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有机硝酸酯的大气化学及测量

邵豆 ,  秦敏 ,  方武 ,  韩宝彬 ,  解建业 ,  赵夏丹 ,  廖知堂 ,  胡嘉琪 ,  任恩伯

化学进展 ›› 2024, Vol. 36 ›› Issue (8) :1145-1156

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化学进展 ›› 2024, Vol. 36 ›› Issue (8) :1145-1156 DOI: 10.7536/PC240111
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有机硝酸酯的大气化学及测量

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Atmospheric Chemistry and Measurement Research on Organic Nitrates

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摘要

Organic nitrates (ONs) are an important class of nitrogenous organic compounds in the atmosphere. ONs in the atmosphere is mainly formed by the photochemical reaction of atmospheric oxidants and volatile organic compounds in the presence of nitrogen oxides, and its formation and destruction process is closely related to the formation of atmospheric nitrogen cycle, ozone and secondary organic aerosols; Some gas-phase ONs can also enter the particle phase through gas-particle distribution or multiple oxidation to form particle-phase ONs, which can promote the formation of PM2.5 and further endanger human health. At present, a variety of chemical and spectroscopic measurement techniques have been successfully applied to the concentration measurement of single species and total ONs in the atmosphere, and joint field observations of various atmospheric components have been carried out in different regions to explore the formation mechanism of ONs involving nitrogen oxides, the impact of ONs on regional nitrogen chemistry, and the contribution of particulate ONs to secondary organic aerosols. In this paper, the important role of ONs in atmospheric chemistry is pointed out from the generation and dissipation mechanism of ONs, and the existing measurement methods of ONs are summarized, and the characteristics and applications of different methods are pointed out.This paper focuses on the indoor smog chamber study related to ONs and the field observation results in different regions at home and abroad, and expounds its role in atmospheric chemistry combined with the atmospheric chemistry model, and points out some shortcomings in the current research, so as to continuously improve in the follow-up study.

Abstract

Organic nitrates(ONs)are an important nitrogen-containing organic compounds in the atmosphere.Atmospheric ONs are primarily produced by secondary photochemical reactions between atmospheric oxidants and volatile organic compounds in the presence of nitrogen oxides.Their generation and removal processes are closely related to the atmospheric nitrogen cycle,ozone,and the formation of secondary organic aerosols.Additionally,partial gas-phase ONs can enter the particle phase through gas-particle distribution or multiple oxidations,forming particle-phase ONs,which will promote the generation of PM2.5and further damage to human health.Currently,various chemical and spectroscopic measurement techniques have been successfully applied to measure the concentrations of single species and total ONs,and comprehensive field observations of various atmospheric components have been carried out in different regions to explore the mechanism of ONs generation involving nitrogen oxides,the impact of ONs on regional nitrogen chemistry,and the contribution of particulate ONs to secondary organic aerosols.This article discusses the important role of ONs in atmospheric chemistry by elucidating their mechanisms of generation and removal.It summarizes the measurement methods for ONs and highlights the characteristics and applications of different methods.The focus is placed on indoor smoke chamber researches related to ONs and field observation results in different regions.The observed data combined with atmospheric chemical models,further explain the atmospheric chemical effects of ONs.Additionally,it identifies some shortcomings in current researches,that need to be improved in subsequent researches 。

Contents

1 Introduction

2 Sources and sinks of atmospheric organic nitrates

3 Quantification methods of atmospheric organic nitrates

4 Researches on indoor smog chamber of organic nitrates

5 Field observations of organic nitrates

5.1 International field observations

5.2 Domestic field observations

6 Conclusion and outlook

Graphical abstract

关键词

有机硝酸酯 / 大气化学 / 测量技术 / 外场观测

Key words

organic nitrates / atmospheric chemistry / measurement technology / field observations

引用本文

引用格式 ▾
邵豆, 秦敏, 方武, 韩宝彬, 解建业, 赵夏丹, 廖知堂, 胡嘉琪, 任恩伯. 有机硝酸酯的大气化学及测量[J]. 化学进展, 2024, 36(8): 1145-1156 DOI:10.7536/PC240111
Dou Shao, Min Qin, Wu Fang, Baobin Han, Jianye Xie, Xiadan Zhao, Zhitang Liao, Jiaqi Hu, Enbo Ren. Atmospheric Chemistry and Measurement Research on Organic Nitrates[J]. Progress in Chemistry, 2024, 36(8): 1145-1156 DOI:10.7536/PC240111

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1 引言

有机硝酸酯(Organic nitrates,ONs)一般是指含有硝酸酯官能团(—ONO2)的一类有机化合物,是一种重要的活性氮氧化物(NOy=NO+NO2+NO3+ ΣONs+HNO3+HONO+2N2O5+…)。根据ONs中其他基团结构的不同,可分为过氧硝酸酯(RO2NO2,PNs)和烷基硝酸酯(RONO2,ANs)。含有酰基的PNs(PANs)热稳定性相对较高,在大气中含量相对较高,而不含酰基的一类则易受热分解,在大气中的含量较少[1]。依据碳链长度的不同,ANs可分为短链ANs(C≤2)、中长链ANs(3≤C≤5)和长链ANs(C>5)[2]。大气中的ONs主要来自挥发性有机物(VOCs)和大气氧化剂的相互作用过程,由$\mathrm{RO} \bullet$/$\mathrm{RO} \bullet _{2}$与NO2反应生成的ONs可以作为氮氧化物(NOx)的储库,经大气传输至偏远地区,再次分解释放NOx,对区域氮循环起着重要的作用,进而影响后续臭氧(O3)的生成[3,4]。此外,不同挥发性的气相ONs还可以通过气粒分配或多次氧化进入颗粒相,形成颗粒相ONs,对高NOx水平地区二次有机气溶胶(SOA)的形成有重要影响。有观测数据显示,美国东南部城市地区颗粒相ONs占有机气溶胶(OA)的9%~25%,农村地区颗粒相ONs占OA的5%~12%[5];贝克斯菲尔德的森林地区由单萜烯氧化主导夜间ONs的生成,对OA生长的贡献约为27%~40%[6];此外,二次转化生成的颗粒相ONs也广泛存在于欧洲城市和农村地区的OA组分中,平均占PM1中有机组分的42%[7];朝鲜半岛上空的机载观测显示,25%的ONs处于颗粒相,预计占OA的15%[8];而在我国北京地区,冬季OA中颗粒相ONs可达25%[9]。大气颗粒物中的颗粒相ONs能进一步影响大气环境,危害人体健康。ONs的源汇及大气化学作用引起越来越多的关注。

实际大气环境中,ONs的前体VOCs种类众多,影响其生成的物理和化学过程也因大气环境的不同而有所差异,因此生成的ONs也多种多样,各种测量技术针对单物种ONs以及ONs总量进行定量,已在全球范围内的多个地区进行了多次外场观测[10⇓⇓⇓⇓⇓⇓⇓~18],但由于缺乏标准品,难以对不同结构和性质的ONs一一定量,目前多将外场观测数据和大气化学模型相结合进行大气化学研究,或在实验室开展针对ONs生成的烟雾箱研究。本文针对ONs的生消机制、测量方法、室内烟雾箱研究以及外场观测情况进行了详细总结,阐明了ONs最新的研究进展,并对未来的发展方向进行了归纳。

2 大气有机硝酸酯的源和汇

大气中的ONs主要分为自然源和人为源。过氧乙酰硝酸酯(PAN)作为PNs中最丰富的物种,最早在洛杉矶烟雾事件中被发现[19]。大气中没有PAN的自然源,只能通过后续的光化学反应二次生成,现已作为光化学污染的重要指示剂之一[20,21]。不同于PAN,ANs既可由自然界直接排放,又可人为产生。海洋[22,23]和生物质燃烧[24⇓~26]的一次排放是其主要的自然源。热带海域中饱和短链ANs的挥发是短链ANs主要的自然来源,例如甲基硝酸酯(MeONO2)受海洋排放影响最大[27,28],随着碳链的增长由海洋直接排放的ANs逐渐减少;而在温带水域中 ANs处于平衡状态,不易挥发。除了自然排放源之外,ANs还可以通过光化学反应二次生成。二次光化学反应生成ONs的三种主要途径包括[29,30]:

(1)OH自由基引发的碳氢化合物氧化

OH自由基引发的碳氢化合物氧化是白天ONs形成的主要途径。在OH自由基的氧化作用下,饱和碳氢化合物脱氢或者不饱和碳氢化合物发生加成反应生成$\mathrm{R} \bullet$(式1),随后$\mathrm{R} \bullet$迅速与O2反应生成$\mathrm{RO}_{2\bullet}$(式2)。

$\mathrm{RH} / \mathrm{R}_{1}=\mathrm{R}_{2}+\mathrm{OH} \rightarrow \mathrm{R} \bullet+\mathrm{H}_{2} \mathrm{O}$
$\mathrm{R} \bullet+\mathrm{O}_{2} \rightarrow \mathrm{RO}_{2} \bullet$

当存在NOx时,$\mathrm{RO}_{2\bullet}$和NO的分支反应生成$\mathrm{RO} \bullet$和NO2(式3),继续参与NOx循环,分支反应(式4)则生成ANs,其中(式3)占主导作用,反应分支比为α。$\mathrm{RO}_{2\bullet}$还与NO2反应生成PNs(式5)。一般来说,不饱和碳烃化合物与OH自由基反应生成ONs的产率比饱和碳烃化合物要高,异戊二烯和α-蒎烯均通过加成与OH自由基反应得到ONs[9,31]。

$\alpha \mathrm{RO}_{2} \bullet+\mathrm{NO} \rightarrow \mathrm{RO} \bullet+\mathrm{NO}_{2}$
$(1-\alpha) \mathrm{RO}_{2} \bullet+\mathrm{NO} \rightarrow \mathrm{RONO}_{2}$
$\mathrm{RO}_{2} \bullet+\mathrm{NO}_{2} \rightarrow \mathrm{RO}_{2} \mathrm{NO}_{2}$

(2)NO3自由基引发的烯烃氧化

NO3自由基引发的烯烃氧化是夜间ONs形成的主要途径。NO3自由基与碳碳双键加成反应生成$\mathrm{R} \bullet$(式6),与(式2)类似,$\mathrm{R} \bullet$迅速与O2反应生成$\mathrm{RO}_{2\bullet}$(式7)。$\mathrm{RO}_{2\bullet}$与HO2、RO2或者NO3反应生成稳定的醛、醇或硝酸酯产物。

$\mathrm{R}_{1}=\mathrm{R}_{2}+\mathrm{NO}_{3} \rightarrow \mathrm{R}_{1}\left(\mathrm{ONO}_{2}\right) \mathrm{R}_{2} \bullet$
$\mathrm{R}_{1}\left(\mathrm{ONO}_{2}\right) \mathrm{R}_{2} \bullet+\mathrm{O}_{2} \rightarrow \mathrm{R}_{1}\left(\mathrm{ONO}_{2}\right) \mathrm{R}_{2} \mathrm{O}_{2}$

(3)O3引发的生物源挥发性有机物氧化

O3与碳碳双键反应生成初代臭氧化合物(POZ)(式8),POZ通过克氏中间体快速分解形成OH和$\mathrm{RO}_{2}$(在O2存在时),在NO存在的情况下,RO2通过一系列氧化反应生成ONs (式9)。此外,O3还可以通过光解产生OH自由基或与NO2反应生成NO3自由基,进一步与VOCs氧化生成ONs。

$\mathrm{R}_{1}=\mathrm{R}_{2}+\mathrm{O}_{3} \rightarrow \mathrm{POZ}$
$\mathrm{POZ}+\mathrm{O}_{2} \rightarrow \mathrm{OH}+\mathrm{RO}_{2} \rightarrow \mathrm{ONs}$

上述过程产生的第一代ONs中,挥发性较低的ONs通过气粒分配直接进入颗粒相,而挥发性较高的则经过多次氧化生成更稳定、饱和蒸气压更低的多官能团ONs,再由气粒分配进入颗粒相[29]。ONs的气粒分配遵循吸附分配理论[32],某种物质在固定相中达到平衡的分数可由公式(1)表示:

$K_{\mathrm{p}}=\frac{C_{\mathrm{i}, \mathrm{p}}}{C_{\mathrm{i}}}=\frac{C_{\mathrm{OA}} / C_{\mathrm{i}}^{*}(T)}{1+C_{\mathrm{OA}} / C_{\mathrm{i}}^{*}(T)}$

其中,$C_{i,p}$和$C_{i}$分别表示物质i在颗粒相中的浓度和在大气中的总浓度(包括气相和颗粒相),$C_{\mathrm{i}}^{*}(T)$表示物质i与温度(T)相关的饱和浓度,$C{OA}$表示OA的浓度。根据公式(1),气粒分配平衡与T以及OA浓度相关[33]。然而由于大气环境的复杂性以及ONs种类的多样性,由不同种类气相ONs多次氧化生成颗粒相ONs的过程仍值得探索,这对于二次有机物的大气化学估算和环境影响评估有重要意义。

生成的ONs通过光解[34]、水解[35]、热分解以及沉降[36]等方式去除。例如,在7 km以上的高空平流层,光解是PAN最重要的去除途径[37],对流层PAN的主要损耗途径为热分解;对ANs来说,与OH反应(式10)、光解(式11)以及水解是其重要的损耗途径[38,39],三者相互竞争[39⇓~41],烷基取代基个数、官能团和碳架是控制ANs水解速率的三个重要因素[35]。

$\mathrm{RONO}_{2}+\mathrm{OH} \rightarrow \mathrm{ROH}+\mathrm{NO}_{3}$
$\mathrm{RONO}_{2}+\mathrm{h} \nu \rightarrow \mathrm{RO}+\mathrm{NO}_{2}$

上述不同种类ONs的生消机制不能一概而论,前体VOCs、氧化剂以及大气环境对ONs的生成均有影响,ONs光解、水解等去除方式相关方面的研究也较为有限,尽可能地深入了解不同ONs的源汇,有助于完善大气模型并对大气氮循环做出更深刻的理解。

3 大气有机硝酸酯的定量方法

ONs种类众多且在大气中浓度较低,对不同种类ONs定量十分困难,目前多针对特定种类的ONs或ONs总量进行定量,常见的定量方法包括气相/液相色谱-质谱法(Gas chromatography/Liquid chromatography mass spectrum, GC/LC-MS)[42⇓⇓⇓~46]、气相色谱-电子捕获法(Gas chromatography-electron capture detector, GC-ECD)[47⇓~49]、化学电离质谱法(Chemical ionization mass spectrum, CIMS)[50⇓~52]、气溶胶质谱法(Aerosol mass spectrum, AMS)[53⇓~55]、傅里叶变换红外光谱法(Fourier transform infrared spectroscopy, FTIR)[56,57]、热解法(Thermal dissociation, TD)[58⇓⇓⇓⇓⇓⇓⇓⇓~67]等。多种定量方法为ONs的外场观测提供了选择。表1总结了不同定量方法的特点及应用。下面对几种测量方法进行详细介绍。

GC-MS是早期用于定量特定ONs的方法之一[29]。该方法通过气相色谱技术,对采集的膜样品进行分离,再由质谱利用离子质荷比不同将碎片分开,实现对特定ONs定量分析。GC-MS适用于半挥发性ONs的分离和测定;LC-MS则适用于热不稳定以及极性ONs的定量分析。两种方法能够为复杂ONs的识别提供强有力的依据。GC-ECD是目前常用的一种定量分析方法。该方法与GC-MS的区别是检测器不同。ECD检测器是放射性离子化检测器的一种,它是利用放射性同位素,在衰变过程中放射的具有一定能量的β-粒子作为电离源,当经过气相色谱分离后的载气中包含带有微量电负性组分进入离子室时,基流发生明显变化,从而得到特定ONs的浓度信息。目前,GC-ECD多用于PAN的定量分析。FIGAERO-CIMS使用反应离子加合到硝酸酯分子,进而进行质谱测定,软电离、响应快、灵敏度高,可以实现实时测量多种ONs。AMS采用硬电离源获得质谱碎片NO+/NO2+信息,利用该比值在有机和无机硝酸盐中的差异区分并定量ΣONs(比值法),但不同ONs的NO+/NO2+比值也有所差异,因此存在不确定性。AMS结合正交因子矩阵受体模型(PMF),解析判断有机和无机硝酸盐的相对贡献,在一定程度上弥补了比值法不确定性带来的误差。

区别于上述化学方法,FTIR是早期用于定量ΣONs的光谱学方法之一[57]。该方法利用硝酸酯官能团在红外光谱的特定吸收(860、1280、1630~ 1640 cm-1)进行总量定量,测量过程不需要前处理,简单方便,但分辨率低,检测限较高。TD法最早由Day等[58]提出,是目前定量ΣONs的常用方法之一。该方法利用了ONs的热分解特性,将ONs加热到不同温度分解为NO2和其他自由基(RO或RO2),结合激光诱导荧光检测器(LIF)测量分解产生的NO2,实现ΣPNs和ΣANs的测量。2009年,Paul等[59]将TD和腔衰荡光谱技术(CRDS)相结合,同步测量大气NO2、ΣPNs和ΣANs。Rollins等[62]结合气体剥离器实现对颗粒相ONs定量。2021年,Li等[64]结合宽带腔增强吸收光谱技术(BBCEAS)同样实现了ΣONs分类测量。

如上所述,多种测量方法已成功应用于不同条件的实验室研究和外场观测。对于特定ONs的测量,多依赖于标准品,需要对仪器进行定期标定,(例如GC/LC-MS以及GC-ECD),此外,将观测数据和模型处理结果对比时,可能由于对特定大气环境下生成的未知ONs缺乏认识而产生测量偏差。为满足长期快速准确的测量要求,对ΣONs的外场观测多采用TD法,但该方法存在多种干扰因素,需要在仪器设计方法做多方面考虑,对已知干扰因子扣除或定量标定,对仪器设计和实验室标定方面要求较高。此外,TD法还可用于ONs气粒分配研究,Aruffo等[68]利用TD-LIF技术,研究了α-蒎烯光氧化形成ONs的气粒分配,Rollins等[32]利用TD-LIF在美国贝克斯菲尔德的观测数据表明,21%的ΣANs处于颗粒相。

4 有机硝酸酯的室内烟雾箱研究

为进一步明确ONs生成机制及其对大气化学的影响,不少研究小组在实验室进行了烟雾箱模拟,将不同VOCs前体物和大气氧化剂反应,测量不同反应体系中生成的ONs。常用于烟雾箱模拟的VOCs包括生物源VOCs(BVOCs)和人为源VOCs(AVOCs)。

目前与ONs烟雾箱实验相关的BVOCs主要有异戊二烯和单萜烯(α-蒎烯、β-蒎烯、柠檬烯等),各种BVOCs在NOx存在时会迅速反应生成SOA和ONs,但因BVOCs种类不同,ONs产率具有差异性。“异戊二烯+NO3”反应的ONs产率为65%~90%[69⇓⇓~72],高产率ONs可以作为夜间NOx的汇。对“α-蒎烯+NO3”反应的研究表明,由于实验条件不同(NO3来源、前体物浓度以及种子颗粒的选择等),RO2的反应途径(“RO2+RO2”、“RO2+NO3”及“RO2+HO2”)不同,导致SOA产率差异较大(0~>21%),因而ONs产率存在不同争议[73⇓⇓⇓~77]。多数研究主要采用“α-蒎烯+OH”反应获得较高的SOA和ONs产率。例如,Rindelaub等[78]报告了“α-蒎烯+OH”在高NOx条件下进行光化学反应,ONs产率为26%±7%。此外,“α-蒎烯+OH”反应所得ONs的气粒分配与OA浓度、温度以及NOx水平相关[68,79]。“α-蒎烯&β-蒎烯+OH”以及“β-蒎烯+NO3”反应均观察到了高含氧ONs(HOM-ONs),其形成可以由RO2自由基的单分子或双分子反应来解释[80,81]。有实验表明“柠檬烯+NO3”与“柠檬烯+OH”的ONs产率相当(~30%)[82,83],但其与OH的反应中显示 RO2存在尚不清晰的反应途径[83],仍需进一步探究。一些研究针对不同体系ONs的光解、水解等去除方式也进行了烟雾箱模拟。“单萜烯+OH”反应生成的气相ONs(MT-ONs)的光解速率小于C1-C6ANs,这可能是由于MT-ONs有更大的吸收截面[39]。相对湿度以及PH值对ONs水解速率的影响较大[78,79,84⇓ ~86]。通过ONs的光解和水解可以有效地去除NOx。总体来说,不同BVOCs氧化体系的烟雾箱研究对于森林等排放量较大地区(例如美国东南部等)的大气化学分析具有重要意义,给复杂的外场观测提供了必要的理论支持,但相关的ONs的生成因实验条件(BVOCs种类和浓度、氧化剂来源和浓度、NOx水平、相对湿度等)不同以及反应机制(RO2损失的主导反应)不清晰等仍存在高度不确定性,ONs水解光解等去除方式的研究也较为有限,未来将进一步完善ONs可控条件下的实验室模拟并结合观测数据进一步分析。

AVOCs氧化生成ONs的烟雾箱模拟相对较少。甲苯等芳香烃的光氧化是城市SOA的潜在来源[87]。苯等芳烃和OH自由基的氧化一般通过加成形成苯-OH加合物,该加合物与O2反应得到RO2自由基,随后进行一系列反应或者得到终止产物,其中包括PNs[88⇓~90]。此外,多个研究结果揭示了芳香烃氧化形成SOA与NOx水平的依赖关系[87,88,91,92],这可能与ONs的形成相关。然而,对AVOCs氧化生成的ONs认识还十分有限,有待进一步研究。

5 有机硝酸酯的外场观测

5.1 国际外场观测

ONs的外场观测研究最早在欧美地区展开。PAN最早作为光化学烟雾污染被发现[19],不同污染程度以及大气环境不同的地区,PAN浓度有明显差异,在清洁地区,PAN浓度可低至pptv量级,而在污染严重的城市地区可达几十ppbv。1988年,Atlas[93]报告了在北太平洋对流层对C≥3 ANs的观测,其浓度水平在pptv量级,直接验证了ANs在对流层的存在与传输。21世纪以来,随着测量技术的不断发展,和ONs相关的外场观测活动陆续开展。表2总结了2010年以来国外地区与ONs相关的外场观测,主要包括欧洲(芬兰[30,94]、英国[95]和德国[16]),北美洲(美国[6,32,50,96⇓⇓⇓⇓⇓⇓ ~103]、加拿大[24,25]以及墨西哥[43]),亚洲(韩国[13,104]和日本[105])以及部分海洋上空[106]的观测。测量方法主要为TD和GC-ECD。从表2可以看出,ONs浓度整体较低,随着观测站点类型的不同,ONs浓度在<0.1~1.87 ppbv的范围内变化,偏远地区浓度较低,而在交通量大、受人类活动影响较大的城市地区浓度则相对较高;ONs浓度水平主要受当地光化学反应以及其他地区污染气团的传输影响[30,96,104];在不受外界老化气团传输影响的地区,ONs生成机制是明确的,且具有明显的日变化及季节变化趋势;多个外场观测表明白天和夜间ONs的形成分别由OH自由基和NO3自由基主导[16,30,96,97,101],产生的ONs可作为NOx的临时储库,Sobanski等[16]在德国西南部山顶森林城市站点观测到通过光化学反应生成的ONs可以作为当地高达75%的NOx储库,在SOAS外场观测中观察到了ONs占NOy的30%~45%[96];另外部分测量结果显示ONs和SOA、O3的形成相关,例如,Rollins等[32]通过观测和计算,预计加州斯菲尔德地区对颗粒相ANs占OA的17%~23%,KORUS-AQ机载观测中有1/4的ONs处于颗粒相,其对OA的贡献≈15%[8],Lindaas等[107]在科罗拉多地区观测到高浓度O3的生成和PANs相关;部分污染事件的发生可能导致ONs浓度出现明显的增加,2010年墨西哥湾海平线石油泄漏[43]以及伦敦烟羽[95]的两次机载测量中,高NOx排放和一些挥发性烷烃快速反应,由于ANs和O3的生成相互竞争,当ANs快速生成时,O3的生成受到抑制,这些污染事件中的大气化学过程可以用已有的NOx-VOCs-ONs氧化机制很好地解释。

目前,在BVOCs排放量较高的地区,已经验证了ONs的氧化生成,而且已经广泛研究了它们与当地SOA、NOx以及O3的相关关系[6,50,94,95,98,100];但在城市和海洋上空的一些观测和模型分析结果表明,仍存在着一些不能解释的ONs源,可能与AVOCs-NOx氧化机制相关[8],需要结合上述提到的实验室实验进一步探索。

5.2 国内外场观测

随着现代工业的发展,我国大气污染日益严重,工业发达和人口密集的城市地区长期遭受灰霾和光化学烟雾等大气污染。针对我国部分地区高NOx高污染的复杂大气环境,近些年对ONs的外场观测逐渐增多,观测地点主要集中在华北平原[17,114⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓ ~128]、黄河三角洲[129⇓~131]、珠江三角洲[132⇓~134]以及香港[27,135⇓⇓⇓ ~139]等地区,外场观测数据还较为缺乏。

1990年春夏季,北大研究团队[140]利用GC-ECD在北京中关村对PAN进行测量,结果表明PAN浓度与O3和NOx水平相关联,夏季浓度明显高于春季,此外实验室模拟还证明了乙烷(C3H6)是大气中PAN的重要前体物。二十世纪以来,针对PAN的外场观测逐渐增多,测量地点多集中于重点城市的城郊地区以及部分偏远地区(青藏高原)。2022年8~9月,Zhang等[141]在北京一个典型城市采样点的观测结果显示,PAN平均浓度和最大浓度分别为(1.00±0.97)ppbv和4.84 ppbv;严重光化学污染期间平均浓度约为清洁期的3.1倍,此外,O3和PAN之间存在良好的正相关关系,分析结果还表明,乙醛(CH3CHO)和甲基乙二醛(CH3COCHO)是生成PNs的最大前体物,二者对总PA自由基贡献分别约为67%~83%和17%~30%。2008年11月,Li等[142]在河北望都的农村地区进行了四个月的观测活动中,PAN的最大值和平均值分别为4.38 ppbv和(0.93±0.67)ppbv,其日变化和形成速率和PM2.5浓度相关,PAN和PM2.5的双峰交错现象为其可能通过SOA的形成加剧雾霾提供了依据。Xu等[143]分别在2011年8月17日至24日和2012年5月15日至7月13日两次在纳木错高原地区进行测量,平均浓度分别为0.36 ppbv和0.44 ppbv,明显低于城市地区,边界层的演化影响PAN和O3的昼夜模式,并指出区域输送对青藏高原高海拔地区对流层光化学有重要影响。表3总结了国内部分代表区域关于PAN的外场观测结果,可以看出,在城市地区(北京、济南等),浓度相对较高,最大可以达到十几ppbv,而在青藏高原等偏远地区,PAN最大浓度仅为0.99 ppbv[143],不同地区因光化学反应和区域输送等因素呈现不同的浓度水平和变化趋势。

2001年,Simpson等[132]在中国香港大澳测量了七种C1-C5ANs。目前,国内关于ANs的外场观测逐渐增多,主要集中于C1-C5ANs的测量,利用模型进行源解析并探究ANs与O3的相互作用。如图1所示,不同AN浓度在pptv量级,C1-C5ANs中,2-BuONO2浓度最高,2-PrONO2次之。Wang等[144]测量了中国城市地区的C1-C4ANs浓度,结果显示2-BuONO2是最丰富的ANs物种,这与在香港的观测结果一致,其浓度范围为48~88 pptv。近两年,Zeng 等[139]在中国香港对ANs的长期观测结果显示2-BuONO2的平均浓度始终最高,其余C1-C4ANs均呈上升趋势,利用PMF进行来源分析可知,光化学二次反应生成和生物质燃烧排放可能是香港大气环境中ANs浓度升高的原因。Zhang等[130]在2017年分别在中国北部黄河三角洲地区的一个农村沿海地区和露天油田进行了C1-C5ANs观测,夏季浓度高于冬春,而其前体VOCs则表现出相反的季节变化模式,论证了油田排放和生物质燃烧对VOCs和ANs形成的显著影响,为制定黄河三角洲地区光化学大气污染控制策略提供了科学支持。

部分外场观测采用AMS对颗粒相ONs进行了测量。例如,Zhu等[115]对华北平原农村地区颗粒相ONs进行了观测,质量浓度为1.48~3.39 μg/m3,颗粒相ONs与生物质燃烧排放的高相关性,揭示了颗粒相ONs的形成可能与华北农村地区的初级排放密切相关。除了上述特定ONs的观测,Li等[18]还报告了2019年夏季在成都对ΣPNs和ΣANs的测量结果,白天ΣPNs和ΣANs的平均浓度分别为(1.3±1.1)ppbv和(0.5±0.3)ppbv,峰值分别为7.7 ppbv和1.9 ppbv,揭示了醛类和酮类的OH氧化是PNs前体物的重要来源,通过模型量化了PNs化学对O3生成的抑制,并强调了芳烃控制对缓解成都光化学污染的重要性,加深了对我国西部城市光化学污染的认识。

6 结论与展望

本文从ONs的大气化学作用、生消机制、测量方法、室内烟雾箱研究以及外场观测几方面进行了详细总结。其生成和去除作为高NOx环境背景下区域大气化学不可或缺的一部分,对大气成分以及大气氧化性都具有重要的影响。多种测量技术为不同要求的ONs外场观测提供了选择。尽管研究人员对ONs大气化学作用有了一定的认识,但仍然存在着一些未知,需要进一步探究:

(1)由于前体VOCs种类众多,进而生成的ONs成分各异,不同ONs的物理和化学特性等认知还存在着一定的局限性,另外,ONs形成机制多关注于BVOCs的大气氧化,白天和夜间分别由OH自由基和NO3自由基氧化主导,而AVOCs是城市区域化学中的重要成分,由其参与形成ONs的研究相对较少,需要进一步探索。

(2)ONs测量技术主要针对于特定ONs(例如PAN、C1-C5ANs等)以及ΣONs(ΣANs和ΣPNs)的测量。测量特定ONs的常用方法为GC-ECD,需要定期校准,定量ΣONs多采用TD法,该方法也因各种干扰因素存在而存在一定误差,依赖于实验室的干扰标定。因此,未来对于ONs的测量,还需针对上述不足,改进测量技术,实现ONs快速准确的在线测量,满足不同观测条件下的测量需求。

(3)ONs烟雾箱研究表明,不同前体VOCs氧化生成的ONs产率因条件(氧化剂浓度,前体物浓度,RH、RO2反应途径,NOx水平等)的不同而有所差异;ONs种类众多,不同ONs的光解、水解等去除方式也不能一概而论,关于ONs的实验室研究仍存在高度不确定性。

(4)针对不同大气环境下ONs的气粒分配缺乏系统分析,挥发性较低的ONs其气粒分配与温度、OA浓度、NOx水平等相关,挥发性较高的ONs结构各异,经过多次氧化进入颗粒相的分配过程极其复杂,另外与观测数据相结合进行实际大气的ONs气粒分配分析的研究相对较少,对气相ONs进入颗粒相形成SOA缺乏更为细节的把握与认知。

(5)国内多数外场观测集中于特定ONs的测量,针对ΣONs以及机载观测数据较少,部分突发污染事件中也缺乏ONs的实时测量,将上述观测数据结合模型进行数据分析,揭示ONs特定情况下的特殊来源以及在大气化学过程的重要作用,进一步完善ONs的大气化学机制。

未来与ONs相关的研究应多侧重于上述不足,结合并改进理论模型,对不同大气条件下ONs的各个方面进行多维度多层次的探索研究,逐步完善对ONs这一类重要物质的全面认知。

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基金资助

国家自然科学基金项目(42175151)

国家自然科学基金项目(U21A2028)

国家重点研发计划(2022YFC3701100)

安徽省科技重大专项(202203a07020003)

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