低温基质隔离研究凝聚相中α-蒎烯臭氧化反应过程

来自天然源的VOC与大气中的O₃等氧化剂发生反应,生成的产物可通过凝结、成核或气-粒分配等物理过程转移至颗粒相中,形成二次有机气溶胶(SOA). 采用低温基质隔离系统与程序升温技术(温度从6 K升至室温)相结合,研究了凝聚相中α-蒎烯与O₃反应的瞬变物种,并采用傅里叶红外光谱仪进行检测. 结果表明:POZ(初级臭氧化物)和SOZ(次级臭氧化物)是α-蒎烯与O₃反应的瞬变物种. POZ的红外特征吸收峰位于699和998 cm-1等处,分别对应于OOO不对称伸缩振动峰、C—O伸缩振动和CH₂摇摆振动耦合,与理论计算结果相吻合;SOZ的红外特征吸收峰位于960和1 205 cm-1等处,分别对应于甲基弯曲振动和OCO弯曲振动,与理论计算结果相吻合. 采用与试验值最为接近的B3LYP方法优化输出了POZ和SOZ的构型,二者均为不对称结构. 未检测到CI(Criegee中间体),可能是由于高能态的CI极不稳定且冷头导热效果不好,致使傅里叶红外光谱仪未能捕捉到CI的吸收峰. 对比乙烯、丙烯、环戊烯的臭氧化过程发现,三者均检测到中间产物POZ和SOZ的生成,其中POZ构型均为O信封式、SOZ构型均为OO半椅式.      

基质隔离傅里叶红外光谱研究臭氧与乙烯的反应机制

用自行组建的低温基质隔离系统结合量子化学计算研究了乙烯与臭氧的反应机制,在试验中应用程序升温方法以检测、识别反应活性中间体.结果表明:试验中经红外吸收光谱识别为乙烯与臭氧反应中间体——POZ(初级臭氧化物)和SOZ(次级臭氧化物)的吸收峰均与文献报道的吸收峰完全吻合;在峰位和吸收强度上,试验测得的POZ和SOZ的大部分吸收峰均与B3LYP/6-311++G(2d,2p)计算的振动频率相一致,表明采用程序升温方法,将基质温度升到更高(200 K),不仅可检测到乙烯与臭氧反应的2个重要中间体——POZ和SOZ,更重要的是还清楚地显示了POZ生成、175 K时裂解和SOZ生成的整个反应历程,有力地支持了Criegee反应机制,证明基质隔离技术结合程序升温是一种研究烯烃与臭氧反应机制的可行方法.      

环戊烯臭氧化反应瞬变物种产生机制

大气中烯烃臭氧化反应产物是二次有机气溶胶(SOA)形成的重要前体物. 运用自行组建的低温基质隔离系统研究环戊烯臭氧化反应的瞬变物种产生机制. 采用程序升温方法,将温度从6 K升至115 K,用傅里叶红外光谱仪检测不同温度下生成的活性中间体,并将试验值与理论计算值、文献报道值进行对比,以确定中间体构型. 结果表明:环戊烯臭氧化反应生成的中间体——POZ(初级臭氧化物)、SOZ(二次臭氧化物)和CI(一分子羰基氧化物和一分子醛或酮)被成功检测到. 其中,POZ的特征吸收峰在705和946 cm-1处,对应O—O—O反对称伸缩振动和环变形振动;SOZ特征吸收峰在939 cm-1处,对应C—O伸缩振动;CI的特征吸收峰在1 733和853 cm-1处,分别对应CO伸缩振动和O—O伸缩振动. 据此,环戊烯臭氧化反应遵循Criegee机制. 采用4种量子化学计算方法——B3LYP/6-311++G(d,2p)、B3LYP/6-311++G(3df,3pd)、MP2/aug-cc-pvdz和PW91PW91/6-311++G(3df,3pd),计算POZ、SOZ和CI特征吸收峰的振动频率,其中POZ在705 cm-1处吸收峰的振动频率计算值分别为725、698、703、680 cm-1;SOZ在1 030 cm-1处吸收峰的振动频率计算值分别为1 017、1 018、1 025和993 cm-1;CI在1 733 cm-1处吸收峰的振动频率计算值分别为1 796、1 803、1 732和1 745 cm-1.表明MP2/aug-cc-pvdz计算的特征振动频率与试验值最接近.      

仲丁醇对苯乙烯臭氧化反应生成二次有机气溶胶的影响:实验和模型研究

通过烟雾箱实验,研究了仲丁醇对苯乙烯臭氧化反应生成二次有机气溶胶(SOA)的影响.结果发现,在烟雾箱实验中,过量仲丁醇的加入导致生成SOA的产率明显下降.同时,结合MCM气相机理和气-粒分配理论,将Criegee中间体与醛类的双分子反应添加到箱式模型中模拟烟雾箱中SOA的生成过程.模拟结果表明,在没有仲丁醇存在的情况下,次级臭氧化物在SOA组分中占1/2左右的比例.仲丁醇的加入消耗了大量的·OH,同时使得[HO_2]/[RO_2]比值升高,影响自由基相关的反应机制,使得SOA产率下降.另外,研究发现,Criegee中间体与醛类反应的速率常数也是影响SOA生成模拟的一个重要参数,需要进一步开展相关的动力学实验和理论研究.     

Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate

The reaction mechanism and kinetics of the simplest Criegee intermediate CH₂OO reaction with hydroperoxymethyl formate (HPMF) was investigated at high-level quantum chemistry calculations. HPMF has two reactive functional groups, -C(O)OH and -OOH. The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CH₂OO with –OOH group of HPMF were more favorable than the reactions of CH₂OO with -C(O)OH group. The calculated overall rate constant was 2.33 × 10^?13 cm³/(molecule?sec) at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K. In addition, we also proved the polymerization reaction mechanism between CH₂OO and -OOH of HPMF. This theoretical study interpreted the previous experimental results, and supplied the structures of the intermediate products that couldn't be detected during the experiment.     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

典型生物质燃烧排放酚类有机物的大气液相氧化动力学

生物质燃烧排放有机物是大气二次有机气溶胶(SOA)的重要前体物,但相关反应参数仍较为匮乏。选择其中4种代表性物质,间苯二酚(RES)、4-乙基苯酚(4-EP)、丁香酚(Eug)和2,4,6-三甲基苯酚(Trmp),利用相对速率法测定了其与·OH在液相(云雾条件)中的二级反应动力学参数,并估算了其在实际大气条件下的液相反应寿命。在pH=5.4,T=298 K条件下,测定以上4种前体物液相氧化的二级动力学常数(K)分别为(7.68±0.04)×109,(18.12±0.56)×109,(23.11±0.60)×109,(16.90±0.58)×109 L/(mol·s),所得到的K值不确定性为3.5%~12%。此外,还测定了体系在T=293,288 K时的K值,发现288 K时的K值比298 K时的低了22%~38%,说明温度对于酚类液相反应的双分子速率常数有一定影响。研究还发现,反应过程中前体物浓度为初始值1/2时,pH降低,说明反应过程中可能生成一定量的有机酸;这些化合物在不同情境下使用CAPRAM 3.0多相机制计算得到的大气寿命在数十秒到数十小时之间,进一步说明生物质燃烧排放酚类化合物对SOA的生成贡献值得重视。     

Characterization, reactivity, source apportionment, and potential source areas of ambient volatile organic compounds in a typical tropical city

Based on one-year observation, the concentration, sources, and potential source areas of volatile organic compounds (VOCs) were comprehensively analyzed to investigate the pollution characteristics of ambient VOCs in Haikou, China. The results showed that the annual average concentration of total VOCs (TVOCs) was 11.4 ppbV, and the composition was dominated by alkanes (8.2 ppbV, 71.4%) and alkenes (1.3 ppbV, 20.5%). The diurnal variation in the concentration of dominant VOC species showed a distinct bimodal distribution with peaks in the morning and evening. The greatest contribution to ozone formation potential (OFP) was made by alkenes (51.6%), followed by alkanes (27.2%). The concentrations of VOCs and nitrogen dioxide (NO₂) in spring and summer were low, and it was difficult to generate high ozone (O₃) concentrations through photochemical reactions. The significant increase in O₃ concentrations in autumn and winter was mainly related to the transmission of pollutants from the northeast. Traffic sources (40.1%), industrial sources (19.4%), combustion sources (18.6%), solvent usage sources (15.5%) and plant sources (6.4%) were identified as major sources of VOCs through the positive matrix factorization (PMF) model. The southeastern coastal areas of China were identified as major potential source areas of VOCs through the potential source contribution function (PSCF) and concentration-weighted trajectory (CWT) models. Overall, the concentration of ambient VOCs in Haikou was strongly influenced by traffic sources and long-distance transport, and the control of VOCs emitted from vehicles should be strengthened to reduce the active species of ambient VOCs in Haikou, thereby reducing the generation of O₃.     

Effectiveness of Poliovirus Concentration and Recovery from Treated Wastewater by Two Electropositive Filter Methods

Enteric viruses are often present in low numbers in various water matrices. Virus sampling therefore involves multiple concentration steps to condense large samples down to small volumes for detection by cell culture or molecular assays. The NanoCeram^® Virus Sampler has been demonstrated to be effective for the recovery of viruses from tap water, surface waters, and seawater. The goal of this study was to evaluate a new method using NanoCeram^® filters for the recovery of poliovirus 1 (PV-1) from treated wastewater. Activated sludge effluent samples were spiked with PV-1 and concentrated in side-by-side tests by two methods: (1) NanoCeram^® filtration, elution with sodium polyphosphate buffer, secondary concentration via centrifugal ultrafiltration; and (2) 1MDS filtration, elution with beef extract, secondary concentration via organic flocculation. The virus retention and elution efficiencies did not differ significantly between the two methods. In contrast, the secondary concentrate volume was smaller for the NanoCeram^® method (8.4 vs. 30 mL) and the secondary concentration efficiencies were different between the two methods with 98 % for centrifugal ultrafiltration (NanoCeram^®) and 45 % for organic flocculation (1MDS). The overall method efficiencies were significantly different (P ≤ 0.05) with the NanoCeram^® method yielding a 57 % and the 1MDS a 23 % virus recovery. In addition, there appeared to be less interference with viral detection via polymerase chain reaction with the NanoCeram^® concentrates. This NanoCeram^® method therefore is able to efficiently recover PV-1 from large volumes of wastewater and may serve as an inexpensive alternative to the standard 1MDS filter method for such applications.     

芬顿阴极-电凝聚臭氧气浮工艺处理MBR出水特性

为去除垃圾渗滤液MBR出水有机物,以铝(Al)为阳极,碳聚四氟乙烯(C-PTFE)为阴极构建了芬顿阴极-电凝聚臭氧气浮工艺,通过与常规电絮凝阴极(Al和SS)对比,探明了该工艺对垃圾渗滤液MBR膜出水的去除特性.结果表明:在pH5和臭氧流量为300mL/min时,芬顿阴极体系相比于SS和Al阴极体系对COD的去除率分别...     

基于PARAFAC分析的二级出水DOM臭氧化特性研究

基于三维荧光平行因子分析(PARAFAC analysis),对污水处理厂二级出水溶解性有机物(DOM)在不同臭氧投加量下的反应特性进行了研究,PARAFAC分析确定了污水厂二级出水中共有3个荧光组分,其中组分1为蛋白质类物质,组分2和3为腐殖质类物质.当臭氧为0.98mgO3/mgTOC时,3个组分中的荧光基团均可以和臭氧发生比较彻底的反应.线性回归分析表明,臭氧与组分1和组分2中荧光基团的反应可以很好地解释臭氧化对色度、UV254、UV280的去除.HPLC-SEC的结果进一步验证了PARAFAC的分析结果.同时,对于蛋白类物质组分1而言,臭氧主要和其中小分子物质的荧光基团发生反应,与其大分子物质几乎不发生反应.     

Removal of reactive gases at indoor surfaces: Combining mass transport and surface kinetics

The rate of deposition of reactive gaseous pollutants onto indoor surfaces is examined, taking into account mass transport processes and the kinetics of gas-surface interactions. A conceptual model for predicting indoor deposition velocities is proposed, and approximate analysis based on this model is used to obtain algebraic expressions for the deposition velocity of reactive gases under three model airflow conditions: (1) forced laminar convection parallel to a flat plate, (2) laminar natural convection flow along an isothermal vertical plate, and (3) homogeneous turbulence in an enclosure. Numerical simulations are used to refine the approximate analysis results and to predict reactive gas deposition under laminar natural convection flow in an enclosure. The kinetics of gas-surface interactions are modeled in terms of the reaction probability γ, defined as the fraction of pollutant molecular collisions with a surface that result in irreversible removal. Values of γ for the reaction of ozone with surfaces are obtained from published reaction chamber and tube penetration experiments. For common indoor materials, values range from as low as O(10⁻⁷) for glass and aluminium to O(10⁻⁵–10⁻⁴) for materials such as bricks, concrete and latex paint. Our results indicate that ozone deposition occurs at the transport-limited rate when γ > − 3 × 10⁻⁴ for typical indoor air flow conditions, and that ozone deposition can be predicted by surface kinetics alone if γ < ∼ 5 × 10⁻⁷.     

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...     

电极旋转放电条件下O3合成效率的理论研究

根据低温等离子体理论和电磁场理论，在实验的基础上研究了电极旋转条件下低温等离子体的产生机制和臭氧的合成机制，分析了放电过程中二次放电重叠对臭氧合成的影响，建立了旋转放电与二次放电的理论模型，并根据这一理论模型导出电极旋转条件下的臭氧合成效率与二次放电重叠概率以及电极旋转速度间的理论关系．这一理论结果表明：二次放电重叠使得臭氧合成效率降低，而电极以适当地速度旋转则可以有效地避免二次放电的重叠，从而提高臭氧的合成效率．理论值和实验结果能够较好地吻合．     

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.     

Theoretical study on the reaction mechanism of ozone addition to the double bonds of keto-limonene

The reaction mechanism of ozone (O₃) addition to the double bonds of gas phase keto-limonene was investigated using ab initio methods. Two different possibilities for O₃ addition to the double bond were considered and two corresponding van derWaals complexes (Complex 1 and Complex 2) were found for 1-endo and 2-endo. The rate constants were calculated using the transition state theory at the CCSD(T)/6-31G(d) + CF//B3LYP/6-31G(d,p) level. The high-pressure limit of the total rate constant at 298 K was 3.51 × 10^-16 cm³/(molecule sec), which was in a good agreement with the experimental data.     

活性炭催化臭氧氧化扑热息痛的机制研究

采用活性炭催化臭氧处理典型解热镇痛药扑热息痛,研究了活性炭/臭氧体系的协同效应,优化了工艺参数,分析了降解产物并探讨了降解机制.结果表明:在臭氧活性炭体系下,反应60 min后,TOC的去除率为55.11%,效果明显优于臭氧体系的20.22%和活性炭体系的27.39%之和,具有明显的协同作用,并且BOD5/COD比值从反应前的0.086提高到反应后的0.543,可生化性显著提高.研究了pH、臭氧投加量、污染物初始浓度和活性炭投加量等操作参数的作用规律.在此基础上,探讨了臭氧活性炭体系在不同pH下的催化反应机制,发现在酸性条件下是吸附和臭氧直接氧化共同作用,在碱性条件下以活性炭催化臭氧氧化为主.     

Relationships between chemical elements of PM2.5 and O3 in Shanghai atmosphere based on the 1-year monitoring observation

Mass level of fine particles(PM_2.5) in main cities in China has decreased significantly in recent years due to implementation of Chinese Clean Air Action Plan since 2013,however,03 pollution is getting worse than before,especially in megacities such as in Shanghai.In this work,O₃ and PM_2.5 were continuously monitored from May 27,2018 to March 31,2019.Our data showed that the annual average concentration of PM_2.5 and O₃(O₃-8 hr,max...     

深圳臭氧污染日的VOCs组成与来源特征

由于挥发性有机物（VOCs）是O₃生成的关键前体物,因此了解VOCs的污染特征以及主要来源对控制O₃污染具有重要的意义.本研究于2019年9~10月在深圳市开展了在线VOCs观测,共计监测104个物种.观测期间,臭氧超标率达17.8%.TVOCs总浓度为38.9×10^-9,污染日浓度明显高于非污染日.从大类物种来看,浓度从高到低依次为烷烃>含氧有机物（OVOCs）>卤代烃>芳香烃>烯烃>乙炔>乙腈,臭氧生成潜势（OFP）中芳香烃、OVOCs以及烯烃贡献较大.由PMF源解析模型分析结果可知,VOCs主要来源包括生物质燃烧、汽油挥发、机动车尾气、工业过程以及溶剂使用等,而其中对OFP贡献较大的排放源为溶剂使用（45.8%）、机动车尾气（27.3%）.臭氧污染日发生时,清晨低风速可能导致了机动车尾气与汽油挥发源在交通早高峰快速积累,而当日高温亦会加快汽油源与溶剂源组分挥发并促进光化学反应.