An amorphous solid state of biogenic secondary organic aerosol particles

Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90?billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.     

SO_2,NO 等离子体净化中自由基行为的分析

建立一个简单而合理的化学反应模型，对等离子体条件下活性自由基在ＳＯ２和ＮＯ净化中的行为和作用进行化学动力学分析．结果表明，ＯＨ，Ｏ和ＨＯ２基在ＳＯ２和ＮＯ气相氧化脱除中起主导作用，在整个净化机制中，气相反应的贡献仅占２０％左右；气溶胶表面的催化作用加强了ＳＯ２和ＮＯ的氧化速度，异相反应对ＳＯ２和ＮＯ净化有重要贡献，一个气溶胶可提供１０７ｃｍ－３的自由基．动力学模拟结果与实验结果定性相符．动力学研究结果为等离子体过程的优化提供依据     

Quantitative relationship between production and removal of OH and HO<Subscript>2</Subscript> radicals in urban atmosphere

Atmospheric oxidizing capacity is the essential feature of urban and regional air. And OH and HO2 radicals are the key species indicating atmospheric oxidizing capacity. Using Guangzhou City as a case, this work has conducted field measurements of photochemistry relevant pollutants including O3, NOx, VOCs, H2O2, HNO2 and CO,SO2. The concentrations of OH radical are measured simultaneously by impregnated filter trapping and HPLC (IFTHPLC) method. The factors influencing OH levels are assessed. Based on understanding of OH and HO2 air chemistry, the production and removal rates of these 2 radicals are calculated. The results show that the budget of OH and HO2 can generally be closed, the radical transformation between OH and HO2 dominates the sources and sinks of them, and also the photolysis of HNO2 and HCHO is the significant source of OH and HO2 respectively.     

大气中二羰基化合物及其生成的二次有机气溶胶

二次有机气溶胶(secondary organic aerosol, SOA)对大气灰霾的贡献是当前大气化学研究的热点. 二羰基化合物(乙二醛和甲基乙二醛)是大气光化学反应的中间产物, 可以通过多种途径形成SOA, 对SOA的形成和总量增加有重要的贡献. 大气中二羰基化合物主要来源于生物源(如异戊二烯)和人为源(如乙炔)等挥发性有机物的氧化. 二羰基化合物可通过气粒分配(可逆过程)形成SOA, 也可被云、雾或水相气溶胶吸收, 发生水合、聚合、氧化等反应,生成的低挥发性产物留在颗粒相中生成SOA(不可逆过程). 目前常用的二羰基化合物检测方法是利用衍生化试剂与二羰基化合物反应生成衍生物, 经溶剂洗脱后再用气相色谱-质谱(gas chromatography-mass spectrometry, GC/MS)仪进行分析.     

呼出气VOCs在上呼吸道感染病患与健康人间的异同

研究健康人与病患呼出气VOCs成分的异同, 为上呼吸道感染分型的无创快速诊断提供信息。采集60例上呼吸道感染患者、30例健康人呼出气, 利用GC-MS定量检测97种VOCs, 分析健康人及病患呼出气中烷烃、烯烃、卤代烃、含氧烃、芳香烃等物质的分布特点, 并利用ANOVA-PCA, 分析室内空气以及健康人和病患呼出气中VOCs的异同。结果表明, 异戊二烯浓度在病患、健康人呼出气及室内空气中均有显著差异(P<0.05), 且呈现病人>健康人>室内空气的特点; 正戊烷浓度在病患组显著高于健康人组(P<0.05); 丙醛浓度在细菌性上感组显著高于健康组(P=0.019)。PCA分析结果显示, 健康人与上呼吸道感染病患呼出气差异明显, 不同类型病患呼出气VOCs没有明显差异。     

Purge and trap method to determine alpha factors of VOC liquid-phase mass transfer coefficients

A theoretical approach and laboratory practice of determining the alpha factors of volatile organic compound (VOC) liquid-phase mass transfer coefficients are present in this study.Using Purge Trap Concentrator, VOC spiked water samples are purged by high-purity nitrogen in the laboratory, the VOC liquid-phase mass transfer rate constants under the laboratory conditions are then obtained by observing the variation of VOCs purged out of the water with the purge time.The alpha factors of VOC liquid-phase mass transfer coefficients are calculated as the ratios of the liquid-phase mass transfer rate constants in real water samples to their counterparts in pure water under the same experimental conditions. This direct and fast approach is easy to control in the laboratory, and would benefit mutual comparison among researchers, so might be useful for thestudy of VOC mass transfer across the liquid-gas interface.     

Effect of CH_3OOH on the atmospheric concentration of OH radicals

Peroxides play an i mportant role in atmosphericchemistry,because they are not only amongthe prin-ciple oxidants in the chemical conversion of O3andSO2,but also act as an atmospheric sink and tempo-rary reservoir for i mportant oxidizing radicals such asOH, HO2and RO2[1 ,2]. With the development ofmeasurement techniques , several organic peroxideswere identified in the atmosphere in addition to hy-drogen peroxide (H2O2)[3—5]. And among these or-ganic peroxides , methyl hydroperoxide ( MH…     

高级氧化技术研究现状及其发展趋势

 中国面临环境保护的重大压力,高级氧化技术(AOT)是解决环境污染的理想绿色技术,而高级氧化技术是指·OH制备以及诱发一系列的攻击污染物及微生物反应,从源头上解决了治理污染过程中再污染的问题。高级氧化技术规模制备·OH是其标志性核心关键问题。基于此,学术界进行了一系列羟基自由基制备研究工作。本文介绍了在水中制备·OH的方法,主要介绍O₃/H₂O₂、O₃/UV、H₂O₂/UV、Fenton、光催化氧化、电子辐射和水激励等方法;也介绍了在气体中制备·OH的方法,主要有脉冲电晕放电法、电子束和强电离放电法等。强电离放电法有望同时解决在水、气中规模制备·OH过程中存在的问题。     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

Effect of CH3OOH on the atmospheric concentration of OH radicals

Methyl hydroperoxide (CH₃OOH, MHP) is known to be a significant sink and reservoir of HO_x and RO_x radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×10⁵ Pa, using the long path Fourier transform infrared (LP-FTIR) spectrometry. OH radicals are generated by the photolysis of O₃ in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10^-12 cm³?molecule^-1?s^-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the redistribution of OH radicals in the troposphere.     

General analytical mass transfer model for VOC emissions from multi-layer dry building materials with internal chemical reactions

A general mass transfer based model was developed for analyzing volatile organic compound (VOC) emissions from dry multi-layer building materials with two emission surfaces.This model adds to an earlier multi-layer model by considering chemical reactions within the materials.Consequently,it can be used to analyze the effect of these chemical reactions on removing VOCs,and for characterizing secondary VOC emissions from the building material.The model was validated with literature data and our experimental results.Some typical secondary emissions were analyzed using this model,and obviously differed from the primary emissions.The model is a useful tool for predicting,analyzing and "designing" the VOC emission characteristics,including secondary emissions,of building materials.     

Photoelectron spectroscopy of terpenoids and prediction of their rate constants in atmospheric oxidation reactions

The electronic structures of six mono-terpenoids and two of their oxygenated derivatives were studied by He I photoelectron spectroscopy (PES). The observed bands were interpreted on the basis of empirical arguments and theoretical calculations. The first vertical ionization potentials for β-pinene, α-terpinene, terpinolene, γ -terpinene, limonene, myrcene, citral, and terpinene-4-ol were determined to be 8.73, 7.57, 8.26, 8.30, 8.53, 8.68, 8.71, and 8.77 eV, respectively. Most of these values have not been determined by PES before. The correlations of the first vertical ionization potentials of these compounds to the natural logarithms of rate constants for their reactions with the radicals OH, NO3, and O3 were determined. The correlation coefficients for their reactions with OH, NO₃, and O₃ were 0.97, 0.91, and 0.95, respectively. This method is a powerful technique for predicting the rate constants for the atmospheric oxidation reactions of terpenoids.     

Measurement of rate constant for gas-phase reaction of DDVP with OH radical by using LP-FTIR

：Pollution caused by organic pesticides has received increasing attention. Until now, studies on organic pesticides pollution are mainly focused on soil and water. For reactions of organic pesticides in gas-phase, there are very little research results reported. Using a long path quartz reactor to simulate the atmospheric reaction of dimethyl_dichloro_vinyl_phosphate(DDVP) with OH radicals, the rate constant for the reaction at room temperature is measured at (3.06±0.46)×10-11 cm3 s-1 with Fourier transform infrared spectrograph.The result indicates that DDVP degrades relatively fast in the atmosphere and is unlikely to cause persistent pollution.     

烘焙和通风对室内VOC浓度分布的影响及预测

为了研究烘焙温度和通风量对室内建材散发挥发性有机化合物(VOC)以及室内VOC浓度分布的影响,对现有的VOC散发和传递模型进行了改进.引入温度对建材中VOC的传质系数的影响,并采用文献中的实验数据验证了该模型的正确性.应用该模型计算了建材内部和室内空气中VOC浓度变化.结果表明,换气次数的提高能够加强空气中VOC的稀释,烘焙温度的升高能够加强材料内VOC的传质速率,使VOC向外扩散速率加快,降低建材中剩余VOC的含量,从根源上解决VOC的长期散发问题.从理论上提出和验证了间歇通风烘焙方法是有效降低室内VOC浓度的措施.     

无声放电场作用下产生OH自由基的实验研究

用一种无声放电方法，使反应器中Ｎ２－Ｈ２Ｏ介质在高频高压电场作用下产生ＯＨ，以促进燃烧反应，抑制碳烟生成，并开发一种追踪化学反应的分子物理测量手段，用共振吸收光谱法测定ＯＨ浓度。     

MnO2催化剂的制备及其催化氧化挥发性有机污染物的研究进展

挥发性有机污染物(VOCs)由于其危害大、来源广,因此受到人们的普遍关注.热催化氧化技术在催化降解挥发性有机污染物方面具有独特的优势,而催化剂二氧化锰(MnO_2)由于其在室温下相对于其他催化剂具有较高的处理效果以及易制备等优点而被广泛研究和使用.本文作者着重讲述了催化剂MnO_2的特点、制备工艺、降解挥发性有机污染物效率的影响因素及其负载方式等在国内外的研究现状.     

A mass transfer model for predicting emission of the volatile organic compounds in wet building materials

A new mass transfer model is developped to predict the volatile organic compounds （VOCs） from fresh wet building materials. The dry section of wet materials during the process of VOC emission from wet building materials is considered in this new model, differing from the mass transfer-based models in other literatures. The mechanism of effect of saturated vapor pressure on the surface of wet building materials in the process of VOC emission is discussed. The concentration of total volatile organic compounds （TVOC） in the building materials gradually decreases as the emission of VOCs begins, and the vapor pressure of VOCs on the surface of wet building materials decreases in the case of newly wet building materials. To ensure the partial pressure of VOCs on the surface of wet building materials to be saturated vapor pressure, the interface of gas-wet layer is lowered, and a dry layer of no-volatile gases in the material is formed. Compared with the results obtained by VB model, CFD model and the experiment data, the results obtained by the present model agree well with the results obtained by CFD model and the experiment data. The present model is more accurate in predicting emission of VOC from wet building materials than VB model.     

气相抽提法去除土壤中挥发性有机污染物现场试验研究

为研究气相抽提技术(SVE)现场去污效果及影响因素,在北京市某化工厂搬迁遗留场地,以苯系物为目标污染物,应用气相抽提法进行场地污染修复现场小试,考察了气相抽提真空度、气体抽排流量、空气渗透率及温度变化等的影响。试验结果表明,抽提真空度存在最优值(试验场地在30 k Pa左右),在该值附近,抽取的气体流量最大(流量为13.5 m3/h);抽出气体的污染物浓度及去污速率随流量增大而提高,在不考虑污染物由土壤中迁移过程的限制时,去污速率基本正比于抽气流量;土壤的透气性越强,气相抽提的影响半径越大,抽气流量以及去除污染物的速率也越高;抽出气体的污染物浓度及去除速率总体随温度的升高而增大。     

用密闭小室测定建材VOC散发特性

建筑材料散发的有机挥发物(VOC)能影响室内空气品质,为研究建材VOC的散发情况,提出了一种测量建材VOC散发特性(初始VOC平均浓度、分离系数)和对流传质系数的方法.选取了几种常见建材(复合地板、大芯板、地板砖和地毯)的甲醛散发作为测试对象,在密闭不锈钢小室内测量建材的甲醛散发曲线,用穿孔萃取仪测量建材内甲醛的平均浓度,通过拟合测量结果可以得出建材的散发参数.测试方法和测量结果为建材的筛选和VOC散发性能评价提供了参考依据.     

CH3SH与简单自由基反应的研究现状

含硫有机化合物在对流层大气化学中起着重要的作用.目前在实验和理论上对CH3SH,CD3SH及CD3SD的反应进行了很多研究,主要集中在CH3SH与原子(O,H,F,Cl,Br等)、双原子分子和双原子自由基(NO,OH,OD,BrO,CN等)、三原子分子和自由基及多原子(O3,NO3等)的反应.本文中,笔者对CH3SH与原子和双原子自由基的反应进行了综述.