Fourier transform infrared analysis of aerosol formed in the photo-oxidation of isoprene and β-pinene

The chemical composition of smog-chamber aerosol generated during the photo-oxidation of isoprene and β-pinene was probed using infrared (i.r.) microscopy interfaced with a low pressure impactor. The low-pressure impactor employed ZnSe impaction surfaces which allowed direct analysis, with no extraction, using i.r. microscopy. The low detection limits of this technique, coupled with direct sample analysis, permitted the chemical analysis of aerosol generated at low to moderate hydrocarbon and ozone loadings. The quantitative analysis of the i.r. spectra is limited, in part, by the absence of calibration standards, however, it is clear that the biogenic aerosols generated in this work were liquid mixtures containing ketone, aldehyde, alcohol and organonitrate functional groups. Molar loadings of each of these functional groups were estimated for nine smog-chamber experiments. For aerosol formed in isoprene photo-oxidation, aldehyde and ketone groups dominated (1.8 groups per average molecule) while for aerosol formed in β-pinene photo-oxidation, alcohols and ketones dominated (a combined 2.7 groups per average molecule).     

The sources and size distributions of aliphatic and carbonyl carbon in Los Angeles aerosol

Size distributions of aerosol phase aliphatic and carbonyl groups were measured during the Southern California Air Quality Study. Samples were collected using a low pressure impactor equipped with ZnSe disks and the aerosol samples were analyzed directly using infrared (i.r.) spectroscopy. For the carbonyl absorbance, the ambient samples showed maxima in the 0.12–0.26 μm and the 0.5–1.0 μm size fractions. For the aliphatic carbon absorbance, the ambient samples generally showed maxima in the 0.076–0.12 μm size fraction. Factors contributing to these two absorbances were examined using principal component analysis. The results indicate that the carbonyl absorbance can be almost entirely attributed to products of atmospheric reactions and the aliphatic absorbances in particles smaller than 0.12 μm is correlated with automotive emissions.     

不同粒径黄河沉积物中可提取腐殖质的含量分布及光谱特性

测定了黄河表层沉积物3种粒径组分（Ⅰ：100～300 μm;Ⅱ: 63～100 μm;Ⅲ: <63 μm）中总有机碳和可提取腐殖质的含量,分析了可提取腐殖质的紫外-可见吸收光谱、红外光谱和三维荧光光谱特征,探讨了不同粒径组分沉积物中可提取腐殖质含量分布及其化学组成特性.结果表明,沉积物有机质主要为粘土矿物吸附的天然腐殖质成分,总有机碳中可提取腐殖质的比例随沉积物有机质与矿物质相互作用的增强而降低,顺序为Ⅰ>Ⅱ>Ⅲ.3种粒径组分沉积物中可提取腐殖质的紫外-可见吸收光谱相似但相对峰强不同;红外光谱主要有5个吸收峰,各吸收峰面积百分含量的计算结果表明酚、醇及羧酸类官能团为主要的活性官能团,占可提取腐殖质组成的75%以上;三维荧光光谱主要有3个荧光峰,除了典型的类腐殖质荧光峰（峰A和峰C）外,还有源于小分子类蛋白或酚类物质的荧光峰（峰T′）.比较3种粒径组分沉积物中可提取腐殖质的紫外-可见、红外及三维荧光光谱的特征参数,发现Ⅰ、Ⅱ组分沉积物中可提取腐殖质的芳香度高,脂肪族和芳香族含量高于Ⅲ组分,而Ⅲ组分沉积物可提取腐殖质中酚、醇及羧酸类活性基团含量相对较高.     

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.     

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.     

环状扩散管-分级采样器的建立和细粒子酸性的测定

建立了国内第一台扩散管－分级采样器，用来研究大气气胶溶胶的组成和细粒子的酸性，实验证明该采样系统能够有效地避免大气中的碱性物质对颗粒物采样的干扰。在北京，湖南等地进行了现场实验，测定了气溶胶的酸性。     

Metals in airborne particulate matter in rural Switzerland

Weekly samples of aerosol in nine size fractions were taken in the period October 1985 to September 1986, and were analyzed for Na, V, Mn, Cu, Zn, As, Cd and Pb.Sampling locations were south of Berne, Switzerland, at elevations of 515, 750, 940 and 1550 m above sea level.The results indicate that the particulate matter concentration decreases with increasing elevation, but the extent of this decrease depends on atmospheric conditions, and is more pronounced during fall and winter when frequent inversion situations occur.During a few weeks in February 1986 unusually high aerosol concentrations were observed with atypical As to Zn ratios. The meteorological situation indicated transport from Eastern Europe.Principal component analysis revealed two to three factors in every size fraction, which were considered to be an ‘anthropogenic’, a ‘soil’ and a ‘large particle’ sodium component.Single particle analysis of one summer and one winter sample (particle size 2–4 μm) provided a variety of particles previously described in the literature as well as nickel and silicon rich particles of unknown origin (summer sample).     

Characterization of particle size distribution of mainstream cigarette smoke generated by smoking machine with an electrical low pressure impactor

Cigarette smoking is a particle-related exposure. Studying the characteristics of the particle size distribution of cigarette smoke can aid in providing knowledge of smoke aerosol attributes. We used an electrical low pressure impactor （ELPI） to measure the particle size distribution of mainstream cigarette smoke generated by a smoking machine and provided a continuum of particle sizes of cigarette smoke from a whole cigarette. The results showed that the aerodynamic diameters （D, geometric mean of a channel） of particles ranged from 0.021 to 1.956 ~m, and the number concentrations were on the order of 105-109 cm-3 for different sizes of particles. The particle number of the size category below 0.1 p,m approximated that of the category 0.1-2.0 Ixm, and the particles in the size category of 0.1-2.0 μm contributed extremely heavily to total particulate mass. In addition, the results with small samples indicated that the tar yields normalized per milligram of nicotine showed an approximately linear increase with increasing concentration of total particles.     

北京郊区农田夏季大气颗粒物质量和离子成分谱分布特征

农业活动是大气颗粒物的重要来源之一.为了研究北京郊区农田大气颗粒物质量和离子成分的分布,探讨其来源,本研究使用8级串联撞击式采样器MOUDI采集了2004年夏季北京远郊菜地的大气颗粒物样品,测量了0.18～18μm粒径段颗粒物质量和水溶性无机离子的粒径分布.细粒子的主要离子成分是SO₄^2-、NO₃^-和NH₄⁺,与温度、湿度和光照等条件相关,推测主要来自农田释放的NH₃与光化学生成的酸性物种的反应.细粒子中的K⁺可能来自植物的排放和生物质的燃烧.粗粒子中Ca²⁺、Mg²⁺、NO₃^-和SO₄^2-可能主要来自土壤颗粒物通过机械过程进入大气,以及其后酸性物种和土壤颗粒物表面的化学反应.研究结果表明,施用的化肥和土壤可能是决定农田大气中颗粒物的重要因素,北京远郊菜地对大气颗粒物可能有着重要的贡献.     

循环流化床电站排放烟尘特性及痕量重金属分析

对35t h循环流化床电厂电除尘器入口和出口的烟气气溶胶进行分级取样,得到飞灰浓度和粒度分布以及电除尘器的分级脱除效率.电除尘器对PM10、PM2 5的脱除效率分别为94 34%和91 38%,使部分可吸入烟尘颗粒穿透除尘设备而直接排放到大气环境中.同时对不同粒度飞灰中重金属含量进行了测试,得到痕量元素浓度从高到低依次为Ni,Cr,Cu,Cd,Pb,Hg.痕量重金属含量与飞灰粒径有一定依附关系,其分布规律与煤成分、锅炉燃烧方式和痕量元素自身的挥发特性等因素有关.     

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.     

Aerosol-soil fractionation for Namib Desert samples

Four soil samples, collected in the central Namib Desert, were fractionated by dry sieving and aerosol generation into 16 size fractions in the range 0.15–300 μm diameter. The mass-size function of each soil and the dust (mineral aerosol) generated from the soil were studied. Due to the preferential lifting of smaller soil particles by the air stream, the soil underwent strong physical fractionation resulting in the bulk of the dust being found in the range of 1.3–10.3 μm, whereas the bulk of the soil was found in the range 63–300 μm. The concentrations of 11 elements in eight soil size fractions (from <45 to >300 μm) obtained by dry sieving were measured by X-ray fluorescence analysis while the concentration for these elements in eight size ranges (from <0.15 to >10.3 μm) obtained by aerosol generation were determined by particle-induced X-ray emission. The concentrations of the elements Al, Si, K, Rb and Sr were found to vary by less than a factor of two throughout the particle size range studied. However, the concentration of the elements Ca, Ti, Mn, Fe, Y and Zr increased when the particle size decreased below 150 μm to reach a maximum around 63-45 μm and then to decrease. The concentrations of the elements in the generated aerosol particles were found to be more similar to those in the bulk soil than any particular size fraction. For the aerosol size fraction, elemental enrichment factors were calculated with respect to the composition of average crustal rock, average soil, the bulk Namib soil and the small size fraction of the Namib soil. For several elements, the enrichment factors varied quite significantly, depending on the choice of the reference material. The elemental ratios in the mineral aerosol were also compared to those in the atmospheric aerosol from the Namib Desert. It was confirmed that there is a marine contribution for S, Cl and Sr in the Namib natural aerosol. The composition of the mineral aerosol generated in this study should be useful in source apportionment studies for the Namib Desert and sorrounding regions.     

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.     

活性艳蓝X-BR染料废水电化学脱色及其机理研究

采用电凝聚技术,对活性艳蓝X-BR模拟染料废水的电凝聚脱色过程进行研究,考察各种参数对脱色效果的影响,并对其脱色机理进行了初步分析.研究表明:采用电凝聚方法可以使活性艳蓝X-BR模拟染料废水的色度得到有效去除;处理时间、电解电压、废水初始浓度、初始pH值、搅拌强度、添加电解质浓度、极板间距等参数均对处理效果有影响,在最...     

标准气溶胶发生系统的建立与性能评估

针对气溶胶测量仪器校准和实验室气溶胶光学特性研究的需求,搭建了一套标准气溶胶发生系统,并对其性能开展了测试研究.系统采用恒定流量的雾化器产生气溶胶,经过扩散干燥管干燥以及电荷中和器带电中和后,产生标准气溶胶粒子.利用氯化钠样品对系统的性能进行了测试,结果表明,当样品溶液浓度增加时,系统雾化产生粒子的数浓度和粒径均随之增加;当载气气压增加,系统雾化产生粒子的数浓度随之增加,而粒径随之减小.在测试时间内,系统发生的多分散气溶胶粒子的几何平均粒径波动小于1%,总粒子数浓度波动小于2%,单分散气溶胶粒子数浓度的稳定性好于4%.     

2002年春季沙尘暴对青岛大气气溶胶的影响

根据TSP,PM10,分级粒子质量浓度观测资料,分析了2002年春季发生于我国北方的2次沙尘天气过程对青岛大气环境的影响.在3月15-19日和21-23日的2次沙尘天气过程中TSP质量浓度分别为0.488和0.721 mg/m\+3,比平时增加了2.8和4.1倍.沙尘天气期间2～7 μm粒子为影响青岛的主要成分,在第2次沙尘暴期间该粒径的粒子质量浓度增加了30倍,其中2.1～3.3 μm粒子质量浓度达到0.13 mg/m\+3.根据地面气象资料和PM10连续监测资料发现,在地面风向转北之前,高空气流携带的沙尘首先影响到青岛.      

一种气溶胶测量仪器标定系统的设计及性能评估

对气溶胶测量仪器进行准确标定是保证大气环境及污染源颗粒物测量数据质量的重要前提.本研究搭建了一套多分散在线标定气溶胶测量仪器的系统,该系统采用超声气溶胶发生装置产生多分散颗粒物,并用空气动力学粒径谱仪对颗粒物粒径分布进行测量.评测结果表明该系统干燥腔室内气溶胶稳定、均匀,且符合对数正态分布.以采样器为例,已有研究多使用单分散离线标定方法对采样器切割性能进行标定,该方法操作繁琐、实验周期长.利用多分散在线标定系统对PM_(2.5)和PM_(10)双级虚拟撞击采样器进行标定,并与单分散离线标定方法进行了对比,两套系统的标定结果呈现较好的一致性,但多分散在线方法大大缩短了标定实验周期.     

不同粒径大气颗粒物中有机碳(OC)和元素碳(EC)的分布

使用Andersen六段分级大流量采样器(粒径:7.2～10,3.0～7.2,1.5～3.0,0.95～1.5,0.49～0.95,＜0.49μm)采集了广州市荔湾区冬季的大气颗粒物样品,并用美国Sunset碳分析仪分析了其中的有机碳(OC)和元素碳(EC)组分.研究表明:OC和EC主要存在于细粒子中,与OC相比,EC则相对更集中于＜0.49 μm粒径上;PM10中二次有机碳占总有机碳(ρ(OCsec)/ρ(OC.))比例的平均值为卵%,OC,EC的对数模型图都为双峰型.对ρ(OCtot),ρ(OCpri)(一次有机碳质量浓度)与ρ(EC)进行相关性分析,结果表明,只用ρ(OC)/ρ(EC)值来评价二次污染是不充分的.      

2-丁烯醛生产废水中溶解性有机物的分级解析

采用超滤膜法将2-丁烯醛生产废水中的有机物分为相对分子质量不同的7个级分,并应用溶解性有机碳(dissolved organic carbon,DOC)、紫外吸收光谱(ultraviolet spectrum,UV)、傅里叶变换红外光谱(fourier transform infrared spectrometer,FT-IR)和气相色谱/质谱联用仪(gas chromatography with mass spectrometry,GC-MS)技术对不同相对分子质量区间的有机物所占比例及物质结构进行了研究.结果表明,废水中相对分子质量1×103的有机物所占比例最高,达到88.57%;采用GCMS对废水中相对分子质量1×103的级分进行分析,定性出27种化合物,包含醛、酮、酯、醇、酚、酸、烷烃类及其他苯系物等,其峰面积占有机物峰面积总和的比例分别为6.9%、5.3%、35.4%、13.2%、4.6%、0.4%、1.7%、16.8%,总和为84%.UV和FT-IR分析结果均显示不同相对分子质量区间的光谱吸收特征没有明显差别,级分中存在含有不饱和双键、羟基、羰基化合物及芳香族化合物,与GC-MS检测结果相吻合.研究结果为废水处理工艺的开发与优化提供了重要的指导作用.     

Size distribution measurements of suspended particulate matter in Ponce,Puerto Rico

Size distribution measurements using a high volume sampler with a cascade impactor have been obtained for the city of Ponce, Puerto Rico from 1985 to 1987. The data indicate that the concentration of particles < 2 μm in diameter remained constant during the sampling period while the concentration of particles > 7 μm showed time variations. Aerosol from this area is greatly composed of particles > 7 μm in diameter, they accounted for over 45% of the Total Suspended Particulate (TSP) of this area. Over 75% of the aerosol concentration is from particles > 3.3 μm, approximately only 20% of the aerosol concentration is from particles < 2 μm in diameter. A linear relationship was observed between the different particle size and the TSP, except for those particles < 1.1 μm in size. The size distribution and its time variation are explained in terms of local sources such as agriculatural burning, natural contributions and industrial activities, as well as contribution from the Sahara haze that crosses the Atlantic from Africa and reaches the Caribbean region during the summer.