上海市亚微米颗粒物中水溶性含氮组分的分布特征

doi:10.12066/j.issn.1007-2861.2232

摘要/Abstract

摘要：

细颗粒态无机和有机含氮组分的形成、转化、传输和沉降在大气氮循环中发挥重要作用. 为了解上海亚微米颗粒物(PM$_{1}$)中含氮物质的质量浓度、组成及季节变化特征, 使用大流量采样器采集了 2017—2018 年 66 个 PM$_{1}$ 样品, 并应用离子色谱仪和紫外/可见光光度计分析了水溶性无机离子和水溶性有机氮(water-soluble organic nitrogen, WSON)的质量浓度. 结果表明: 上海 PM$_{1}$中NH$_{4}^{+}$-N、NO$_{3}^{-}$-N、WSON 的年平均质量浓度分别为 1.79、0.97、0.41 μg/m³; NH$_{4}^{+}$-N 对水溶性总氮(water-soluble total nitrogen, WSTN)的贡献最高(56%), NO$_{3}^{-}$-N 次之(31%), WSON 为 13%. 上海PM$_{1}$中含氮组分的质量浓度存在冬季最高、夏季最低的季节变化趋势, 但NH$_{4}^{+}$-N、NO$_{3}^{-}$-N 和 WSON 对 WSTN 贡献的季节变化存在明显的不同, NH$_{4}^{+}$-N 在不同季节变化较小, NO$_{3}^{-}$-N 表现出显著的冬高(38%)、夏低(18%)的特点, 而 WSON 夏季最高(22%)、冬季最低(8%). 正矩阵因子分解(positive matrix factorisation, PMF)法的源解析结果表明: 二次反应和生物质燃烧贡献了上海 PM$_{1}$ 中 WSON 的 48%, 燃煤贡献了 11%, 植物源挥发性有机化合物二次转化贡献了 20%, 餐饮和机动车贡献了 21%. WSON 的来源有显著的季节变化.

关键词: 亚微米颗粒物, 含氮组分, 季节变化, 来源解析

Abstract:

The formation, transformation, transportation, and deposition of inorganic and organic nitrogen within fine particles is critical in the nitrogen cycle. To understand the concentrations, compositions, and seasonal variations of the nitrogen-containing components within submicron particles (PM$_{1}$) in Shanghai, PM$_{1}$ samples were collected in Shanghai during 2017—2018 using a high-volume sampler. The concentrations of water-soluble ions and water-soluble organic nitrogen (WSON) were measured using ion chromatography and UV/Vis photometry. The annual average concentrations of NH$_{4}^{+}$-N, NO$_{3}^{-}$-N, and WSON within PM$_{1}$ in Shanghai were 1.79, 0.97, and 0.41 μg/m³ respectively. NH$_{4}^{+}$-N showed the highest contribution (56 %) to the water-soluble total nitrogen (WSTN), followed by NO$_{3}^{-}$-N (31 %), while the annual contribution of WSON to WSTN was 13 %. The concentrations of the nitrogen-containing components within PM$_{1}$ in Shanghai were highest in winter and lowest in summer. However, the contributions of NH$_{4}^{+}$-N, NO$_{3}^{-}$-N, and WSON to WSTN differed. The contribution of NH$_{4}^{+}$-N to WSTN showed a small seasonal variation, and a distinct trend of higher in winter (38 %) and lower in summer (18 %) was observed for the contribution of NO$_{3}^{-}$-N, while the contribution of WSON to WSTN was the highest in summer (22 %) and lowest in winter (8 %). Positive matrix factorisation (PMF) showed that secondary formation and the burning of biomass contributed 48 % of the WSON within PM$_{1}$ in Shanghai, with coal combustion contributing 11 %, secondary formation from biogenic volatile organic compounds 20 %, and emissions from kitchens and vehicles 21 %. The sources of WSON varied significantly according to season.

Key words: submicron particles, nitrogen-containing components, seasonal variation, source distribution

中图分类号:

X513

张玉莹, 陈浩, 冯加良. 上海市亚微米颗粒物中水溶性含氮组分的分布特征[J]. 上海大学学报(自然科学版), 2022, 28(1): 80-90.

ZHANG Yuying, CHEN Hao, FENG Jialiang. Characteristics of nitrogen-containing components within submicron particles in Shanghai[J]. Journal of Shanghai University（Natural Science Edition）, 2022, 28(1): 80-90.

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参考文献 41

[1]	Kulmala M. Atmospheric chemistry: China's choking cocktail[J]. Nature, 2015, 526(7574): 497-499. doi: 10.1038/526497a
[2]	何立平, 田茂平, 吴红, 等. 大气氮沉降对三峡库区消落带土壤呼吸的影响[J]. 中国环境科学, 2019, 39(3): 1132-1138.
[3]	Matsumoto K, Sakata K, Watanabe Y. Water-soluble and water-insoluble organic nitrogen in the dry and wet deposition[J]. Atmospheric Environment, 2019, 218: 117022. doi: 10.1016/j.atmosenv.2019.117022
[4]	Liu X, Zhang Y, Han W, et al. Enhanced nitrogen deposition over China[J]. Nature, 2013, 494(7438): 459-462. doi: 10.1038/nature11917
[5]	Ho K F, Ho S S, Huang R J, et al. Characteristics of water-soluble organic nitrogen in fine particulate matter in the continental area of China[J]. Atmospheric Environment, 2015, 106: 252-261. doi: 10.1016/j.atmosenv.2015.02.010
[6]	Adams P J, Seinfeld J H, Koch D M. Global concentrations of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a general circulation model[J]. Journal of Geophysical Research: Atmospheres, 1999, 104(D11): 13791-13823. doi: 10.1029/1999JD900083
[7]	Duce R A, Laroche J, Altieri K, et al. Impacts of atmospheric anthropogenic nitrogen on the open ocean[J]. Science, 2008, 320(5878): 893-897. doi: 10.1126/science.1150369 pmid: 18487184
[8]	Chen H Y, Chen L D, Chiang Z Y, et al. Size fractionation and molecular composition of water-soluble inorganic and organic nitrogen in aerosols of a coastal environment[J]. Journal of Geophysical Research: Atmospheres, 2010, 115(D22): D22307. doi: 10.1029/2010JD014157
[9]	黄伊宁, 张胜华, 徐玢花, 等. 上海 PM$_{2.5}$ 中碳、氮、硫元素的浓度及其季节分布特征[J]. 上海大学学报(自然科学版), 2020, 26(3): 433-442. doi: 10.12066/j.issn.1007-2861.2050
[10]	刘随心, 曹军骥, 何建辉, 等. 大气气溶胶中有机氮和无机氮的测试方法及应用[J]. 中国粉体技术, 2013, 19(5): 7-11.
[11]	Cape J N, Cornell J N, Jickells T D, et al. Organic nitrogen in the atmosphere—Where does it come from? A review of sources and methods[J]. Atmospheric Research, 2011, 102(1/2): 30-48. doi: 10.1016/j.atmosres.2011.07.009
[12]	Lin M, Walker J, Geron C, et al. Organic nitrogen in PM$_{2.5}$ aerosol at a forest site in the Southeast US[J]. Atmospheric Chemistry and Physics, 2010, 10: 2145-2157.
[13]	Shi J H, Gao H W, Qi J H, et al. Sources, compositions, and distributions of water-soluble organic nitrogen in aerosols over the China Sea[J]. Journal of Geophysical Research, 2010, 115, D17303. doi: 10.1029/2009JD013238
[14]	徐玢花, 杜艳, 胡俊超, 等. 上海 PM$_{2.5}$ 中水溶性有机氮的污染特征[J]. 地球化学, 2016, 45(2): 190-198.
[15]	Zhang Q, Anastasio C, Jimenez-Cruz M. Water-soluble organic nitrogen in atmospheric fine particles (PM$_{2.5})$ from northern California [J]. Journal of Geophysical Research: Atmospheres, 2002, 107(D11): AAC 3-1-AAC 3-9.
[16]	Smith J N, Barsanti K C, Friedli H R, et al. Observations of aminium salts in atmospheric nanoparticles and possible climatic implications[J]. Proceedings of the National Academy of Sciences of the United States of America, 2010, 107: 6634-6639.
[17]	Lee B H, Mohar C, Hilfiker F D. Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets[J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(6): 1516-1521.
[18]	Wang Yj, Hu M, Lin P, et al. Molecular characterization of nitrogen-containing organic compounds in humic-like substances emitted from straw residue burning[J]. Environmental Science and Technology, 2017, 51: 5951-5961. doi: 10.1021/acs.est.7b00248
[19]	Yu X, Yu Q, Zhu M, et al. Water soluble organic nitrogen (WSON) in ambient fine particles over a megacity in South China: spatiotemporal variations and source apportionment[J]. Journal of Geophysical Research: Atmospheres, 2017, 122: 13045-13060.
[20]	Rollins A W, Smith J D, Wilson K R, et al. Real time in situ detection of organic nitrates in atmospheric aerosols[J]. Environmental Science & Technology, 2010, 44: 5540-5545. doi: 10.1021/es100926x
[21]	Luo L, Yao X H, Gao H W, et al. Nitrogen speciation in various types of aerosol in spring over the northwestern Pacific Ocean[J]. Atmospheric Chemistry and Physics, 2016, 15(25): 583-625.
[22]	Violaki K, Sciare J, Williams J, et al. Atmospheric water-soluble organic nitrogen (WSON) over marine environments: a global perspective[J]. Biogeosciences, 2015, 12(10): 3131-3140. doi: 10.5194/bg-12-3131-2015
[23]	Kang H Q, Zhu B, Su J F, et al. Analysis of a long-lasting haze episode in Nanjing, China[J]. Atmospheric Research, 2013, 120/121: 78-87. doi: 10.1016/j.atmosres.2012.08.004
[24]	Cao J J, Lee S C, Ho K F, et al. Spatial and seasonal variations of atmospheric organic carbon and elemental carbon in Pearl River Delta Region, China[J]. Atmospheric Environment, 2004, 38(27): 4447-4456. doi: 10.1016/j.atmosenv.2004.05.016
[25]	Feng J, Li M, Zhang P, et al. Investigation of the sources and seasonal variations of secondary organic aerosols in PM$_{2.5}$ in Shanghai with organic tracers[J]. Atmospheric Environment, 2013, 79: 614-622. doi: 10.1016/j.atmosenv.2013.07.022
[26]	周志刚, 胡芳伟, 鲍宗炜, 等. 兰溪市 PM$_{2.5}$ 中有机物的组成特征、季节变化及来源研究[J]. 环境科学学报, 2018, 38(6): 2253-2261.
[27]	Paatero P. Least square formulation of robust non-negative factor analysis[J]. Chemometrics and Intelligent Laboratory Systems, 1997, 37(1): 23-35. doi: 10.1016/S0169-7439(96)00044-5
[28]	Lesworth T, Baker A R, Jickells T. Aerosol organic nitrogen over the remote Atlantic Ocean[J]. Atmospheric Environment, 2010, 44(15): 1887-1893. doi: 10.1016/j.atmosenv.2010.02.021
[29]	Violaki K, Mihalopoulos N. Water-soluble organic nitrogen (WSON) in size-segregated atmospheric particles over the Eastern Mediterranean[J]. Atmospheric Environment, 2010, 44(35): 4339-4345. doi: 10.1016/j.atmosenv.2010.07.056
[30]	Miyazaki Y, Fu P, Ono K, et al. Seasonal cycles of water-soluble organic nitrogen aerosols in a deciduous broadleaf forest in northern Japan[J]. Journal of Geophysical Research: Atmospheres, 2014, 119(3): 1440-1454. doi: 10.1002/2013JD020713
[31]	Rastogi N, Zhang X, Edgerton E S, et al. Filterable water-soluble organic nitrogen in fine particles over the southeastern USA during summer[J]. Atmospheric Environment, 2010, 45: 6040-6047. doi: 10.1016/j.atmosenv.2011.07.045
[32]	Matsumoto K, Yamamoto Y, Kobayashi H, et al. Water-soluble organic nitrogen in the ambient aerosols and its contribution to the dry deposition of fixed nitrogen species in Japan[J]. Atmospheric Environment, 2014, 95: 334-343. doi: 10.1016/j.atmosenv.2014.06.037
[33]	Ho S S H, Li L, Qu L, et al. Seasonal behavior of water-soluble organic nitrogen in fine particulate matter (PM$_{2.5})$ at urban coastal environments in Hong Kong[J]. Air Quality, Atmosphere & Health, 2019, 12: 389-399.
[34]	石金辉, 韩静, 范得国, 等. 青岛大气气溶胶中水溶性有机氮对总氮的贡献[J]. 环境科学, 2011, 32(1): 1-8.
[35]	程玉婷, 王格慧, 孙涛, 等. 西安冬季非灰霾天与灰霾天 PM$_{2.5}$ 中水溶性有机氮污染特征比较[J]. 环境科学, 2014, 35(7): 2468-2476.
[36]	Fan M Y, Zhang Y L, Lin Y C, et al. Isotope-based source apportionment of nitrogen-containing aerosols: a case study in an industrial city in China[J]. Atmospheric Environment, 2019, 212: 96-105. doi: 10.1016/j.atmosenv.2019.05.020
[37]	Galloway J N, Dentener F J, Marmer E, et al. The environmental reach of Asia[J]. Annual Review of Environment and Resources, 2008, 33: 461-481. doi: 10.1146/energy.2008.33.issue-1
[38]	Ng N L, Brown S S, Archibald A T, et al. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol[J]. Atmospheric Chemistry and Physics 2017, 17(3): 2103-2162.
[39]	鲁慧莹, 彭龙, 张国华, 等. 广州大气颗粒物水溶性有机氮的粒径分布特征和来源分析[J]. 地球化学, 2019, 48(1): 57-66.
[40]	Jordan TB, Seen AJ, Jacobsen GE. Levoglucosan as an atmospheric tracer for woodsmoke[J]. Atmospheric Environment, 2006, 40: 5316-5321. doi: 10.1016/j.atmosenv.2006.03.023
[41]	Edeny E O, Kleindienst T E, Jaoui M, et al. Formation of 2-methyl tetrols and 2-methylglyceric acid in secondary organic aerosol from laboratory irradiated isoprene/NO$_\alpha$/SO$_2$/air mixtures and their detection in ambient PM$_{2.5}$ samples collected in the eastern United States[J]. Atmospheric Environment, 2005, 39(29): 5281-5289. doi: 10.1016/j.atmosenv.2005.05.031