres, 1993,98(D4):7149-7163.
[8] Hudman R C, Jacob D J, Cooper O R, et al. Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California [J]. Journal of Geophysical Research: Atmospheres, 2004,109(D23):D23S10.
[9] Singh H B, Herlth D, Kolyer R, et al. Reactive nitrogen and ozone over the western Pacific: Distribution, partitioning, and sources [J]. Journal of Geophysical Research: Atmospheres, 1996,101(D1):1793- 1808.
[10] Forster E J, Healey J R, Dymond C, et al. Commercial afforestation can deliver effective climate change mitigation under multiple decarbonisation pathways [J]. Nature Communications, 2024,12: 24084.
[11] Tabazadeh A, Jacobson M Z, Singh H B, et al. Nitric acid scavenging by mineral and biomass burning aerosols [J]. Geophysical Research Letters, 1998,25(22):4185-4188.
[12] Parrish D D, Fehsenfeld F C. Methods for gas-phase measurements of ozone, ozone precursors and aerosol precursors [J]. Atmospheric Environment, 2000,34(12-14):1921-1957.
[13] Miller D F, Spicer C W. Measurement of nitric acid in smog [J]. Journal of the Air Pollution Control Association, 2012,25(9):940-942.
[14] Shaw R, Stevens R K, Bowermaster J, et al. Measurements of atmospheric nitrate and nitric acid: The denuder difference experiment [J]. Atmospheric Environment, 1982,16(4):845-853.
[15] Tuazon E C, Winer A M, Pitts J N. Trace pollutant concentrations in a multiday smog episode in the California South Coast Air Basin by long path length Fourier transform infrared spectroscopy [J]. Environmental Science & Technology, 1981,15(10):1232-1237.
[16] Gregory G L, Hoell J M, Huebert B J, et al. An intercomparison of airborne nitric acid measurements [J]. Journal of Geophysical Research: Atmospheres, 1990,95(D7):10089-10102.
[17] Neuman J A, Huey L G, Ryerson T B, et al. Study of inlet materials for sampling atmospheric nitric acid [J]. Environmental Science & Technology, 1999,33(7):1133-1136.
[18] Sun J, Qin M, Xie X, et al. Seasonal modeling analysis of nitrate formation pathways in Yangtze River Delta region, China [J]. Atmospheric Chemistry and Physics, 2022,22(18):12629-12646.
[19] He L Y, Huang X F, Xue L, et al. Submicron aerosol analysis and organic source apportionment in an urban atmosphere in Pearl River Delta of China using high-resolution aerosol mass spectrometry [J]. Journal of Geophysical Research: Atmospheres, 2011,116:D12304.
[20] Tian M, Liu Y, Yang F, et al. Increasing importance of nitrate formation for heavy aerosol pollution in two megacities in Sichuan Basin, southwest China [J]. Environmental Pollution, 2019,250:898- 905.
[21] Malik A O, Jones P G, Chan P S, et al. Association of long-term exposure to particulate matter and ozone with health status and mortality in patients after myocardial infarction [J]. Circulation: Cardiovascular Quality and Outcomes, 2019,12(4):e005598.
[22] Furutani H, Akimoto H. Development and characterization of a fast measurement system for gas-phase nitric acid with a chemical ionization mass spectrometer in the marine boundary layer [J]. Journal of Geophysical Research: Atmospheres, 2002,107(D2):ACH1-1- ACH 1-13.
[23] Werbos P J. Beyond regression: New tools for prediction and analysis in the behavioral sciences [D]. Cambridge: Harvard University, 1974.
[24] Rumelhart D E, Hinton G E, Williams R J. Learning representations by back-propagating errors [J]. Nature, 1986,323(6088):533-536.
[25] Chen X, Ma W, Zheng F X, et al. Identifying driving factors of atmospheric N₂O₅ with machine learning [J]. Environmental Science & Technology, 2024,58(15):11568-11577.
[26] Tang M X, Huang X F, Sun T L, et al. Decisive role of ozone formation control in winter PM_2.5 mitigation in Shenzhen, China [J]. Environmental Pollution, 2022,(May):301.
[27] Dao X, Lin Y C, Cao F, et al. Introduction to the National Aerosol Chemical Composition Monitoring Network of China: Objectives, Current Status, and Outlook. Bulletin of the American Meteorological Society [J]. 2019,100(12):ES337-ES351.
[28] Nojiri R, Osada K, Kurosaki Y, et al. Variations in gaseous nitric acid concentrations at Tottori, Japan: Long-range transport from the Asian continent and local production [J]. Atmospheric Environment, 2022, 274:118988.
[29] Zbieranowski A L, Aherne J. Ambient concentrations of atmospheric ammonia, nitrogen dioxide and nitric acid in an intensive agricultural region [J]. Atmospheric Environment, 2013,70:289-299.
[30] Huey L G, Tanner D J, Slusher D L, et al. CIMS measurements of HNO₃ and SO₂ at the South Pole during ISCAT 2000 [J]. Atmospheric Environment, 2004.
[31] Danalatos D, Glavas S, Kambezidis H. Atmospheric nitric acid concentrations in a Mediterranean site, Patras, Greece [J]. Atmospheric Environment, 1995,29(15):1849-1852.
[32] Parmar R S, Satsangi G S, Lakhani A, et al. Simultaneous measurements of ammonia and nitric acid in ambient air at Agra (27°10'N and 78°05'E) (India) [J]. Atmospheric Environment, 2001, 35(34):5979-5988.
[33] Li Y, Schwandner F M, Sewell H J, et al. Observations of ammonia, nitric acid, and fine particles in a rural gas production region [J]. Atmospheric Environment, 2014,83:80-89.
[34] Acker K, Spindler G, Brüggemann E. Nitrous and nitric acid measurements during the INTERCOMP2000 campaign in Melpitz [J]. Atmospheric Environment, 2004,38(38):6497-6505.
[35] 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. The impact of atmospheric nighttime heterogeneous chemical reactions in the Pearl River Delta on secondary aerosols and ozone [J]. Chinese Science Bulletin, 2022, 67(18):2060-2068.
[36] 罗遥,林晓玉,牛英博,等.深圳市冬季大气中硝酸分配特征观测研究 [J].中国环境科学, 2023,43(8):3877-3885. Luo Y, Lin X Y, Niu Y B, et al. The impact of nighttime heterogeneous chemical reactions in the atmosphere of the Pearl River Delta on secondary aerosols and ozone [J]. China Environmental Science, 2023,43(8):3877-3885.
[37] Oniwa S, Abe M, Aikawa M. Significant parameter for controlling the partition of ambient nitrate species between HNO₃ (g) and NH₄NO₃(p) [J]. Environmental Monitoring and Assessment, 2023,195:1134.
[38] Guo H, Liu J, Froyd K, et al. Fine particle pH and gas-particle phase partitioning of inorganic species in Pasadena, California, during the 2010 CalNex campaign [J]. Atmospheric Chemistry and Physics, 2017, 17(9):1-33.