Chemical composition and size distribution of secondary organic aerosol formed from the photooxidation of isoprene

Photooxidation of isoprene leads to the formation of secondary organic aerosol (SOA). In this study, the chemical composition of SOA formed from OH-initiated photooxidation of isoprene has been investigated with gas chromatography/mass spectrometry (GC/MS) and a home-made aerosol time-of-flight mass spectrometer. Sampling particles generated in a home-made smog chamber. The size distribution of SOA particles was detected by a TSI 3321 aerodynamic particle size spectrometer in real time. Results showed that SOA created by isoprene photooxidation was predominantly in the form of fine particles, which have diameters less than 2.5 m. The obtained mass spectra of individual particles show that products of the OH-initiated oxidation of isoprene contain methyl vinyl ketone, methacrolein, formaldehyde, and some other hydroxycarbonyls. The possible reaction mechanisms leading to these products were also discussed.     

氨对甲苯二次有机气溶胶形成和化学组分的影响研究

氨(NH_3)是大气中常见的主要碱性污染气体,能够影响二次有机气溶胶(SOA)的形成和化学组分.本文利用自制的烟雾腔系统开展了NH_3对甲苯SOA形成和化学组分的影响研究,先后采用扫描移动粒径谱仪(SMPS)、气溶胶激光飞行时间质谱仪(ALTOFMS)、紫外-可见分光光度计(UV-Vis)、衰减全反射傅里叶变换红外光谱仪(ATR-FTIR)和荧光光谱仪(MF)测量反应产生的SOA粒子的物理化学性质.结果显示,在光照60 min的时间范围内,有NH_3条件下形成的SOA质量浓度和中心粒径相比于无NH_3条件下分别增加了50%和25%,这说明NH_3能够显著促进甲苯SOA的形成.与无NH_3条件下相比,NH_3存在时甲苯SOA化学组分的紫外可见吸收光谱在270 nm处有明显的吸收峰;红外吸收光谱出现了CN、C—N、N—H键的吸收峰;激光解吸附质谱图中含有m/z=67(C_3H_3N_2~+)、m/z=41(C_2H_2N~+)和m/z=28(CH2N+)碎片峰.这些谱图信息综合表明是NH_3和甲苯SOA中的二醛组分反应形成了咪唑类新产物.这为研究人为源SOA的形成机制提供了实验依据.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

Effect of illumination intensity and light application time on secondary organic aerosol formation from the photooxidation of α-pinene

Secondary organic aerosol (SOA) formation from hydroxyl radical (OH.) initiated photooxidation of α-pinene was investigated in a home-made smog chamber. The size distribution of SOA particles was measured using aerodynamic particle sizer spectrometer. The effects of illumination intensity and light application time on SOA formation for α-pinene were evaluated. Experimental results show that the concentration of SOA particles increased significantly with an increasing of illumination intensity, and the light...     

Size distribution of the secondary organic aerosol particles from the photooxidation of toluene

In a smog chamber, the photooxidation of toluene was initiated by hydroxyl radical （OH.） under different experimental conditions. The size distribution of secondary organic aerosol（SOA） particles from the above reaction was measured using aerodynamic particle sizer spectrometer. It was found from our experimental results that the number of SOA particles increased with increasing the concentration of toluene. As the reaction time prolonged, the sum of SOA particles was also increased. After a reaction time of 130 min, the concentration of secondary organic aerosol particles would be kept constant at 2300 particles/cm^3. Increasing illumination power of blacklamps could significantly induce a higher concentration of secondary organic aerosol particle. The density of SOA particles would also be increased with increasing concentration of CH30NO, however, it would be decreased as soon as the concentration of CH30NO was larger than 225.2 ppm. Nitrogen oxide with initial concentration higher than 30. 1 ppm was also found to have little effect on the formation of secondary organic aerosol.     

氯化钙种子气溶胶对甲苯二次有机气溶胶与氨形成含氮有机物的影响

苯系物光氧化反应形成的二次有机气溶胶(SOA)是大气细粒子的重要组成部分.SOA羧酸和二元醛组分能与氨反应形成有机酸铵和咪唑类含氮有机物,它们能够吸收205 nm和270 nm的紫外辐射,是棕色碳的主要组分.氯化钙等无机种子气溶胶具有较大的比表面积,可为气相羰基化合物和氨提供凝结与反应载体,从而影响含氮有机物的形成.基于此,本文利用烟雾腔研究氯化钙种子气溶胶存在时甲苯SOA与氨的反应,采用紫外-可见分光光度计测量产物溶液在205 nm和270 nm处的吸光度,并定性研究不同浓度、湿度和酸度的氯化钙种子气溶胶对含氮有机物形成的影响.结果表明:氯化钙种子气溶胶能够促进甲苯SOA含氮有机物的形成;含氮有机物的生成浓度随着氯化钙种子气溶胶浓度和pH值的增加而逐渐增大.但当氯化钙种子气溶胶为碱性时,OH~-会与凝结的有机酸发生酸碱中和反应并抑制二元醛化合物水合形成四醇产物,从而不利于含氮有机物的生成;水分子的增加占据了氯化钙种子气溶胶表面的吸附活性位点,氨被吸附和凝结的量减少,从而导致含氮有机物的生成浓度随着相对湿度的增大而降低.本研究可为人为源SOA棕色碳的形成机制和化学组成研究提供实验依据.     

苯水相光氧化反应形成二次有机气溶胶的实验研究

来源于机动车尾气的苯能溶于大气水滴、云雾等水相中并发生水相光氧化反应,在水分蒸发后,产物保留在颗粒相中形成二次有机气溶胶(SOA)粒子.本文采用雾化器将羟基启动苯水相光氧化反应溶液雾化产生气溶胶粒子,通过扩散干燥管除去水蒸气后产生SOA粒子,采用气溶胶激光飞行时间质谱仪进行在线检测,利用紫外可见吸收光谱仪、红外光谱仪和液相色谱串联质谱仪离线测量SOA的化学组分.实验结果表明,激光解吸附质谱中存在醛类(m/z=29(CHO~+)、57(CHOCO~+))、羧酸(m/z=44(COO~+))和苯环(m/z=39(C_3H~+_3)、65(C_5H~-_5))特征裂解碎片峰.SOA粒子的红外光谱图中存在苯环C—H和C=C双键,以及C=O双键、C—O、O—H和C—O—C键的伸缩振动吸收峰,电喷雾电离质谱中存在m/z高达915的离子峰.这表明醛类、羧酸、酚类、芳香醚类产物和酚类产物发生聚合形成的高分子量化合物是SOA粒子的主要化学组分.这为研究人为源挥发性有机化合物水相反应形成SOA的机理提供了实验依据.     

Effect of NOx and RH on the secondary organic aerosol formation from toluene photooxidation

The secondary organic aerosol (SOA) formation mechanism and physicochemical properties can highly be influenced by relative humidity (RH) and NOx concentration. In this study, we performed a laboratory investigation of the SOA formation from toluene/OH photooxidation system in the presence or absence of NOx in dry and wet conditions. The chemical composition of toluene-derived SOA was measured using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). It was found that the mass concentration of toluene decreased with increasing RH and NOx concentration. However, the change of SOA chemistry composition (f₄₄, O/C) with increased RH was not consistent in the condition with or without NOx. The light absorption and mass absorption coefficient (MAC) of the toluene-derived SOA only increased with RH in the presence of NOx. In contrast, MAC is invariant with RH in the absence of NOx. HR-ToF-AMS results showed that, in the presence of NOx, the increased nitro-aromatic compounds and N/C ratio concurrently caused the increase of SOA light absorption and O/C in wet conditions, respectively. The relative intensity of CHON and CHO_xN family to the total nitrogen-containing organic compounds (NOCs) increased with the increasing RH, and be the major components of NOCs in wet condition. This work revealed a synergy effect of NOx and RH on SOA formation from toluene photooxidation.     

在线表征萘二次有机气溶胶硝基多环芳烃

硝基多环芳烃(NPAHs)广泛存在于大气气溶胶中,是棕色碳的重要组成部分.萘和其他多环芳烃是NPAHs的重要前体物.为研究NO₂对NPAHs形成的影响,本文利用气溶胶激光飞行时间质谱仪(ALTOFMS)在线测定不同NO₂浓度下萘光氧化形成的二次有机气溶胶(SOA)的NPAHs组分.实验结果表明,NO₂对NPAHs的产生和萘SOA的形成有促进作用.通过ALTOFMS在线检测、模糊C均值(FCM)聚类分析,结合离线电喷雾电离质谱验证,测得萘酚和羰基化合物是不存在NO₂时萘SOA粒子主要成分,而通过OH-萘加合物和萘酚硝化产生的硝基萘、二硝基萘、硝基萘酚和二硝基萘酚及其衍生物是NO₂存在时萘SOA粒子的主要组分.这为城市大气高浓度NO_x背景下,研究NPAHs的化学组分和形成机理提供了实验依据.     

深圳市城区VOCs对PM2.5和O3耦合生成影响研究

为了探究珠江三角洲城市大气PM_2.5和O₃的协同污染特征,在深圳市大学城开展了秋季光化学反应活跃季大气污染加强观测.发现O₃日最大8h平均值(O₃_8h)和PM_2.5在日间具有较强的正相关关系,且O₃_8h与典型挥发性有机物(VOCs)甲醛的相关性显著高于NO₂.利用气溶胶质谱仪在线测量了亚微米气溶胶化学组成,并利用正交矩阵因子模型(PMF)对其中有机气溶胶进行来源解析,解析出5类因子,其中二次有机气溶胶(SOA)占总有机物浓度的50%.通过对污染物之间的相关性分析发现,O₃_8h和SOA具有良好的相关性,但与硝酸盐(NO₃^-)未表现出相关性,说明VOCs在深圳城区大气PM_2.5和O₃耦合生成过程中的作用比NOx明显,VOCs减排是深圳市协同控制PM_2.5和O₃污染的关键.     

Characterization of products from photooxidation of toluene

Photooxidation reaction of toluene in smog chamber systems was initiated by the UV radiation of tolucne/CH5ONO/NOx mixtures. The products of the photooxidation reaction of toluene and its subsequent reactions were analyzed directly utilizing Fourier transform infrared spectrometer （FTIR）. Detailed assignments to FTIR spectrum of gas-phase products were given. The information of some important functional groups in the products, such as, carbonyl groups （C-O）, hydroxyl groups （-OH）, carboxylic acid （- COOH）, C-C bonding, N O bonding and C-H bonding （C H）, was got from this analysis. These results were compared to those analyzed by aerosol time of flight mass spectrometer （ATOFMS）. It was found that there are some differcnccs between FTIR analysis of gas-phase products and that of particle-phase, for example, the products with carbonyl groups, which were connected to unsaturated chemical bonds, was relatively higher in the gas phase, while kctoncs, aldehydes, carboxylic acid and organonitrates were the dominant functional groups in the aerosol-phase reaction products. The possible reaction pathways of some important products in the gas phase were also discussed.     

Experimental studies on ozonation of ethylenethiourea

The experimental study on ozonation of ethylenethiourea(ETU) is conducted.The reaction of gas-phase ETU with 0.63 × 10-6 mol/L ozone is carried out in a 200-L reaction chamber.The secondary organic aerosol(SOA) resulted from the ozonation of gas-phase ETU is observed with a scanning mobility particle size(SMPS).The rapid exponential growth of SOA reveals that the atmospheric lifetime of ETU vapor towards ozone reaction is less than four days.The ozonation of dry ETU particles,ETU-contained water droplets an...     

北京大气气溶胶表面无机组分的静态飞行时间二次离子质谱研究

采用特定的样品处理方式,利用静态飞行时间二次离子质谱(Static-TOF-SIMS)技术,对使用通用型大气污染物采样仪VAPS(URG-3000K)采集于非导电性的滤膜(聚碳酸酯滤膜)上的大气气溶胶细粒子(PM_2.5)与粗粒子(PM_2.5～10)的表面无机组分进行了探索性的比较分析.结果表明:大气气溶胶细粒子与粗粒子的表面无机组分组成特征具有明显的差异;气溶胶细粒子表面存在着大气中二次形成的亲水性化合物,会对其表面的疏水性/亲水性特征产生影响,从而影响其大气化学行为;气溶胶粗粒子表面存在氟化物,对生态环境和人体健康具有潜在的危害性,应该重视对气溶胶中氟污染的研究与控制;静态飞行时间二次离子质谱可以成为研究大气气溶胶表面化学组成特征的有利分析手段.      

南京雾过程对大气气溶胶谱分布及化学组成的影响

为探究南京地区雾过程对气溶胶粒子化学组成和尺度分布的影响,在2017年冬季的雾观测中平行收集了3级分档雾水和分粒径气溶胶样品,并对雾微物理量与气溶胶谱分布、3级分档雾水与雾前、雾中、雾后分粒径气溶胶化学组成对比分析。结果表明,2017年冬季南京第1次雾过程的雾滴液态水含量随粒径分布为不对称“V”型,最低值位于7μm处,第2次雾过程的雾滴液态水含量随粒径分布为3峰型,峰值分别位于5,15,21.5μm处。在雾形成、发展阶段,粒径<0.33μm的气溶胶质量浓度降低,粒径0.38μm气溶胶质量浓度升高,雾成熟阶段,气溶胶粒子质量浓度在全粒径段均达到最低,粒径0.38μm的气溶胶质量浓度大幅降低,与雾前相比,雾后气溶胶质量浓度峰值向大粒径方向移动。雾前,气溶胶水溶性离子组分富集在粒径<0.43μm的小粒子中,随着雾过程进行,成核作用和吸湿增长使得水溶性离子向较大粒径段富集。雾中新生成的气溶胶随着雾滴的蒸发被释放,导致雾后NO₃^-、SO₄^2-和NH₄⁺浓度升高。较小粒径的气溶胶中和率更高,雾形成初期的新生雾滴酸性较强,随着雾过程的进行逐渐中和,雾水pH值逐渐升高。     

大气中挥发性有机物(VOCs)对二次有机气溶胶(SOA)生成贡献的参数化估算

大气中二次有机气溶胶(SOA)是PM25中的重要组成部分,挥发性有机物(VOCs)的光化学氧化是其主要来源之一.从VOCs转化生成SOA的过程非常复杂,参数化方法是一种相对简化的估算方式,可以用于区分不同VOCs物种对SOA生成的贡献.本文介绍了基于二产物和基于挥发性分级两种常用的参数化估算方法,并总结分析文献报道的SOA估算结果.文章中也指出现在的参数化估算还存在一些问题,如何准确量化VOCs向SOA的转化过程将是大气化学未来的重要研究工作.     

Second organic aerosol formation from the ozonolysis of -pinene in the presence of dry submicron ammonium sulfate aerosol

An indoor chamber facility is described for investigation of atmospheric aerosol chemistry. Two sets of α-pinene ozonolysisexperiments were conducted in the presence of dry ammonium sulfate seed particle: ozone limited experiments and α-pinene limitedexperiments. The concentration of gas phase and particle phase species was monitored continuously by on-line instruments andrecorded automatically by data sampling system. The evolution of size distribution was measured by a scanning mobility particlesizer (SMPS), and α-pinene consumed was measured using GC-FID. Secondary organic aerosol (SOA) produced for seed-free systemis 100% organic in content, resulting from a sufficient supersaturation of low volatility organics to produce homogeneous nucleationfollowed by condensation to the aerosol. Secondary organic aerosol produced in seeded system is a mixture of organic and inorganicconstituents, initially forms via condensation onto the inorganic particles, and subsequent growth occurs via absorption into the organicsurface coating the inorganic core. Although the formation process and the size distribution for seed-free system and seeded system isdifferent, the ultimate mass of SOA formed is equal, and SOA yield for the two system located in the same regression line when usingone-product model, suggesting that the presence of dry ammonium sulfate seed has no measurable effect on the total aerosol yield, and the dry seed particle acts solely as a site upon which organic deposition occurs.     

鹤山气溶胶光学性质和单颗粒化学组分的研究

2014年10~11月在广东省鹤山大气超级站利用单颗粒气溶胶质谱仪（SPAMS）、积分式浊度仪和黑碳仪在线观测了单颗粒气溶胶的化学组成与气溶胶光学特征.采用Art-2a分类法将单颗粒分为9类：有机碳-硫酸盐/硝酸盐颗粒（OC-Sulfate/Nitrate）、元素碳-硫酸盐/硝酸盐颗粒（EC-Sulfate/Nitrate）、元素碳有机碳-硫酸盐/硝酸盐颗粒（ECOC-Sulfate/Nitrate）、高分子有机碳颗粒（HOC）、海盐颗粒（Sea-salt）、硅酸盐颗粒（Si-rich）、左旋葡聚糖颗粒（Lev）、钾-硫酸盐/硝酸盐颗粒（K-Sulfate/Nitrate）、金属颗粒（Metal）.从清洁期到灰霾期气溶胶的吸收系数、散射系数和单次散射反照率（SSA）显著升高,气溶胶消光能力增强,同时EC-Sulfate/Nitrate颗粒占比从34.8%降至31%,OC-Sulfate/Nitrate颗粒从9.9%增加至23.6%,K-Sulfate/Nitrate二次颗粒从8.5%增加至14%,且灰霾期OC-Sulfate/Nitrate颗粒与硫酸盐、硝酸盐和铵盐的混合程度增强,因此老化的OC-Sulfate/Nitrate颗粒和二次组分颗粒对气溶胶消光系数的增加有重要贡献.在大气相对湿度从50%增加到70%以上的过程中,气溶胶散射系数和吸收系数升高,消光系数由326.1Mm^-1增加到362.9Mm^-1,SSA有所下降,PM_2.5质量消光效率由4.98增加到5.99,EC-Sulfate/Nitrate颗粒和K-Sulfate/Nitrate二次颗粒占比下降,而OC-Sulfate/Nitrate颗粒的占比由7.79%增加到14.29%,且OC-Sulfate/Nitrate颗粒中富含硫酸盐、硝酸盐和铵盐,表明高相对湿度下老化的OC-Sulfate/Nitrate颗粒数目增多对气溶胶消光系数的增强有重要影响.     

冬季德州市大气颗粒物消光与化学组成关系研究

为了深入探究华北地区冬季大气颗粒物的消光特性和化学组分之间的关系,本研究于2017年11月—2018年1月在山东省德州市平原县对大气颗粒物消光和化学组成进行了连续在线观测.运用多元线性回归方法和MIE散射模型定量分析了颗粒物各化学组成对颗粒物消光的贡献,进一步地,利用高分辨飞行时间气溶胶质谱(HR-ToF-AMS)结合正矩阵因子解析模型(PMF)得出二次气溶胶(OOA)、生物质燃烧有机气溶胶(BBOA)、还原性气溶胶(HOA)、燃煤燃烧排放的有机气溶胶(CCOA)的浓度,并进一步结合线性回归模型得到OOA、BBOA、HOA、CCOA对消光的贡献.结果显示元素碳(EC)是颗粒物吸光的最主要贡献者, OOA、BBOA和CCOA对颗粒物吸光也具有一定贡献,这主要是由于二次生成和一次排放的棕色碳的吸光造成的.颗粒物各组分与散射关系的分析结果表明,有机物对颗粒物散射影响最大,其中OOA的散射截面最大,对颗粒物散射的贡献也最高,可以占到总散射的53.4%.颗粒物中有机物对大气总消光的贡献可达75.5%,其中OOA、BBOA、CCOA和HOA对总消光的贡献分别为47.8%、14.7%、9.0%、4.0%. Mie散射的结果与多元回归结果比较一致,但部分时间段偏差较大,因此在不同的研究中应根据不同情况选择研究方法.     

青岛沿海地区大气气溶胶浓度与主要无机化学组成

从 1997-09～1998-11期间 ,5次监测大气气溶胶 ,获得了青岛沿海地区气溶胶 (TSP、PM₁₀ 、PM_2.5)的质量浓度 .气溶胶中直径 <2.5μm的细粒子质量浓度约占TSP总浓度的 50% ;<10μm的粒子的质量浓度则占TSP总浓度的 75% .对气溶胶中主要可溶性离子组分的分析表明 :TSP中可溶性离子的质量浓度占总质量浓度的40%以上 .其中主要可溶性离子为SO^2-₄、NO^-₃ 、NH⁺₄ .这 3个离子的质量浓度约占可溶性离子总浓度的 70% ,而且主要存在于细粒子中 ,表明其主要来自二次气溶胶 .冬季气溶胶浓度大大高于其它季节 .