Experimental study of photooxidation products of ethylbenzene

Smog chamber experiments were performed to investigate the composition of products formed from photooxidation of aromatic hydrocarbon ethylbenzene. Vacuum ultraviolet photoionization mass spectrometer and aerosol time-of-flight mass spectrometer were used to measure the products in the gas and particle phases in real-time. Experimental results demonstrated that ethylphenol, methylglyoxal, phenol, benzaldehyde, and 2-ethylfurane were the predominant photooxidation products in both the gas and particle phases. However, there were some di erences between detected gas phase products and those of particle phase, for example, 2-ethylfurane, ethylglyoxylic acid, nitroethylbenzene, 3,4-dioxopentanal and ethyl-nitrophenol were only existing in the particle-phase. The possible reaction mechanisms leading to these products were also discussed and proposed.     

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.     

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.     

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.     

NOx存在条件下相对湿度对甲苯氧化产物的影响

利用流动管反应器模拟甲苯与氧化剂×OH在NO_x存在条件下的反应,定量测定了不同相对湿度条件下（17.5%、35%、50%、70%）反应生成的部分气相产物和颗粒相产物,计算了不同相中产物产率,测量了不同相对湿度下的颗粒相有机碳（OC）产率,推导了相对湿度对甲苯氧化反应的影响机制.结果表明,相对湿度不仅对甲苯与×OH反应途径比例有影响,还对产物的产率及氧化程度有影响.     

西安城区秋季大气中多溴联苯醚的污染特征及来源分析

为了评估西安大气中多溴联苯醚（PBDEs）的污染程度,2008年8～10月,利用大流量主动采样器采集了西安城区气态和颗粒态大气样品.分别利用GC-MS和GC/ECD对低溴PBDEs和BDE-209进行分析,12种PBDEs的总浓度（气相＋颗粒相）范围为37.43～620.30 pg/m3,平均值为216.28 pg/m...     

包气带水气二相流CO2运移规律

利用土柱实验装置模拟CO₂在土壤中的迁移转化规律,重点研究湿润峰处水、气二相间污染物转化实验土柱长1m,过饱和CO2溶液浓度为748mg/L.分析表明水相运移受对流、弥散、反应及水-气质量传输机制控制,气相运移受对流、扩散和水-气质量传输机制控制.对土柱中水气二相动态条件下的取样方法进行了探索,确定了CO₂在渗透湿润峰水-气二相间分配系数为0.00061,表明水相向气相有一定传输,但不显著.可进一步为低中水平放射性废物地质处置安全评价及固体废物填埋处置环境影响评价提供定量科学依据.     

基于热扩散管的深圳大气气溶胶半挥发性分析

在气溶胶质谱仪采样口前接入热扩散管,对深圳市2013年8月7日-9月7日大气细颗粒物进行连续在线观测,实现对气溶胶半挥发性的同步测定,量化其半挥发性水平.结果表明:加热温度为50℃时,约63%质量浓度的硝酸盐组分挥发至气相,是颗粒物中半挥发性最高的组分;而硫酸盐仍有约90%的颗粒残留,是半挥发性最低的组分;有机物的平均半挥发性高于硝酸盐,但低于硫酸盐.加热温度为200℃时,各组分的半挥发性接近,约有20%~30%的颗粒残留.在较为接近实际大气温度的50℃时,硝酸盐、有机物和硫酸盐的半挥发性因细颗粒物污染程度加剧而呈现不同的变化趋势.本文结果表明,深圳夏季大气细颗粒物具有显著的半挥发性,其大气环境影响值得今后深入研究.     

乌鲁木齐市典型城区大气PAHs气-粒分配特征

大气中PAHs的气-粒分配是影响其在大气中分布、迁移和转化的一个重要因素,于2011年12月—2012年12月在乌鲁木齐市天山区采集大气气相和颗粒相样品,对聚氨酯泡沫样品的气相和石英纤维膜的颗粒相(TSP)中的16种PAHs进行分析.结果表明:采样期间颗粒相和气相中ρ(∑₁₆PAHs)总和的年均值为(116.71±92.74) ng/m3,采暖期〔(173.16±84.26) ng/m3〕是非采暖期〔(39.46±16.19) ng/m3〕的4.4倍;采暖期颗粒相中ρ(∑₁₆PAHs)平均值为(40.60±3.03) ng/m3,气相为(134.46±13.05) ng/m3,2～3环PAHs主要存在于在气相中,4～6环PAHs主要存在于颗粒相中.在非采暖期,颗粒相ρ(∑₁₆PAHs)平均值为(25.37±3.21) ng/m3,气相为(14.95±1.06) ng/m3.采用吸附和吸收模型对PAHs的分配特征进行了研究,表明PAHs的lg K_p(K_p为分配系数)与lg P_L0(P_L0为过冷蒸汽压)线性关系显著,在采暖期斜率绝对值为0.34,说明PAHs的气-粒分配以吸收为主;在非采暖期的斜率绝对值为0.78,表明PAHs的气-粒分配受吸收和吸附共同作用.PAHs的lg K_p与lg K_oa(K_oa为正辛醇-大气分配系数)线性关系显著,在采暖期斜率为0.38,表明PAHs气-粒分配并未达到平衡;在非采暖期,斜率为1.22,表明PAHs气-粒分配接近平衡.研究显示,乌鲁木齐市城区大气PAHs气-粒分配在采暖期及非采暖期特征不同,应区别制订政策和管理措施.      

北京市石景山区夏季雨水和大气中PCBs的特征解析

利用气相色谱-质谱联用技术(GC-MS)对北京市石景山城区夏季雨水和大气中多氯联苯(PCBs)的分布特征进行了解析.结果表明,雨水中主要为溶解态PCBs,比例高达65.23%.大气中的PCBs以气态为主,占67.70%.研究表明,雨水对大气中颗粒态和气态PCBs的清除系数相当,分别为6.00×104和5.37×104.8种类二 PCBs同类物的毒性当量总和在大气气相、颗粒相和雨水中分别为0.36pg/m3、0.02pg/m3和0.29ng/L.北京石景山地区8种类二 PCBs同类物对成人呼吸暴露值为0.08pg/(kg·d),说明北京石景山地区人群呼吸暴露风险比较低.     

在TiO2催化剂上苯酚光催化氧化反应研究1．降解产物分布及反应途径

选择ＴｉＯ２粉末催化剂，考察了在中压汞灯作用下，苯酚光催化氧化途径及产物分布。对反应过程中的羟基物、羧酸及二氧化碳３个反应阶段的产物进行了详细的全组份分析。对其中８种主要产物追踪其浓度的变化。尤其对目前人们尚地确定的中间极性物，进行很好的分离测定。     

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol (SOA) formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer (ALTOFMS), respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 m (i.e., PM2.5), and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.     

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.     

西安城区大气中多氯联苯的气粒分配研究

为了解西安城区大气中多氯联苯(PCBs)的气粒分配规律,于2012年春季对西安城区大气中气态和颗粒态样品进行每周一次的主动采样.结果表明,西安城区大气中PCBs的总浓度(气态和颗粒态)为62.05~454.18pg/m3,主要以气态为主.由Clausius-Clapeyron方程得到的斜率较陡(-5193.24),表明春季大气中的PCBs主要受西安城区附近地面挥发释放的影响.PCBs的气粒分配系数(KP)与过冷饱和蒸汽压(PoL)高度相关,由logKP和logPoL线性回归得到的斜率mr(-0.46~-0.37)均高于平衡状态理论值-1,说明西安城区大气中的PCBs气粒分配尚未达到平衡状态.采用Junge-Pankow吸附模型和Harner-Bidleman吸收模型对PCBs颗粒态百分比(φ)及KP进行了模拟,结果显示两种模型均较好地预测了PCBs的气粒分配行为,但与实验测得的值相比,两种模型均高估了φ值及KP值.     

低温条件下基于TMVOC的土壤气相抽提技术数值模拟

为研究低温条件下土壤气相抽提技术对包气带中苯系物的去除效果、解决修复技术有效性评估等难题,基于TMVOC模型模拟砂箱试验,从浓度梯度、相间转化、饱和度变化等方面分析土壤气相抽提技术对污染物空间分布规律的影响机理.结果表明,TMVOC模拟苯系物浓度的计算值与试验测量值的拟合效果较好;低温条件下,砂箱土体中苯、甲苯、乙苯、邻二甲苯的去除率分别为89.8%、71.3%、29.7%、14.4%.两次抽提过程中,苯在"气-液-NAPL（non-aqueous phase liquid）"三相中的质量均减少,减少比例近似为2:7:1,苯在液相中的质量减幅最大;在间歇期,苯由"NAPL相"以近似3:7的比例向"气、液"两相运移.在砂箱土体上部和中部NAPL相饱和度保持为0,"气-液"两相共存,间接表明苯系物在"气-液"两相间发生运移;在砂箱土体底部污染源附近"气-液-NAPL"相共存,间接表明苯系物在"气-液-NAPL"相间发生运移,抽提作用使得气相与液相饱和度升高、NAPL相饱和度降低.      

杭州市办公场所室内空气中PBDEs的污染现状与特征

分析评价了杭州市办公场所中PBDEs的污染现状、污染特征.结果表明,办公场所中PBDEs气相和颗粒相总浓度范围为40.66~141.00 pg·m-3,平均浓度为93.22 pg·m-3,是家庭室内、室外浓度的1.87、5.01倍.BDE-47、BDE-99为办公场所中最重要的两种同系物,分别占总浓度的33.29%、31.99%.PBDEs气相浓度是颗粒相的1.34倍,其中BDE-28、BDE-47、BDE-99主要存在于气相中,BDE-153、BDE-183主要存在于颗粒相中.     

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.     

燃煤电厂排放PAHs的气粒分配机制和排放通量

对循环流化床锅炉(CFB)布袋除尘器进口和出口的多环芳烃(PAHs)进行了分析,研究了PAHs在气相和颗粒相中的分配机理.结果表明,除尘过程气相和颗粒相PAHs对应的去除率分别为45.59％与70.67％～89.06％.气相中主要为低分子量PAHs,颗粒相中主要为高分子量PAHs.随着粒径的增加,低分子量PAHs比例呈...     

A VUV photoionization mass spectrometric study on the OH-initiated photooxidation of isoprene with synchrotron radiation

The gas-phase organic compounds resulting from OH-initiated photooxidation of isoprene have been investigated on-line by VUV photoionization mass spectrometry based on synchrotron radiation for the first time. The photoionization efficiency curves of the corresponding gaseous products as well as the chosen standards have been deduced by gating the interested peaks in the photoionization mass spectra while scanning the photon energy simultaneously, which permits the identification of the pivotal gaseous products of the photooxidation of isoprene, such as formaldehyde (10.84 eV), formic acid (11.38 eV), acetone (9.68 eV), glyoxal (9.84 eV), acetic acid (10.75 eV), methacrolein (9.91 eV), and methyl vinyl ketone (9.66 eV). Proposed reaction mechanisms leading to the formation of these key products were discussed, which were completely consistent with the previous works of different groups. The capability of synchrotron radiation photoionization mass spectrometry to directly identify the chemical composition of the gaseous products in a simulation chamber has been demonstrated, and its potential application in related studies of atmospheric oxidation of ambient volatile organic compounds is anticipated.     

Potential particulate pollution derived from UV-induced degradation of odorous dimethyl sulfide

UV-induced degradation of odorous dimethyl sulfide (DMS) was carried out in a static White cell chamber with UV irradiation. The combination of in situ Fourier transform infrared (FT-IR) spectrometer, gas chromatograph-mass spectrometer (GC-MS), wide-range particle spectrometer (WPS) technique, filter sampling and ion chromatographic (IC) analysis was used to monitor the gaseous and potential particulate products. During 240 min of UV irradiation, the degradation e ciency of DMS attained 20.9%, and partially oxidized sulfur-containing gaseous products, such as sulfur dioxide (SO2), carbonyl sulfide (OCS), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2) and dimethyl disulfide (DMDS) were identified by in situ FT-IR and GC-MS analysis, respectively. Accompanying with the oxidation of DMS, suspended particles were directly detected to be formed by WPS techniques. These particles were measured mainly in the size range of accumulation mode, and increased their count median diameter throughout the whole removal process. IC analysis of the filter samples revealed that methanesulfonic acid (MSA), sulfuric acid (H2SO4) and other unidentified chemicals accounted for the major non-refractory compositions of these particles. Based on products analysis and possible intermediates formed, the degradation pathways of DMS were proposed as the combination of the O(1D)- and the OH- initiated oxidation mechanisms. A plausible formation mechanism of the suspended particles was also analyzed. It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.