大气烷基硝酸酯的实地测量

doi:10.6023/A23100460

化学学报 ›› 2024, Vol. 82 ›› Issue (3): 323-335.DOI: 10.6023/A23100460 上一篇下一篇

综述

大气烷基硝酸酯的实地测量

李春萌^a, 毕哲^a, 王海潮^b^,^*(), 陆克定^c^,^d^,^*()

a 中国计量科学研究院环境计量中心北京 100029
b 中山大学大气科学学院珠海 519082
c 北京大学环境科学与工程学院环境模拟与污染控制国家重点联合实验室北京 100871
d 国家环境保护大气臭氧污染防治重点实验室北京 100871

投稿日期:2023-10-23 发布日期:2024-01-04

作者简介:

李春萌, 中国计量科学研究院环境计量中心博士后, 研究方向为大气痕量物种标准物质研发和以有机硝酸酯为代表的大气化学研究.

毕哲, 中国计量科学研究院环境计量中心副研究员, 研究方向包括气体计量、仪器开发和校准, 致力于开发用于臭氧/PM_2.5前体监测的挥发性有机化合物气体标准, 并逐步开展温室气体、室内空气质量和呼出气体监测等相关领域的研究.

王海潮, 中山大学大气科学学院副教授, 研究方向为大气测量技术和大气污染成因研究.

陆克定, 研究员、博士生导师. 主要研究方向为大气环境化学和减污降碳协同防控策略, 基于自由基及其关键前体物的直接观测和动力学模拟等研究手段, 关注典型城市环境中大气自由基的来源和转化以及相应大气化学机理的研发. 曾获得国家自然科学基金优秀青年科学基金(2015)、北京市科技新星(2015)、国家环境保护专业技术青年拔尖人才(2016)、长江学者青年项目(2017)、北京市杰出青年基金项目(2019)及国家杰出青年基金项目(2023), 获得教育部自然科学奖一等奖(2017)和中国环境学会青年科学家奖金奖(2019)等.

基金资助:
国家自然科学基金(21976006); 国家自然科学基金(42175111); 广东省基础与应用基础研究基金(2020B0301030004); 中国计量科学研究院探索性创新项目(AKYCX2313)

Field Measurement of Alkyl Nitrates in the Atmosphere

Chunmeng Li^a, Zhe Bi^a, Haichao Wang^b(), Keding Lu^c^,^d()

a Center for Environmental Metrology, National Institute of Metrology, Beijing 100029
b School of Atmospheric Sciences, Sun Yat-sen University, Zhuhai, 519082
c State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871
d State Key Laboratory of Environmental Protection Atmospheric Ozone Pollution Control, Beijing 100871

Received:2023-10-23 Published:2024-01-04
Contact: *E-mail: wanghch27@mail.sysu.edu.cn;k.lu@pku.edu.cn
Supported by:
National Natural Science Foundation of China(21976006); National Natural Science Foundation of China(42175111); Guangdong Major Project of Basic and Applied Basic Research(2020B0301030004); Exploratory Innovation Project of National Institute of Metrology, China(AKYCX2313)

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摘要/Abstract

烷基硝酸酯(ANs)是对流层大气中重要的污染物, 其收支过程对大气氮、碳的分布, 光化学循环以及二次有机气溶胶生成等具有重要影响. 大气ANs种类繁多, 浓度低且化学性质活泼, 因此ANs的准确测量是大气监测领域的巨大挑战. 概述了大气ANs化学机理, 系统梳理并总结了ANs单物种和总量的实地测量技术进展, 主要包括气相色谱电子捕获技术、质谱技术、荧光光谱技术和吸收光谱技术. 研究表明吸收光谱技术具有结构简单易维护的特征, 是具有较大发展潜力的ANs总量测量方法, 质谱技术在ANs分物种测量方面具有其独特优势, 但物种化的标准源和标定技术是亟待突破的关键瓶颈. 最后, 系统归纳了不同环境类型的ANs浓度分布特征, 并对ANs化学研究难点和发展趋势进行展望.

关键词: 烷基硝酸酯, 化学机理, 单物种测量, 总量测量, 实地测量

Alkyl nitrates (ANs), chemicals with the formula RONO₂, are important oxidation products during the reaction between atmospheric nitrogen oxides (NO_x) and volatile organic compounds (VOCs). The generation of ANs removes NO_x from the atmosphere, and inhibits atmospheric oxidation by terminating the HO_x cycle. Some ANs are easily taken up by particulate, as important precursors of secondary organic aerosols, thereby affecting atmospheric air quality and global climate change. Atmospheric model simulations and field campaigns have shown that ANs are important for local complex pollution and nitrogen cycling. However, as ANs are widely distributed in the atmosphere, with a wide variety and active chemical properties, it makes the field measurements of ANs very scarce due to the lack of measurement methods and standard substances. In this study, firstly, the atmospheric chemical mechanism focused on ANs is introduced, and then the measurement techniques for single species and total ANs are summarized, which mainly include gas chromatography electron capture (GC-ECD), mass spectrometry (MS), thermal dissociation laser-induced fluorescence (TD-LIF) and absorption spectrometry. Overall, mass spectrometry is an important development direction for single-species measurement methods of ANs, while absorption spectroscopy is an emerging total measurement method with great development potential. Field measurements of ANs were carried out mainly in Europe and the United States. However, the atmospheric environment of high NO_x and high anthropogenic VOCs in China is different from that of low NO_x and high biogenic VOCs in Europe and the United States, and thus there are differences in the atmospheric distributions of ANs, which introduces challenge for field measurements of ANs. Finally, the distribution characteristics of ANs in the environments of ocean, forest, city, and free atmosphere in the troposphere are summarized, and an outlook on the difficulties and development trends of ANs chemistry at present is given, which will provide a reference for the development of the measurement technology and the research on the chemical mechanism of ANs in China.

Key words: alkyl nitrate (AN), chemical mechanism, single-species measurement, total measurement, field measurement

引用此文

李春萌, 毕哲, 王海潮, 陆克定. 大气烷基硝酸酯的实地测量[J]. 化学学报, 2024, 82(3): 323-335.

Chunmeng Li, Zhe Bi, Haichao Wang, Keding Lu. Field Measurement of Alkyl Nitrates in the Atmosphere[J]. Acta Chimica Sinica, 2024, 82(3): 323-335.

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Technique	Measuring paramater	Measure species	Calibration	Temporal resolution	Detection limit	Accuracy/%	Main interference	Ref.
GC-CL NO₂	electrical signal	C₃~C₆ alkyl nitrates; C₂~C₄ OH-AN; C₂~C₄ dinitrates	A mixed standard of 19 organic nitrates	30 min	0.25 nmol/L		—	[53]
GC-MS	mass spectrum	C₃~C₇ alkyl nitrates	C₃~C₇ AN	off-line	0.1 pL/L	5	—	[54]
GC-ECD	electrical signal	C₁~C₄ ONs	PANs standard	12 min	10 pL/L	5	halogenated hydrocarbon	[55]
TD-LIF	fluorescence spectrum	ANs, PNs, NO₂	PAN, 2 alkyl nitrate, NO₂ standard	10 s	90 pL/L	10~15	Ambient NO_x; HNO₃	[56]
CIMS	mass spectrum	ISOPN, MOBN, PROPNN, MVKN＋MACRN, ETHLN	nitric acid (relative sensitivity)	1.6 h	0.1 pL/L	40	humidity; ¹³C isotope signal	[57]
GC-MS	mass spectrum	2 β-IHN, 4 ICN, propanone nitrate	n-butyl nitrate (relative sensitivity)	1 h	1 pL/L	14	humidity	[58]
TD-CAPS	phase shift	ONs, PNs, NO₂	PAN, PPN, 5 alkyl nitrates, NO₂ standard	2 min	21 pL/L	—	Ambient NO₂; HNO₃	[59]
TD-CRDS	ring-down time	ANs, PNs, NO₂	i-propyl nitrate, PAN, NO₂standard	4 min	80/94/59 pL/L	8	humidity; ClNO₂; ambient NO₂	[60]
TD-CEAS	absorption spectrum	ANs, PNs, NO₂	PAN standard	3 min	91 pL/L	8	ambient NO_x	[61]

Technique	Measuring paramater	Measure species	Calibration	Temporal resolution	Detection limit	Accuracy/%	Main interference	Ref.
GC-CL NO₂	electrical signal	C₃~C₆ alkyl nitrates; C₂~C₄ OH-AN; C₂~C₄ dinitrates	A mixed standard of 19 organic nitrates	30 min	0.25 nmol/L		—	[53]
GC-MS	mass spectrum	C₃~C₇ alkyl nitrates	C₃~C₇ AN	off-line	0.1 pL/L	5	—	[54]
GC-ECD	electrical signal	C₁~C₄ ONs	PANs standard	12 min	10 pL/L	5	halogenated hydrocarbon	[55]
TD-LIF	fluorescence spectrum	ANs, PNs, NO₂	PAN, 2 alkyl nitrate, NO₂ standard	10 s	90 pL/L	10~15	Ambient NO_x; HNO₃	[56]
CIMS	mass spectrum	ISOPN, MOBN, PROPNN, MVKN＋MACRN, ETHLN	nitric acid (relative sensitivity)	1.6 h	0.1 pL/L	40	humidity; ¹³C isotope signal	[57]
GC-MS	mass spectrum	2 β-IHN, 4 ICN, propanone nitrate	n-butyl nitrate (relative sensitivity)	1 h	1 pL/L	14	humidity	[58]
TD-CAPS	phase shift	ONs, PNs, NO₂	PAN, PPN, 5 alkyl nitrates, NO₂ standard	2 min	21 pL/L	—	Ambient NO₂; HNO₃	[59]
TD-CRDS	ring-down time	ANs, PNs, NO₂	i-propyl nitrate, PAN, NO₂standard	4 min	80/94/59 pL/L	8	humidity; ClNO₂; ambient NO₂	[60]
TD-CEAS	absorption spectrum	ANs, PNs, NO₂	PAN standard	3 min	91 pL/L	8	ambient NO_x	[61]

Time	Location	Environmental type	Measured species	Technique	Major finding	Ref.
April~July, 1986	North Pacific Ocean	Remote	C₃~C₅ AN	GC-ECD/GC-NI-MS	The first direct evidence for existence and transport of C₃~C₅ alkyl nitrates in the troposphere are provided	[62]
July~August, 1986	Pennsylvania, USA	Rural	C₂~C₅ AN	GC-ECD	Each of the organic nitrates exhibited a marked diurnal variation, about 15% of the measured NO_y could not be accounted for by the sum of the individually measured species	[23]
August, 1992	Ontario, Canada	Rural	C₃~C₆ ANs, C₂~C₄ OH-ANs, 1,2-diANs	GC-ECD-CL	First report about the field observation of multifunctional nitrates	[94]
March~May, 1993	Alaska, USA	Forest	C₂~C₆ AN	GC-ECD/GC-MS	PAN is correlated with ozone, and alkyl nitrates are correlated with alkane	[54]
August~September, 1993	Nova Scotia, Canada	Suburban	C₁~C₄AN	GC-ECD	The comparison of the ratios of alkyl nitrates to their parent hydrocarbons to that of 2-butyl nitrate/butane showed significant deviations from trends predicted from rate constants, branching ratios, and loss rates	[95]
August, 1995	California, USA	Coastline	C₁~C₁₅ AN, di-ANs and benzyl nitrate	GC-ECD/GC-MS	The ≥C₆ alkyl nitrates in continental air can contribute 1%~2% to the total NO_y, and the relative abundance of benzyl nitrate compared to alkyl (mono) nitrates is used as a tool for global air mass characterization	[18]
May~June, 1994	The South Atlantic	Remote	C₃~C₁₄ AN	GC-ECD/GC-MSD	Higher concentrations in the west wind belt reveal the influence of the South American continent as the source for the alkyl nitrates, long chain alkyl nitrates is useful as trace indicators to distinguish continental and marine air masses	[80]
October~November, 1996	Atlantic Ocean	Ship-based	C₁~C₁₃ AN, C₃~C₆ di-AN, C₂~C₆ OH-AN, benzyl nitrate	GC-ECD/GC-MSD	The low concentrations in marine air reflect chemical and physical loss processes during long-range transport of the air starting from the continent	[96]
14 July~19 August, 1998	Michigan, US	Forest -Tower	Isoprene nitrates	GC-TD-PL	Concentrations of isoprene nitrates exhibited a strong diurnal variation consistent with their expected chemical and physical removal rates	[85]
February, 1999	Neumayer Station, Antarctic	Remote	C₁~C₉ AN, C₂~C₄ di- =AN, C₂~C₄ OH-AN	GC-ECD	The common assumption are confirmed that there are no biogenic marine sources of C₂~C₉ organic nitrates in Antarctic	[97]
October, 2000; August, 2000; July, 2001	Blodgett Forest/ La Porte/Granite Bay, USA	Rural/Suburban/ Urban	ANs	TD-LIF	ANs are a large part, if not all, of the ‘missing NO_y’ reported in many prior experiments	[1]
March, 2003~ February, 2004	Big Hill, USA	Remote	ANs	TD-LIF	The important contribution of ANs to NO_y in the region suggests that they should be considered with regards to export of NO_y from the boundary layer	[98]
August, 2001~December, 2002	Hong Kong, China	Coastline	C₁~C₅AN	GC-ECD	The C₃~C₄ (rather than C₁~C₂) alkyl nitrates were most abundant, showing the importance of photochemical (rather than marine) RONO₂ production	[99]
July~August, 2004	North Atlantic	Airborne	C₁~C₅ AN	GC-MS	The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place	[100]
July~August 2004	North America	Airborne	C₁~C₅ AN, ANs	GC-ECD/GC-MS/TD-LIF	The sum of isoprene nitrate and other alkyl and multifunctional nitrates contribute about 10% to the mean NO_y in the continental boundary layer	[101]
Spring of 2006	Mexico City	Airborne	ANs	TD-LIF	ANs were observed to be 10%~20% of NO_y in the Mexico City plume, and ANs formation suppressed peak ozone production rates by as much as 40% in the near-field of Mexico City	[81]
17 March and 29 March 2006	Mexico City	Urban	ANs	TD-LIF	Reductions in VOC reactivity that inadvertently reduce organic nitrate production rates will be counterproductive without concurrent reductions in NO_x or other organics	[3]
June~August 2009	Sierra Nevada, US	Forest	multifunctional RONO2, ANs	CIMS/TD-LIF	The sum of the individual biogenically derived nitrates account for two-thirds of the ANs, confirming predictions of the importance of biogenic nitrates to the NO_y budget	[57]
2012	Beijing, China	Urban	C₁~C₄ AN	canister samples & GC	Ox/RONO₂ could indicate the relative importance of carbonyls to Ox formation	[102]
June~July 2008	Boreal forest, Canada	Airborne	ANs	TD-LIF	ANs account for ≈20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO₃	[84]
July~August 2011	Colorado, USA	Forest	ANs	TD-LIF	Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site	[11]
January~February, 2012	Utah, USA.	Tower	ANs	TD-LIF	ANs were a large fraction (≈60%) of the HO_x free radical chain termination and the temperature dependence of the alkyl nitrate yields enhances the role of ANs in local chemistry during winter	[83]
May~July, 2013	Centerville, USA	Forest	Isoprene hydroxy nitrates	CIMS	NO as the limiting factor for ambient IN production during SOAS	[92]
September~November, 2010	Hong Kong, China	Remote/Urban	C₁~C₄ AN	GC-ECD	Secondary formation was the prominent contributor of ANs in the meso scenario, while biomass burning and secondary formation made comparable contributions to ANs in the nonmeso scenario	[7]
June~July, 2013	Bibb County, Alabama, USA	Rural	ANs	TD-LIF	The lifetime of NO_x during the daytime is controlled primarily by the production and loss of ANs which were predominantly produced during isoprene oxidation	[67]
August~September, 2011	Kleiner Feldberg, Germany	Rural	ANs	TD-CRDS	A significant fraction of NO_x (up to 75%) is sequestered as organics nitrates, and the night-time production of alkyl nitrates by reaction of NO₃ with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways	[60]
May, August, November, 2011; February, 2012	Hong Kong, China	Suburban	C₁~C₄ AN	GC-ECD	The photochemical formation and biomass burning were the major sources of C₂~C₄ RONO₂, whereas MeONO₂ was mainly from oceanic emissions during the entire sampling period	[103]
June, 2005/July, 2008	Beijing, China	Urban/Rural	C₁~C₅ AN	GC-ECD/MSD	The mixing ratios of RONO₂ were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution	[104]
February~April, June~July, 2017	Yellow River Delta, China	Rural	C₁~C₅ AN	GC-ECD/MSD	Alkyl nitrates showed well-defined diurnal variations, elucidating the effects of in-situ photochemical production and regional transport of aged polluted plumes	[105]
December, 2012~December, 2015	Suzu, Japan	Remote	ANs	TD-CAPS	PNs and ONs showed similar seasonal variations with maximum concentrations in spring and minimum concentrations in summer	[106]
May~June, 2017	Beijing, China	Urban	Isoprene nitrates	GC-NI-MS	In the summertime conditions experienced in Beijing the ratio of (1-OH, 2-ONO₂) IHN to (4-OH, 3-ONO₂)-IHN (the numbers indicate the carbon atom in the isoprene chain to which the radical is added) increases at NO mixing ratios below 2 nL/L	[93]
August~September, 2019	Chengdu, China	Suburban	ANs	TD-CEAS	The production of both O₃ and ANs was in the VOC-limited regime and highlights the importance of VOC control (especially aromatics) to mitigate photochemical pollution in Chengdu	[8]

Time	Location	Environmental type	Measured species	Technique	Major finding	Ref.
April~July, 1986	North Pacific Ocean	Remote	C₃~C₅ AN	GC-ECD/GC-NI-MS	The first direct evidence for existence and transport of C₃~C₅ alkyl nitrates in the troposphere are provided	[62]
July~August, 1986	Pennsylvania, USA	Rural	C₂~C₅ AN	GC-ECD	Each of the organic nitrates exhibited a marked diurnal variation, about 15% of the measured NO_y could not be accounted for by the sum of the individually measured species	[23]
August, 1992	Ontario, Canada	Rural	C₃~C₆ ANs, C₂~C₄ OH-ANs, 1,2-diANs	GC-ECD-CL	First report about the field observation of multifunctional nitrates	[94]
March~May, 1993	Alaska, USA	Forest	C₂~C₆ AN	GC-ECD/GC-MS	PAN is correlated with ozone, and alkyl nitrates are correlated with alkane	[54]
August~September, 1993	Nova Scotia, Canada	Suburban	C₁~C₄AN	GC-ECD	The comparison of the ratios of alkyl nitrates to their parent hydrocarbons to that of 2-butyl nitrate/butane showed significant deviations from trends predicted from rate constants, branching ratios, and loss rates	[95]
August, 1995	California, USA	Coastline	C₁~C₁₅ AN, di-ANs and benzyl nitrate	GC-ECD/GC-MS	The ≥C₆ alkyl nitrates in continental air can contribute 1%~2% to the total NO_y, and the relative abundance of benzyl nitrate compared to alkyl (mono) nitrates is used as a tool for global air mass characterization	[18]
May~June, 1994	The South Atlantic	Remote	C₃~C₁₄ AN	GC-ECD/GC-MSD	Higher concentrations in the west wind belt reveal the influence of the South American continent as the source for the alkyl nitrates, long chain alkyl nitrates is useful as trace indicators to distinguish continental and marine air masses	[80]
October~November, 1996	Atlantic Ocean	Ship-based	C₁~C₁₃ AN, C₃~C₆ di-AN, C₂~C₆ OH-AN, benzyl nitrate	GC-ECD/GC-MSD	The low concentrations in marine air reflect chemical and physical loss processes during long-range transport of the air starting from the continent	[96]
14 July~19 August, 1998	Michigan, US	Forest -Tower	Isoprene nitrates	GC-TD-PL	Concentrations of isoprene nitrates exhibited a strong diurnal variation consistent with their expected chemical and physical removal rates	[85]
February, 1999	Neumayer Station, Antarctic	Remote	C₁~C₉ AN, C₂~C₄ di- =AN, C₂~C₄ OH-AN	GC-ECD	The common assumption are confirmed that there are no biogenic marine sources of C₂~C₉ organic nitrates in Antarctic	[97]
October, 2000; August, 2000; July, 2001	Blodgett Forest/ La Porte/Granite Bay, USA	Rural/Suburban/ Urban	ANs	TD-LIF	ANs are a large part, if not all, of the ‘missing NO_y’ reported in many prior experiments	[1]
March, 2003~ February, 2004	Big Hill, USA	Remote	ANs	TD-LIF	The important contribution of ANs to NO_y in the region suggests that they should be considered with regards to export of NO_y from the boundary layer	[98]
August, 2001~December, 2002	Hong Kong, China	Coastline	C₁~C₅AN	GC-ECD	The C₃~C₄ (rather than C₁~C₂) alkyl nitrates were most abundant, showing the importance of photochemical (rather than marine) RONO₂ production	[99]
July~August, 2004	North Atlantic	Airborne	C₁~C₅ AN	GC-MS	The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place	[100]
July~August 2004	North America	Airborne	C₁~C₅ AN, ANs	GC-ECD/GC-MS/TD-LIF	The sum of isoprene nitrate and other alkyl and multifunctional nitrates contribute about 10% to the mean NO_y in the continental boundary layer	[101]
Spring of 2006	Mexico City	Airborne	ANs	TD-LIF	ANs were observed to be 10%~20% of NO_y in the Mexico City plume, and ANs formation suppressed peak ozone production rates by as much as 40% in the near-field of Mexico City	[81]
17 March and 29 March 2006	Mexico City	Urban	ANs	TD-LIF	Reductions in VOC reactivity that inadvertently reduce organic nitrate production rates will be counterproductive without concurrent reductions in NO_x or other organics	[3]
June~August 2009	Sierra Nevada, US	Forest	multifunctional RONO2, ANs	CIMS/TD-LIF	The sum of the individual biogenically derived nitrates account for two-thirds of the ANs, confirming predictions of the importance of biogenic nitrates to the NO_y budget	[57]
2012	Beijing, China	Urban	C₁~C₄ AN	canister samples & GC	Ox/RONO₂ could indicate the relative importance of carbonyls to Ox formation	[102]
June~July 2008	Boreal forest, Canada	Airborne	ANs	TD-LIF	ANs account for ≈20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO₃	[84]
July~August 2011	Colorado, USA	Forest	ANs	TD-LIF	Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site	[11]
January~February, 2012	Utah, USA.	Tower	ANs	TD-LIF	ANs were a large fraction (≈60%) of the HO_x free radical chain termination and the temperature dependence of the alkyl nitrate yields enhances the role of ANs in local chemistry during winter	[83]
May~July, 2013	Centerville, USA	Forest	Isoprene hydroxy nitrates	CIMS	NO as the limiting factor for ambient IN production during SOAS	[92]
September~November, 2010	Hong Kong, China	Remote/Urban	C₁~C₄ AN	GC-ECD	Secondary formation was the prominent contributor of ANs in the meso scenario, while biomass burning and secondary formation made comparable contributions to ANs in the nonmeso scenario	[7]
June~July, 2013	Bibb County, Alabama, USA	Rural	ANs	TD-LIF	The lifetime of NO_x during the daytime is controlled primarily by the production and loss of ANs which were predominantly produced during isoprene oxidation	[67]
August~September, 2011	Kleiner Feldberg, Germany	Rural	ANs	TD-CRDS	A significant fraction of NO_x (up to 75%) is sequestered as organics nitrates, and the night-time production of alkyl nitrates by reaction of NO₃ with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways	[60]
May, August, November, 2011; February, 2012	Hong Kong, China	Suburban	C₁~C₄ AN	GC-ECD	The photochemical formation and biomass burning were the major sources of C₂~C₄ RONO₂, whereas MeONO₂ was mainly from oceanic emissions during the entire sampling period	[103]
June, 2005/July, 2008	Beijing, China	Urban/Rural	C₁~C₅ AN	GC-ECD/MSD	The mixing ratios of RONO₂ were comparable between both sites, emphasizing the regional nature of alkyl nitrate pollution	[104]
February~April, June~July, 2017	Yellow River Delta, China	Rural	C₁~C₅ AN	GC-ECD/MSD	Alkyl nitrates showed well-defined diurnal variations, elucidating the effects of in-situ photochemical production and regional transport of aged polluted plumes	[105]
December, 2012~December, 2015	Suzu, Japan	Remote	ANs	TD-CAPS	PNs and ONs showed similar seasonal variations with maximum concentrations in spring and minimum concentrations in summer	[106]
May~June, 2017	Beijing, China	Urban	Isoprene nitrates	GC-NI-MS	In the summertime conditions experienced in Beijing the ratio of (1-OH, 2-ONO₂) IHN to (4-OH, 3-ONO₂)-IHN (the numbers indicate the carbon atom in the isoprene chain to which the radical is added) increases at NO mixing ratios below 2 nL/L	[93]
August~September, 2019	Chengdu, China	Suburban	ANs	TD-CEAS	The production of both O₃ and ANs was in the VOC-limited regime and highlights the importance of VOC control (especially aromatics) to mitigate photochemical pollution in Chengdu	[8]

大气烷基硝酸酯的实地测量

Field Measurement of Alkyl Nitrates in the Atmosphere

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