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.     

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.     

紫外大气甲醛卫星遥感反演方法和研究现状

在我国长期稳定的甲醛观测站点十分缺失,卫星平台高时频、大面积覆盖等优势使得通过卫星遥感探测大气甲醛成为了一种重要的研究手段.本文讨论了现有载荷的反演理论和方法,分析了我国大气甲醛的研究现状及不足.简述了从20世纪至今可用于甲醛探测的主要载荷：GOME/ERS-2,SCIAMACHY/ENVISAT,OMI/Aura,GOME-2/MetOp-A（B）,OMPS/Suomi-NPP,总结归纳了各个卫星载荷仪器的轨道信息、时间空间分辨率等相关参数,以及各个传感器在大气甲醛遥感反演中的可行性.由于卫星自上而下的观测方式与地基平台不同,其反演方法也有不同之处,因此本文针对卫星平台综合论述了两种甲醛反演算法：传统的差分吸收光谱法（DOAS）和针对于甲醛反演的一系列改进算法以及近几年提出的主成分分析法（PCA）;另外,本文针对现有反演算法和时空分布在我国中东部地区的研究现状和不足进行了综合讨论,并给出了一定的改进策略.     

Intercomparison of tunable diode laser and gas filter correlation measurements of ambient carbon monoxide

An intercomparison that involved a standards intercomparison, interferant spiking tests and simultaneous ambient measurements was carried out between two CO measurement systems: a tunable diode laser absorption spectrometer (TDLAS) and a gas filter correlation, non-dispersive infrared absorption instrument (GFC). Both the TDLAS and the GFC techniques responded to CO. No major interferences were found for the TDLAS system; tested species included H₂O, O₃ and OCS. The GFC instrument exhibited no interference from H₂O or O₃, but only a relatively high upper limit could be placed on the O₃ interference. For CO measurements in ambient air at levels from 100 to 1500 ppbv, the results from the two instruments agreed within their combined uncertainties. On average the GFC technique was 6% higher than the TDLAS system, and there was no systematic, constant offset. The precision of the GFC instrument was about 10%, and the precision of the TDLAS system was better than 4%.     

连续测量大气·OH的化学电离飞行时间质谱仪的研制

搭建了一套化学电离飞行时间质谱仪用于连续测量大气·OH.该仪器采用了基于63Ni放射源的双管正交式结构大气压化学电离源电离大气中的·OH,最大程度地避免了试剂气体电离及滴定、转化反应间的相互干扰.63Ni放射源首先电离HNO3试剂气体得到试剂离子NO-3,·OH在反应管中与SO2反应最终转化为H2SO4,NO-3与H2SO4发生化学电离反应生成HSO-4离子,进入到质谱仪中进行检测,通过测量NO-3与HSO-4离子的强度,利用化学电离反应方程可直接计算出大气中OH的浓度.所研制仪器用于实验室内·OH的在线检测,在5 s内测得·OH的浓度为1.6×106个·cm-3,实验结果显示该仪器可用于原位连续测量大气中的超痕量自由基.     

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...     

华北农村夏季大气甲醛浓度变化特征

为研究华北农村大气污染状况,于2013年夏季和2014年夏季先后在华北两个农村站点——固城站、饶阳站,采用基于汉栖(Hantzsch)反应的在线甲醛荧光分析仪开展大气甲醛在线观测,结合同期φ(O₃)、φ(PAN)(PAN为过氧乙酰硝酸酯)、φ(CO)和光解速率系数等数据,分析φ(甲醛)日变化及其光解速率等特征. 结果表明:华北农村夏季大气甲醛污染较重. 固城站和饶阳站φ(甲醛)分钟均值范围分别为0.05×10-9 ~59.18 ×10-9和1.66×10-9 ~ 46.83×10-9,平均值分别为12.82×10-9±7.59×10-9和13.73×10-9±5.82×10-9,高于文献报道的国内外其他地区的观测值,与同期观测的φ(NO_x)相当. 两个站点φ(甲醛)具有典型的日变化特征,φ(甲醛)小时均值峰值(固城站为17.43×10-9,饶阳站为17.57×10-9)均出现在上午10:00左右,与φ(O₃)和φ(PAN)的日变化趋势相似,但峰值早1 h出现. 光解速率系数观测结果表明,两个站点甲醛光解过程主要发生在06:00—18:00,固城站甲醛小时光解量峰值(2.59×10-9)出现在11:00,饶阳站甲醛小时光解量于正午12:00达到峰值(3.00×10-9),甲醛光解成稳定分子的速率是光解成自由基速率的1.2~1.7倍. 研究表明,两个站点φ(甲醛)的变化主要受局地过程的影响,光化学生成是甲醛的重要来源.      

光化学烟雾箱的表征及初步应用

介绍了一套自制的用于光化学臭氧和二次有机气溶胶生成研究的室内烟雾箱系统,对该烟雾箱系统进行了一系列表征实验,包括活性物种的壁损失速率常数的测定,以及由CO-NOx光氧化实验确定的反应器内·OH源,并进行了乙烯-NOx和苯-NOx光氧化的初步实验.结果表明,O3和NO2在新反应袋中壁损失受湿度影响很小,而在旧反应袋中影响...     

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.     

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.     

羊草草原和贝加尔针茅草原生态系统呼吸的差异分析

应用静态暗箱-气相色谱法对羊草草原和贝加尔针茅草原的生态系统呼吸CO2通量进行了测算,分析了生态系统呼吸的影响因素,比较了2种草原生态系统呼吸的差异并分析了产生差异的原因.观测期间羊草草原生态系统呼吸CO2通量平均为(12.03±2.10)mg·(m2·min)-1,显著低于贝加尔针茅草原[(20.09±4.41)mg·(m2·min)-1];而羊草草原生物量显著大于贝加尔针茅草原(p0.001).羊草草原和贝加尔针茅草原生态系统呼吸都与温度(箱内气温、5cm和15cm地温)具有显著的指数函数关系.通过偏相关分析发现,在地温作为控制变量时,生态系统呼吸与土壤Eh、pH间不再具有显著的相关性,Eh、pH对CO2通量的影响可能是由地温变化间接引起的,而CO2通量与活体生物量呈现出了一定的相关性,与凋落物生物量无显著相关性.2种草原的CO2通量都可以用温度指数模型进行很好地模拟,基于地温的模拟效果(R2为0.568～0.639)显著好于基于箱内气温的(R2为0.323～0.426).地温是2种草原生态系统呼吸最重要的影响因素,它掩盖了地上部植物体对生态系统呼吸的影响.在该区域,土壤呼吸占生态系统呼吸比例较高,贝加尔针茅草原较高的有机质含量导致了其生态系统呼吸CO2通量较高.     

沿海城市秋季大气甲醛污染来源及其环境影响

基于大气综合观测站的气态污染物(HCHO、O₃、PAN、CO、NOx、异戊二烯)及气象要素(温度、湿度、风速、风向)等在线观测数据,研究沿海城市厦门秋季大气HCHO的时间变化特征及其关键影响因子,利用多元线性回归分析方法定量识别HCHO的主要来源,并估算HCHO对·OH生成的贡献.结果表明:HCHO平均浓度为(3.15±1.40)×10^-9,范围为(0.55～7.96)×10^-9,呈现明显“单峰”日变化特征,峰值出现在13:00左右.HCHO与O₃、PAN显著正相关;温度、湿度和UV是影响HCHO浓度的主要气象因素,强辐射、高温、低湿、低风速和西南风的条件促进了厦门大气HCHO的二次生成. HCHO小时光解量(PHCHO)范围为(0.01～3.02)×10^-9/h,平均PHCHO为0.61×10^-9/h,同时,大气HCHO光解成稳定分子H2和CO的速率是光解成自由基H·和HCO·速率的1.1～1.6倍.观测期间大气HCHO来源主要包括二次生成(39.2%)...     

珠江三角洲光化学活跃期甲醛及其前体物的源解析研究

选取珠江三角洲大气超级站的三个代表性超级站点（东莞东城城市超级站、深圳莲花山城市超级站和鹤山花果山区域超级站）,同步在线监测和分析了2021年5~10月大气光化学活跃期甲醛（HCHO）及其前体物挥发性有机物（VOCs）组分的时空变化特征,利用多元线性回归法对HCHO来源进行解析,识别出了关键VOCs前体物及其贡献,并对比了三个点位来源及前体物的差异.结果表明：三个站点的HCHO体积浓度存在明显差异,鹤山区域站浓度最高达5.82×10^-9,与历史研究数据相比浓度升高,而城市超级站东城与莲花山浓度水平降低.臭氧浓度与甲醛浓度存在一定相关性,各站点臭氧浓度最高的9月,HCHO的平均浓度水平也高;臭氧超标日的HCHO浓度显著高于臭氧非超标日.利用多元线性回归法,选择甲苯、异戊二烯和O₃作为源示踪剂,结果表明二次源对HCHO来源贡献占比最多,范围为43.5%~54.9%,其中区域站点二次源占比高于其它两个城市站点.基于生成产率法得到各站点二次转化生成HCHO的前体物主要为烯烃,其中贡献最大的是异戊二烯,其次为乙烯和丙烯.综合对比,HCHO的一次人为源的下降导致城市站点HCHO浓度降低,较高的二次转化导致了区域站点HCHO浓度升高,需重点关注甲醛的人为源直接排放和异戊二烯、苯乙烯、乙烯等前体物.     

Elimination of formaldehyde over Cu-Al2O3 catalyst at room temperature

Catalytic elimination of formaldehyde (HCHO) was investigated over Cu-Al2O3 catalyst at room temperature. The results indicated that no oxidation of HCHO into CO2 occurs at room temperature, but the adsorption of HCHO occurs on the catalyst surface.With the increase of gas hourly space velocity(GHSV) and inlet HCHO concentration, the time to reach saturation was shortened proportionally. The results of the in situ DRIFTS, Density functional theory calculations and temperature programmed desorption(TPD) showed that HCHO was completely oxidized into HCOOH over Cu-Al2O3 at room temperature. With increasing the temperature in a flow of helium, HCOOH was completely decomposed into CO2 over the catalyst surface, and the deactivated Cu-Al2O3 is regenerated at the same time. In addition, although Cu had no obvious influence on the adsorption of HCHO on Al2O3, Cu dramatically lowered the decomposition temperature of HCOOH into CO2. It was shown that Cu-Al2O3 catalyst had a good ability for the removal of HCHO, and appeared to be promising for its application in destroying HCHO at room temperature.     

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.     

成都郊区(新津)夏季甲醛污染特征分析

甲醛（HCHO）是大气光化学重要污染物之一,为研究西南地区郊区大气夏季甲醛污染特征选取了四川省成都市新津区进行大气甲醛观测,结合NO_x、O₃、PAN、J-value、温湿度、风速风向、天气数据进行分析.观测期间成都市新津区夏季甲醛浓度为0.76×10^-9~12.50×10^-9（V/V）,均值为3.47×10^-9±2.05×10^-9（V/V）,呈现明显的日变化规律.结合数据分析可知,一次人为排放源在成都郊区夏季日间甲醛贡献中占比较低.观测期间甲醛受光照的影响较大,与O₃、PAN、J-value普遍呈现一致的变化规律,因此成都市夏季日间甲醛主要来源为甲醛前体物的二次光化学反应.     

大气模拟烟雾箱中HONO的表征

NO2与H2O在烟雾箱表面生成HONO的异相反应是导致烟雾箱实验数据不确定性增加的主要原因之一,因此.必须对该反应进行表征.本研究采用烟雾箱实验与箱式模型模拟相结合的方法,确定实验系统特有的HONO释放速率.实验在室内烟雾箱实验系统完成,通过NO、NO2沉积实验获得的气态反应物在烟雾箱壁面(Teflon膜)上的沉积速率分别为0.0026 h-1及0.0025 h-1;光解实验得到NO2的光解速率为0.21min-1,在此基础上利用量子产率、吸收截面积、光谱分布计算出其它6个光解反应的速率常数.将实验获取的速率常数与CB-Ⅳ反应机理联合使用建立箱式模拟系统,利用c0一NO实验数据对模拟参数进行优化,得到该系统的HONO的释放速率为1.65×10-5cm3·mol-1·s-1.由此提供了一种表征实验与箱式模型联合使用确定烟雾箱系统HONO释放速率的有效方法.     

基于OMI数据的中国中东部臭氧及前体物的时空分布

基于OMI卫星资料,分析了2005—2014年中国中东部地区对流层低层ρ(O₃)、对流层NO₂柱浓度及甲醛总柱浓度的时空演变趋势及相互关系. 结果表明:近10年来,中国中东部地区对流层低层ρ(O₃)呈上升趋势,2005年及2014年分别为60.64、69.43 μg/m3,年均增长率为1.6%;对流层低层ρ(O₃)增长的区域面积不断扩大,部分地区增长超23 μg/m3;呈春夏季高,冬季最低的分布趋势. 2005—2012年,对流层NO₂柱浓度呈上升趋势,2005年及2012年分别为4.41×1015、5.90×1015 mol/cm2,年均增长率为4.8%;2012年后呈下降趋势,下降的区域面积逐步扩大,部分地区降低约 15×1014 mol/cm2;呈冬季最高、夏季最低的分布特征;2005—2010年甲醛总柱浓度呈上升趋势,2005年及2010年分别为9.74×1015、1.59×1016 mol/cm2,年均增长率为12.6%,2010年后呈下降趋势;呈夏季最高、冬季最低的分布特征;甲醛总柱浓度增长的区域面积逐渐扩大. 利用甲醛与NO₂柱浓度比值探讨臭氧控制区的空间分布特征,表明鲁豫晋、京津冀、长三角及珠三角地区中心城市属于VOCs控制区,周围城市属于VOCs-NO_x协同控制区,其他地区属于NO_x控制区.      

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.      

Formaldehyde concentration and its influencing factors in residential homes after decoration at Hangzhou, China

Air pollution surveys of formaldehyde(HCHO) were conducted in 2324 rooms decorated within one year in 2007-2009 in Hangzhou,China.The mean HCHO concentration(C HCHO) was 0.107 ± 0.095 mg/m 3,and 38.9% of samples exceeded the Chinese National Standard GB 50325-2010.Over the past 3 years,the C HCHO decreased with time(p < 0.05).Relationships of potential factors to indoor C HCHO were also evaluated.C HCHO was related to temperature(T),relative humidity(RH),time duration of the windows and doors being closed before sampling(DC),time duration from the end of decoration to sampling(DR) and source characteristics(d).A model to relate indoor C HCHO to these five factors(T,RH,DC,DR,d) was established based on 298 samples(R 2 = 0.87).Various factors contributed to C HCHO in the following order:T,43.7%;d,31.0%;DC,10.2%;DR,8.0%;RH,7.0%;specifically,meteorological conditions(i.e.,RH plus T) accounted for 50.7%.The coefficient of T and RH,R TH,was proposed to describe their combined influence on HCHO emission,which also had a linear relationship(R 2 = 0.9387) with HCHO release in a simulation chamber test.In addition,experiments confirm that it is a synergistic action as T and RH accelerate the release of HCHO,and that is a significant factor influencing indoor HCHO pollution.These achievements could lead to reference values of measures for the efficient reduction of indoor HCHO pollution.