Reactor characterization and primary application of a state of art dual-reactor chamber in the investigation of atmospheric photochemical processes

Increasing attention has been paid to the air pollution more recently. Smog chamber has been proved as a necessary and effective tool to study atmospheric processes, including photochemical smog and haze formation. A novel smog chamber was designed to study the atmospheric photochemical reaction mechanism of typical volatile organic compounds (VOCs) as well as the aging of aerosols. The smog chamber system includes an enclosure equipped with black lights as the light source, two parallel reactors (2 m³ of each) with separate control of light source and temperature, with a series of coupled instruments for online monitoring of gas phase and particle phase reactants and products. Chamber characterization, including air source stability, effective light intensity, temperature stability, as well as gas phase and particle phase wall losses, were carried out before further research. The results showed that our smog chamber systems developed by other domestic and international groups. It was also observed that the wall loss of aromatic VOCs varied with different functional groups as well as the isomerism. The results of preliminary simulation experiment from styrene-NO_x demonstrated that the chamber can be well utilized to simulate gas-particle conversion progresses in the atmosphere.     

A detailed mechanism for the gas-phase atmospheric reactions of organic compounds

A gas-phase reaction mechanism for the atmospheric photooxidations of over 100 alkanes, alkenes, aromatic hydrocarbons, alcohols, ethers and other compounds representative of the range of reactive organics emitted into polluted atmospheres is described. Most of these organic species are represented using generalized reactions with variable rate constants and product yield coefficients for which individual assignments were made or estimated. This mechanism employs 19 species to repsent the reactive oxygenated and organic nitrate products, and includes the gas-phase reactions of SO₂, but does not include heterogeneous or liquid-phase reactions. The evaluation of this mechanisms, by comparison of its predictions against the results over 500 environmental chamber experiments, described in a separate paper. This detailed mechanism can be used in assessments of relative atmospheric reactivities of organic compounds, and can provide the basis for the derivation of more condensed mechanisms for use in air quality simulation models.     

田间原位开顶式臭氧熏蒸系统研究

臭氧污染造成的粮食作物减产及经济损失受到普遍关注,研究植被对臭氧的响应是评估臭氧污染造成影响的重要依据. 针对国内外已有开顶式熏蒸系统的缺点,改进布气管的布气孔大小和形状,以保证气室内布气的均匀性;改进风机的供气方式,采用一供三的方式以提高各平行样间的平行性;通过计算机负反馈控制和采用引流装置,以提高臭氧浓度控制和测定的准确性. 在国内率先尝试在跟随环境臭氧浓度的基础上增加一定浓度的臭氧作为熏蒸气体. 田间实测表明:该装置气室内臭氧浓度与设定浓度一致且分布均匀,平行样的平行性好,气室内外温度、相对湿度及光照强度衰减均达到了国内外同类装置水平,可广泛用于田间原位大气污染物对植被影响的研究.      

Geological emission of methane from the Yakela condensed oil/gas field in Talimu Basin, Xinjiang, China

A static flux chamber method was applied to study natural emissions of methane into the atmosphere in the Yakela condensed oil/gas field in Talimu Basin, Xinjiang, China. Using an online method, which couples a gas chromatography/high-temperature conversion/isotope ratio mass spectrometry (GC/C/MS) together, the 13C/12C ratios of methane in the flux chambers were measured. The results demonstrated that methane gases were liable to migrate from deep oil/gas reservoir to the surface through microseepage and p...     

胜坨油田原油温室气体排放特征及其影响因素

为研究油田开发过程中原油在大气条件下的碳排放特征,完善油气系统潜在温室气体排放清单,以胜利油田典型区块——胜坨油田原油为研究对象,通过改进的静态室-气相色谱及质谱法对原油在大气条件下的自然脱气(排放)过程进行模拟试验研究. 结果表明:CH₄和CO₂是胜坨油田原油溶解气中的两种主要温室气体;将模拟时间(48 h)均分为4个时段,CH₄、CO₂的主要排放阶段为0~12 h,并且其排放量远高于>12~24、>24~36和>36~48 h,其中,不同温度下CH₄、CO₂的最大排放率均出现在0~2 h. 原油在空气中暴露时间的长短及所处大气温度的高低直接影响温室气体的累积排放,CH₄、CO₂的累积排放量均随模拟试验的进行而递增;原油所处环境温度越高,累积排放量越大,3 ℃时CH₄、CO₂的累积排放量分别为12.498、15.071 g/m3,13 ℃时为20.626、21.004 g/m3,27 ℃时为31.353、26.954 g/m3. CH₄、CO₂在不同温度下的相对排放量存在差异,表现为低温(3、13 ℃)条件下CH₄排放量低于CO₂,相对高温(27 ℃)条件下表现相反. 研究显示,原油所处大气环境的温度及暴露时间是影响原油温室气体排放的重要因素.      

Evaluation of a detailed gas-phase atmospheric reaction mechanism using environmental chamber data

This paper describes an evaluation of the performance of a detailed gas-phase reaction mechanism in simulating the results of 561 experiments carried out in four different environmental chambers. The experiments included background air, NO_x-air, CONO_x-air and aldehyde-air irradiations used for chamber characterization, NO_x-air irradiations of single organics as well as simple and complex organic mixtures, and irradiations of auto exhaust. The methods used to represent the major chamber effects and the lighting characteristics in the model simulations of the experiments are described and their associated uncertainties are discussed. Statistical measures of the performance of the mechanism in simulating results of the various types of experiments are summarized and discussed. The mechanism was able to predict maximum ozone yields and rates of NO oxidation to within ±30% for 63% of the experiments modeled, and to within ±50% for 85% of the runs. There is a slight bias (∼15%) towards overprediction of ozone in mixture runs. Although there are cases where the simulations suggest possible problems with the gas-phase mechanism, much of the variability in the goodness of the fits could be attributed to uncertainties in chamber effects. It is concluded that better characterization of chamber conditions are needed if more comprehensive tests of atmospheric photochemical mechanisms are desired.     

Mechanism and kinetic properties of NO3-initiated atmospheric degradation of DDT

In this article, the NO3 radical-initiated atmospheric oxidation degradation of DDT was theoretically investigated using molecular orbital theory calculations. All the calculations of intermediates, transition states and products were performed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level of theory. Several energetically favorable reaction pathways were revealed. The formation mechanisms of secondary pollutants were presented and discussed. The rate constants were deduced over the temperature range of 273–333 K using canonical variational transition-state(CVT) theory with the small curvature tunneling(SCT) method. Our study shows that H abstraction from the alkyl group and NO3 addition to the C3 atom of the benzene ring are the dominant reaction pathways. The rate-temperature formula of the overall rate constants is k(T)(DDT+NO3) =(7.21 × 10.15)exp(–153.81/T) cm3/(mol·sec) over the possible atmospheric temperature range of 273–333 K. The atmospheric lifetime of DDT determined by NO3 radical is about 52.5 days, which indicates that it can be degraded in the gas phase within several months.     

Knudsen cell and smog chamber study of the heterogeneous uptake of sulfur dioxide on Chinese mineral dust

The heterogeneous uptake processes of sulfur dioxide on two types of Chinese mineral dust（Inner Mongolia desert dust and Xinjiang sierozem） were investigated using both Knudsen cell and smog chamber system. The temperature dependence of the uptake coefficients was studied over a range from 253 to 313 K using the Knudsen cell reactor, the initial uptake coefficients decreased with the increasing of temperature for these two mineral dust samples, whereas the steady state uptake coefficients of the Xinjiang sierozem increased with the temperature increasing, and these temperature dependence functions were obtained for the first time. In the smog chamber experiments at room temperature, the steady state uptake coefficients of SO2 decreased evidently with the increasing of sulfur dioxide initial concentration from 1.72 × 1012 to 6.15 × 1012mol/cm3. Humid air had effect on the steady state uptake coefficients of SO2 onto Inner Mongolia desert dust.Consequences about the understanding of the uptake processes onto mineral dust samples and the environmental implication were also discussed.     

大气模拟烟雾箱系统的研究进展

烟雾箱是研究大气光化学反应的主要工具.30年来国内外有多个研究机构建立了烟雾箱,并对各种光化学反应进行了研究,以收集数据来发展和检验大气光化学反应机理.从系统构造、配置仪器及所进行的光化学实验几个方面,综述了国内外烟雾箱系统的研究进展,其中背景影响较小的烟雾箱能为评价化学反应机理提供精度较高的数据,二次有机气溶胶(secondary organic aerosol,SOA)的形成机理成为目前的研究热点.     

专用霉菌试验箱技术特点

针对霉菌及其孢子对人体的潜在危害和对环境的污染,着重从生物安全和试验的实际需要出发研制出专用霉菌试验箱--MJ-1000霉菌试验箱.该款试验箱在结构、循环风速、灭菌、换气、清洗以及安全防护设施等方面有明显优势.结果表明,MJ-1000霉菌试验箱具有良好的温湿度均匀性和稳定性,使用该款试验箱所得试验结果的重现性和可靠性明显高于其它类型霉菌试验箱.     

A tunable diode laser absorption spectrometer for formaldehyde atmospheric measurements validated by simulation chamber instrumentation

A tunable diode laser absorption spectrometer (TDLAS) for formaldehyde atmospheric measurements has been set up and validated through comparison experiments with a Fourier transform infrared spectrometer (FT-IR) in a simulation chamber. Formaldehyde was generated in situ in the chamber from reaction of ethene with ozone. Three HCHO ro-vibrational line intensities (at 2909.71, 2912.09 and 2914.46 cm^-1) possibly used by TDLAS were calibrated by FT-IR spectra simultaneously recorded in the 1600-3200 cm^-1 domain during ethene ozonolysis, enabling the on-line deduction of the varying concentration for HCHO in formation. The experimental line intensities values inferred confirmed the calculated ones from the updated HITRAN database. In addition, the feasibility of stratospheric in situ HCHO measurements using the 2912.09 cm^-1 line was demonstrated. The TDLAS performances were also assessed, leading to a 2σ detection limit of 88 ppt in volume mixing ratio with a response time of 60 sec at 30 Torr and 294 K for 112 m optical path. As part of this work, the room-temperature rate constant of this reaction and the HCHO formation yield were found to be in excellent agreement with the compiled literature data.     

空冷塔对大气环境温度湿度影响的数值模拟

运用FLUENT建立空冷塔模型进行数值模拟,研究不同出口温度、环境温度和侧风速度下空冷塔与大气环境之间的传热.结果表明：不同出口温度及环境温度对空冷塔与大气环境间的换热有显著影响.其中,当出口温度升高到328K时,空冷塔近地面层空气温度上升6.22K,而其相对湿度由47.7%降至31.78%,空气干燥程度增大;随着环境温度与排气温度间温差增大,换热效果更为显著,表现为冬季空气干燥程度变化最大,春秋次之,夏季最小.不同环境风速对空冷塔与大气环境间换热区域影响显著,其中,当侧风风速为7m/s时,热交换影响区域可达11.17km,且空冷塔近处相对湿度由47.7%降至39.47%.     

宁东基地大气PAHs污染特征及呼吸暴露风险

利用主动观测技术对宁东能源化工基地大气PM_2.5、PM_1.0和气相中的PAHs浓度水平、族谱特征、时空分布及来源进行研究,并基于该观测数据对居民呼吸暴露健康风险进行评估.结果表明,宁东基地大气PM_2.5、PM_1.0及气相中∑₁₆PAHs浓度范围分别为：17.95~325.12ng/m³、12.66~311.96ng/m³和26.33~97.88ng/m³,年均浓度分别为（99.42±117.48）ng/m³、（78.88±100.58）ng/m³和（57.89±47.39）ng/m³.宝丰基地冬夏季大气PM_2.5、PM_1.0和气相中∑₁₆PAHs浓度水平均明显高于英力特;宝丰和英力特基地冬季大气PM_2.5、PM_1.0中∑₁₆PAHs浓度水平均明显高于夏季浓度.宁东基地大气中∑₁₆PAHs的浓度水平要高于国内外其他城市,大气PAHs污染较为严重.源解析表明夏季宁东基地PAHs的主要排放源是工业煤燃烧和机动车尾气,冬季则主要来自工业煤燃烧和木材、薪柴等生物质燃烧排放.宁东基地人群暴露于大气PAHs可能会造成平均冬季每百万人中约有33~2628人罹患癌症,夏季每百万人中约有11~834人罹患癌症的风险.     

Quantification of carbon dioxide and methane emissions in urban areas: source apportionment based on atmospheric observations

Anthropogenic emissions of carbon dioxide (CO₂) and methane (CH₄) in the atmosphere constitute an important component of the related carbon budget. The main source of anthropogenic CO₂ is burning of fossil fuels, especially in densely populated areas. Similar emissions of CH₄ are associated with the agricultural sector, coal mining, and other human activities, such as waste management and storage and natural gas networks supplying methane to large urban, industrial centers. We discuss several methods aimed at characterizing and quantifying atmospheric loads and fluxes of CO₂ and CH₄ in Krakow, the second largest city in Poland. The methods are based on atmospheric observations of mixing ratios as well as isotopic composition of the investigated gases. Atmospheric mixing ratios of CO₂ and CH₄ were measured using gas chromatography (GC) and cavity ring-down spectroscopy (CRDS). The isotopic composition of CO₂ and CH₄ was analyzed using isotope ratio mass spectrometry (IRMS), accelerator mass spectrometry (AMS), and CRDS techniques. These data, combined with auxiliary information characterizing the intensity of vertical mixing in the lower atmosphere (height of the nocturnal boundary layer [NBL] and atmospheric ²²²Rn concentration), were further used to quantify emission rates of CO₂ and CH₄ in the urban atmosphere of Krakow. These methods provide an efficient way of quantifying surface emissions of major greenhouse gases originating from distributed sources, thus complementing the widely used bottom-up methodology based on emission statistics.

     

Progress in quantitative research on the relationship between atmospheric oxidation and air quality

Atmospheric oxidizing capacity (AOC) is an essential driving force of troposphere chemistry and self-cleaning, but the definition of AOC and its quantitative representation remain uncertain. Driven by national demand for air pollution control in recent years, Chinese scholars have carried out studies on theories of atmospheric chemistry and have made considerable progress in AOC research. This paper will give a brief review of these developments. First, AOC indexes were established that represent apparent atmospheric oxidizing ability (AOIe) and potential atmospheric oxidizing ability (AOIp) based on aspects of macrothermodynamics and microdynamics, respectively. A closed study refined the quantitative contributions of heterogeneous chemistry to AOC in Beijing, and these AOC methods were further applied in Beijing-Tianjin-Hebei and key areas across the country. In addition, the detection of ground or vertical profiles for atmospheric OH·, HO₂·, NO₃· radicals and reservoir molecules can now be obtained with domestic instruments in diverse environments. Moreover, laboratory smoke chamber simulations revealed heterogeneous processes involving reactions of O₃ and NO₂, which are typical oxidants in the surface/interface atmosphere, and the evolutionary and budgetary implications of atmospheric oxidants reacting under multispecies, multiphase and multi-interface conditions were obtained. Finally, based on the GRAPES-CUACE adjoint model improved by Chinese scholars, simulations of key substances affecting atmospheric oxidation and secondary organic and inorganic aerosol formation have been optimized. Normalized numerical simulations of AOIe and AOIp were performed, and regional coordination of AOC was adjusted. An optimized plan for controlling O₃ and PM_2.5 was analyzed by scenario simulation.     

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.     

On-line enrichment and determination of polycyclic aromatic hydrocarbons in atmospheric particulates using high performance liquid chromatography with fluorescence as detector

Seven polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulates were determinated by high performance liquid chromatography (HPLC) with fluorescence detector using direction injection and an on-line enrichment trap column.The method simplified the sample pretreatment,saved time and increased the efficiency.With the on-line trap column,PAHs were separated availably even underground injecting 1.0 ml sample with relatively high column efficiency.The recoveries of the seven PAHs were from 85% to 120% for spiked atmospheric particulate sample.The limit of detection was 15.3-39.6 ng/L (S/N=3.3).There were good linear correlations between the peak areas and concentrations of the seven kinds of PAHs in the range of 1-50 ng/ml with the correlation coefficients over 0.9970.Furthermore,it also indicated that the method is available to determine PAHs in atmospheric particulates well.     

A new method of simultaneous determination of atmospheric amines in gaseous and particulate phases by gas chromatography-mass spectrometry

As more attention is being paid to the characteristics of atmospheric amines, there is also an increasing demand for reliable detection technologies. Herein, a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry (GC-MS). The amine samples were collected with and without phosphoric acid filters, followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis. Furthermore, the method was optimized and validated for determining 14 standard amines. The detection limits ranged from 0.0408-0.421 µg/mL (for gaseous samples) and 0.163-1.69 µg/mL (for particulate samples), respectively. The obtained recoveries ranged from 68.8%-180% and the relative standard deviation was less than 30%, indicating high precision and good reliability of the method. Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully. Methylamine, dimethylamine and diethylamine together accounted for 76.7% and 75.6% of particulate and gaseous samples, respectively. By comparing the measured and predicted values of gas-particle partition fractions, it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption. Moreover, the reaction between unprotonated amines and acid (aq.) in water phase likely promoted water absorption. Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl. The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.     

天津大气扩散条件对污染物垂直分布的影响研究

利用2017~2019年夏、冬季天津市大气污染物监测和气象观测数据,基于天津气象铁塔垂直观测,针对大气垂直扩散条件对PM_2.5和O₃的影响进行研究.结果显示:近地面PM_2.5浓度随高度的升高而下降,O₃浓度则随高度的升高而上升,受大气垂直扩散条件的季节和日变化影响,冬季,地面与120m PM_2.5质量浓度相关明显,与200m PM_2.5质量浓度无明显相关.夏季,120m和200m PM_2.5质量浓度相关系数为0.72,午后通常出现120m和200m PM_2.5质量浓度高于地面的情况.夏季,不同高度O₃浓度差异小于冬季,地面与120m高度O₃浓度接近.以大气稳定度、逆温强度和气温递减率作为大气垂直扩散指标,对地面PM_2.5和O₃垂直分布具有指示作用.冬季,TKE与PM_2.5质量浓度相关系数为到-0.65,夏季,TKE与ΔPM_2.5相关系数为-0.39.夏、冬季TKE与地面O₃浓度的相关系数分别为0.46和0.53,与ΔO₃的相关系数分别为0.73和0.70.弱下沉运动对地面O₃浓度影响较强,40m高度垂直运动速度与地面O₃浓度的相关系数在冬、夏季分别为-0.54和-0.61.对冬季典型PM_2.5重污染过程的分析发现,雾霾的生消维持和PM_2.5浓度的变化与大气稳定度、气温垂直递减率和TKE的变化有直接关系.对夏季典型O3污染过程的分析发现,近地面的O₃污染的形成与有利光化学反应的气象条件密切相关,同时,垂直向下输送和有利垂直扩散条件对O₃污染的形成和爆发影响明显.     

核电厂野外示踪试验的三维数值模拟研究

为深入分析国内某拟选滨海核电厂址的大气扩散特征,在现场野外示踪试验的基础上,采用计算流体动力学（CFD）软件Fluidyn-PANACHE,结合三维GIS、结构化贴体网格构建、区域加密等技术方法,创建了可模拟野外示踪试验的精细化大气扩散模拟系统.相比于高斯模式,CFD模式能够更好地模拟示踪剂在不同下风距离处的峰值浓度和烟羽宽度,对近场及复杂下垫面条件下的扩散模拟更贴合实际,且可在稳态模拟的基础上获得连续变化风场中接近实时模拟的仿真效果.模拟结果的偏差统计分析表明,CFD稳态模拟和高斯模拟的统计学评价指标均位于国际公认的可接受范围内,CFD模拟的随机偏差优于高斯模拟.因此,CFD模式可用于辅助和优化其他核电厂址的野外示踪试验工作,提高我国核安全审评的效率和针对性.