北京夏季典型臭氧污染分布特征及影响因子

为研究北京地区O₃分布特征及其影响因子,利用AML-3车载式大气环境污染激光雷达系统(下称AML-3)对北京地区2011年5月7日—6月9日的φ(O₃)进行观测. 通过AML-3自带的污染物地面观测系统和差分吸收激光雷达,分析近地面、高空φ(O₃)时空分布特征,并将φ(O₃)与温度、风速及风向3个气象要素进行相关分析. 结果表明:近地面φ(O₃)日变化明显,06:00左右为低谷,下午14:00左右达到峰值. 高空φ(O₃)的空间分布很不均匀,上层气流易使O₃富集层向下输送造成污染,同时稳定边界层对大气扩散的不利影响也是形成O₃污染的重要原因. φ(O₃)的日变化趋势与温度的日变化趋势呈显著正相关,R(相关系数)为0.74;上下层湍流交换使风速与近地面φ(O₃)呈正相关,而水平扩散使二者呈负相关;通过分析风向的分布规律发现,东北风易造成北京地区O₃污染.      

北京地区边界层大气臭氧浓度变化特征分析

利用2001-03～2006-10的大气臭氧探空资料,分析了近6 a北京边界层（2 km以下）大气臭氧浓度的平均月变化和季节变化规律.结果表明,边界层大气臭氧浓度的月变化很明显,1月臭氧浓度最小,地面臭氧浓度不到10×10^-9(体积分数,下同),上层（即2 km）臭氧浓度也不到50×10^-9.而6月臭氧浓度最大,地面达到85×10^-9,上层大于90×10^-9.臭氧浓度具有明显的季节特征,从臭氧浓度值来看,冬季最小,夏季最大.从地面到上层的臭氧浓度的变化幅度来看,冬季变化最大,夏季变化最小.根据廓线变化方式,臭氧浓度廓线可分为3种类型,冬季型、夏季型、春秋季型.不同高度臭氧月平均浓度也明显不同.分析地面及上层臭氧浓度与气象因子如温度和湿度的相关关系,发现地面臭氧浓度与温度具有较好的线性关系,相关系数在0 .85以上.     

Polynuclear aromatic hydrocarbon degradation by heterogeneous reactions with N2O5 on atmospheric particles

The degradation of particulate polynuclear aromatic hydrocarbons (PAH) on atmospheric soot particles in the presence of gas phase dinitrogen pentoxide (N₂O₅) was explored. Dilute diesel and wood soot particles containing PAH were reacted with∼10ppm of N₂O₅ in a 200 ℓ continuous stirred tank reactor (CSTR). To provide a stable source of particles for reaction in the CSTR, diesel or wood soot particles were injected at night into a 25 m³ Teflon outdoor chamber. The large chamber served as a reservoir for the feed aerosol, and the aerosol could then be introduced at a constant flow rate into the CSTR. PAH-N₂O₅ heterogeneous rate constants for wood soot at 15°C ranged from2 × 10⁻¹⁸to5 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. For diesel soot the rate constants at 16°C were higher and ranged from5 × 10⁻¹⁸to30 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. Comparisons with other studies suggest that sunlight is the most important factor which influences PAH decay. This is followed by ozone, NO₂, N₂O₅ and nitric acid. The rate constants of nitro-PAH formation from a parent PAH and N₂O₅ were of the order of1 × 10⁻¹⁹−1 × 10⁻¹⁸ molecules⁻¹s⁻¹. The uncertainty associated with all of these rate constants is± a factor of 3. Given, however, the small magnitude of the rate constants and the low levels of N₂O₅ present in the atmosphere, we concluded that PAH heterogeneous reactions with gas phase N₂O₅ degrade particle-bound PAH or to form nitro-PAH from PAH arenot very important. (Direct application of the specific rate constants derived in this study to ambient atmospheres should not be undertaken unless the ambient particle size distributions and chemical composition of the particles are similar to the ones reported in this study.)     

Laboratory measurements of ozone deposition to sea water and other saline solutions

Measurements of ozone deposition velocity to fresh seawater samples collected over the course of a year have been made using a static chamber technique. The magnitude of the ozone deposition velocity (ca 0.01 cm s⁻¹) was in broad agreement with the relatively few values reported in the literature. A strong correlation between ozone deposition and dissolved surfactant concentrations was found which is reflected in their similar seasonal trends. Stirring the water resulted in a significant increase in the rate of ozone uptake at the surface which suggests that wave motion may increase deposition velocity by constantly and rapidly replenishing the reactive surface organic layer.     

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.     

夜间近地表臭氧观测

2018年12月15~18日使用激光雷达在河北望都观测气溶胶与O₃,利用气溶胶消光系数廓线判断边界层的变化,进而研究大气边界层对于近地表层（300m）O₃浓度的影响.结果表明,边界层主要影响O₃的干沉降以及高空O₃的垂直输送,在受本地污染控制时,近地表O₃浓度受干沉降控制明显,随着边界层高度的下降而减少;西北地区气团占主导时,O₃浓度主要受水平传输以及高空垂直输送影响.     

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO₂) and superoxide (O₂⁻) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO₂/O₂⁻. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO₂/O₂⁻, and cycled between the Cu(II) and Cu(I) forms. Cu⁺ reacted with FeOH²⁺ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10⁷ M⁻¹s⁻¹. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO₂/O₂⁻. Only at high oxalate concentrations was the Fe(II)C₂O₄ complex also formed, and it reacted relatively rapidly with hydrogen peroxide (k = (3.1 ± 0.6) × 10⁴ M⁻¹s⁻¹). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH²⁺ with Cu(I) and HO₂/O₂⁻, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO₂ present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO₂/O₂⁻, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO₂/O₂⁻.     

海洋大气边界层内臭氧和氮氧化物浓度日变化的模拟研究

利用MECCA大气化学模式,考虑卤素类(Br,Cl和I)物质的化学过程,对海洋大气边界层内臭氧和NOx的日变化进行了模拟,并与实测数据进行了对比.结果表明,当考虑这些影响后,ψ(O3)略有降低并且产生峰值的时间提前,这主要是由于Br,BrO,Cl和ClO等物质浓度在日出后很快达到峰值所致,基于同样的原因,NO2变化也有类似的特点.在清洁环境下,海洋大气边界层内臭氧的消耗主要由HOx,O(1D)+H₂O和卤素控制,白天以卤素对臭氧的消耗为主.此外还模拟了不同ψ(NOx)下臭氧的日变化,得出在高ψ(NOx)情况下,边界层内臭氧可由净损耗变为净增长.      

Detailed design features of a new wind tunnel for studying the effects of thermal stratification

A new wind tunnel has been developed for the Sonderforschungsbereich 210 at the University of Karlsruhe to study the effects of thermal stratification on flow and diffusion in the atmospheric boundary layer, particularly to simulate a convective boundary layer and diffusion processes in this flow condition. The wind tunnel is of the closed circuit type. The return section is subdivided into 10 layers, each of which is heated individually and driven by a separate fan. The temperature in the return section can be controlled in the range of 20–200°C and the velocities in the range of 0.5–8 ms⁻¹. The individual control of temperature and velocity in each layer generates temperature and velocity profiles at the test section entrance. Thus, the test section length and the energy requirements can be reduced considerably in comparison with conventional stratified wind tunnels, and a wide range of thermal stratifications can be generated.In this paper the concept and details of the construction will be discussed; furthermore, details of the control device and the facility safety system will be presented.     

Structure of the Indian southwesterly pre-monsoon and monsoon boundary layers: Observations and numerical simulation

Characteristics of pre-monsoon and monsoon boundary layer structure and turbulence were studied in New Delhi and Bangalore, India during the summer of 1987. Micrometeorological towers were installed and instrumented at these locations to provide mean and turbulent surface layer measurements, while information on the vertical structure of the atmosphere was obtained using miniradiosondes. Thermal structures of the pre-monsoon and monsoon boundary layers were quite distinct. The daytime, pre-monsoon boundary layer observed over New Delhi was much deeper than that of the monsoon boundary layer observed over Bangalore and at times was characterized by multiple inversions. Surface, turbulent sensible heat fluxes at both sites were approximately the same (235 and 200 Wm⁻² for New Delhi and Bangalore, respectively). Diurnal variations in the monsoon boundary layer at Bangalore were more regular compared to those under pre-monsoon conditions at New Delhi. One-dimensional numerical simulations of the pre-monsoon boundary layer using a turbulent energy closure scheme show good agreement with observations.     

Partitioning ozone fluxes to sparse grass and soil and the inferred resistances to dry deposition

A two-source (Penman-Monteith type) model, used in a preceding companion study as a diagnostic tool to partition objectively half-hourly measurements of evapotranspiration into bare soil and plant components and to derive in situ estimates of the bulk plant and soil resistances to evaporation, is extended to include ozone deposition. At the time this study was performed, the total leaf area index (LAI) of the site varied between 0.5 and 0.8. Live plant material accounted for 60–75% of the LAI while the remaining LAI was dead plant material. For present purposes this two-source model augments measurements of the major components of the surface energy balance and other micrometeorological measurements with measurements of the ambient ozone concentration and eddy correlation measurements of the total dry depositional flux of ozone. This study employs the bulk canopy resistances estimated previously with this model along with additional ozone measurements: (1) to partition the ozone dry deposition flux into bare soil and plant components in a region of partial canopy cover and (2) to estimate the intrinsic soil resistance to ozone destruction. The results of this study suggest: (a) that the plant component probably receives no more than 25% of the total ozone depositional flux and this percentage decreases as the soil water available to the plants decreases and (b) that the soil resistance to ozone destruction has a near-surface boundary layer component of about 0.7 s cm⁻¹ and an intrinsic component of about 1.0 s cm⁻¹.     

大气臭氧污染对冬小麦气孔吸收通量的影响机制及其时空格局

近地层臭氧作为一种二次污染物,其不断增加的浓度及其对作物的影响已经成为各国政府和公众关注的焦点.本文以冬小麦为研究对象,基于大田OTC试验,对OTC内气象因子和气孔导度进行连续观测.引进气孔导度模型,并进行本地参数化研究,结合通量模型,研究冬小麦气孔臭氧吸收通量的变化特征,并对江苏省各市冬小麦气孔导度和O_3吸收通量的时空分布进行模拟.结果表明,O_3浓度增加会限制其叶片气孔导度,浓度越高,限制作用越明显;利用修订后的气孔导度模型对冬小麦叶片气孔导度进行模拟,表明模型解释了实测气孔导度90%、77%和83%的变异性.结合通量模型对冬小麦气孔O_3通量进行模拟,则CK(约为53.67 n L·L~(-1))、100 n L·L~(-1)和150 n L·L~(-1)O_3浓度处理下冬小麦在整个O_3熏期的累积吸收通量分别为6.42、12.27和13.90 mmol·m-2;江苏地区冬小麦在其生长季期间O_3浓度呈逐渐增加的趋势,冬小麦平均气孔导度的大小表现为:中期后期前期的时间变化特点,在整个中期时段气孔O_3累积吸收通量最多.     

Deposition and forest canopy interactions of airborne sulfur: Results from the integrated forest study

The Integrated Forest Study (IFS) was a long-term research project designed to determine the effects of atmospheric deposition on forest nutrient cycles. Concentrations and fluxes of airborne sulfur compounds were determined for several years at the 13 IFS research forests in North America and Europe using a standard set of protocols. Annual mean air concentrations of sulfur ranged from ∼1.5 to 8 μgSm⁻³ and were generally dominated by SO₂ (∼60% of total sulfur on the average). Atmospheric deposition of sulfate at these forests was highest at the high elevation (∼ 1000–2000 eq ha⁻¹yr⁻¹) and at the southeastern U.S. sites (∼800–1000 eq ha⁻¹yr⁻¹), and lowest in the Pacific northwest (∼300 eq ha⁻¹yr⁻¹). Cloud water contributed significantly to the sulfur flux at the mountain sites (45–50%), and dry deposition was comparable to wet at the drier southeastern sites (>40% of total). Deposited sulfur appeared to behave more or less conservatively in these canopies, showing little net uptake (ofSO₂) and minor foliar leaching (of soil-derived, internal SO₄²⁻) relative to the total atmospheric flux. The estimated fluxes in total deposition were generally within 15% of the measured fluxes in throughfall plus stemflow, indicating that useful estimates of total atmospheric deposition of sulfur can be derived from measurements of throughfall.     

Evaluation of absorption properties of atmospheric aerosols at solar wavelengths based on chemical characterization

The imaginary part of the complex index of refraction of atmospheric aerosols was determined by calculation based on chemical characterization. Atmospheric aerosols in Sapporo were chemically characterized, and were estimated to be mainly composed of elemental C, organics, (NH₄)₂SO₄, NH₄NO₃, sea salt and soil particles. Using the complex index of refraction of each chemical species, the volume extinction and scattering coefficients of the particles composed of the chemical species were calculated, using Mie scattering theory. The single scattering albedo of the aerosols was obtained as the ratio of the total volume scattering coefficient to the total volume extinction coefficient. The imaginary part of the complex index of refraction of the aerosols was determined by matching the calculated sigle scattering albedo for the aggregate aerosol to that calculated from the sum of the individual aerosol components. The monthly mean imaginary part of the complex index of refraction of aerosols in Sapporo ranged from 0.024 in August to 0.047 in February in 1982.The atmospheric solar heating rate was calculated by solving the equation of radiative transfer in turbid atmospheres. It was estimated that the atmospheric boundary layer in Sapporo was heated at the rate of 2.0–2.5°C day⁻¹ in February as a result of absorption of visible solar radiation by aerosols.     

一个沿海城市大气臭氧的本地生成过程及其对前体物的敏感性

在威海市两个采样点用苏码罐采集了全空气样品,利用三级冷阱预浓缩-GC/MS方法离线测定了空气样品中109种大气挥发性有机物(VOCs).使用基于观测的MCM机理大气化学模式(OBM-MCM)分析了大气臭氧生成对VOCs组分的敏感性及本地生成过程.结果表明:观测期间两个采样点的总挥发性有机物(TVOCs)平均浓度分别为27.84×10~(-9)和17.85×10~(-9),对TVOCs贡献最大的均是烷烃.模拟分析表明,大气臭氧生成与前体物的控制关系存在空间差异性,在一个观测点受VOCs控制,而在另一个观测点受NO_x和VOCs共同控制;模拟结果还表明,臭氧生成对活性烃类最为敏感,但是,含氧有机物、卤代烃和高碳烷烃对臭氧生成的影响和贡献也不可忽视;此外,计算了日平均臭氧净生成速率P(O_3)_(net),分别为6.41×10~(-9) h~(-1)和3.22×10~(-9) h~(-1),臭氧的本地生成过程扮演重要角色.     

夏季对流层臭氧辐射强迫对华北地区天气和空气质量的影响

自2013年我国实施《大气污染防治行动计划》以来,大气颗粒物浓度显著降低,但臭氧（O₃）污染日益严峻,同时对流层O₃作为一种重要的温室气体,其辐射强迫能够影响天气和空气质量.利用双向耦合的区域空气质量模型WRF-Chem,再现2017年6月发生在华北地区的一次O₃污染事件,通过敏感性试验分析对流层臭氧辐射强迫（TORF）对当地气象场的影响,以及改变的气象变量对O₃空气质量的反馈作用.结果表明,WRF-Chem模式在气象要素的模拟上表现出较好的性能,并且能够很好地捕捉到O₃浓度的时空演变特征.TORF使北京-天津-河北-山东地区的近地面气温平均升高0.23 K （最大增温可达0.8 K）、近地面相对湿度降低1.84%、边界层高度增加27.73 m.TORF对风速的影响较弱（-0.02 m ·s^-1）,但产生的西南风异常容易将上游污染地区的O₃和其前体物输送至华北地区.在臭氧辐射反馈的影响下,研究区域内φ（O₃）平均增加1.7%（1.23×10^-9）,而在污染严重的北京和天津地区,φ（O₃）增加量最高可达5×10^-9.进一步利用过程诊断分析法可以发现,增强的气相化学反应是TORF恶化近地面O₃污染的主导原因.     

Laboratory tests of KI and alkaline annular denuders

Annular denuders coated with KI and with alkaline solutions have been tested for their ability to remove atmospheric pollutants including ozone, NO₂, SO₂, formaldehyde, methyl nitrate and peroxyacetyl nitrate. Tests were carried out at flow rates of 0.4–2.0 ℓ min⁻¹, using particle-free ambient air as well as purified air to study the effect of atmospheric CO₂ on alkaline denuder performance. Denuders coated with KI were efficient in removing O₃, NO₂, SO₂ (> 95%) and PAN (84±3%) but not methyl nitrate (44%) and formaldehyde (<5%). Selective removal of PAN from NO₂, and vice versa, could be obtained with annular denuders coated with NaOH, which removed 100% PAN and ⩽15% NO₂, and with alkaline guaiacol, which removed ⩾99% NO₂ and ⩽6% PAN.     

Wind tunnel experiments on the resuspension of particulate material

A programme of wind tunnel experiments has been carried out in which the resuspension of particulate material of four sizes (4, 10, 18 and 22 μm diameter) from concrete and grass surfaces has been studied. The importance of wind speed has been investigated and the time dependence of the resuspension rate has been evaluated for periods shortly after the onset of resuspension. The results indicate rapidly falling values of the resuspension rate which are approximately related to 1/time. The increase in the resuspension rate with increasing wind speed was most pronounced for large particles, leading to the conclusion that resuspension can be dominated by short-duration episodes which coincide with conditions that favour resuspension. Resuspension rates, averaged over approximately 1 h after the onset of conditions leading to resuspension, were in the range 1 × 10⁻⁶ to 5 × 10⁻⁶ s⁻¹, at moderate wind speeds (less than 5 m s⁻¹), with little difference between the grass and concrete surfaces. For high wind speeds (greater than 6.5 m s⁻¹), several per cent of the total surface deposit of 22 μ diameter particles was removed from both the concrete and grass surfaces within 10 s of the onset of wind.     

佛山地区干季边界层垂直风温结构对空气质量的影响

利用佛山地区2013年12月大气边界层观测试验得到的垂直风温资料和相应逐日AQI资料、逐时PM_(2.5)浓度资料,研究了佛山地区大气边界层垂直风温结构对空气质量的影响.结果表明:佛山地区干季持续存在的逆温结构是导致PM_(2.5)污染较重的重要原因.干季污染日近60%的最低逆温层高度低于1000 m,而非污染日低于1000 m的最低逆温层仅占36%,污染日佛山贴地逆温频率高达31.2%.逆温层出现高度较低,将污染物压缩积累在贴地层大气中导致污染较重.在大陆冷高压控制下,佛山地区的边界层结构演化非常典型,最大边界层高度和最大边界层通风量表现出了显著相关,污染日日平均边界层高度始终维持在较低的水平,多数时候不足500 m,最大边界层高度则大部分小于1000 m,日平均边界层通风量主要分布在500~1500 m~2·s~(-1)之间,在极端情况下甚至不足300 m~2·s~(-1),最大边界层通风量大部分处于1500~5000 m~2·s~(-1)之间,导致污染物始终聚集在较低的大气边界层内,使得PM_(2.5)浓度长时间维持在较高的污染水平.佛山地区风场存在显著的3层结构,较小的底层风速意味着大气的输送和扩散能力较弱,高度较低的中层使得污染物进一步被压缩累积在大气底层,垂直风场的不稳定性使得污染日佛山地区局地回流活跃,回流(RF)指数极小值多分布在0.2~0.4之间,污染日RF指数普遍小于非污染日,垂直风场的有效输送能力被显著削弱.     

基于风廓线雷达对成都地区典型持续性重污染天气的研究

基于风廓线雷达数据、大气污染数据及气象数据对2017年12月17日—2018年1月3日成都地区的一次持续性重污染天气过程进行研究,并对两次污染物浓度爆发式增长阶段的污染原因及污染物来源进行了分析.结果表明:①在这次重污染天气过程中,风廓线雷达高精度的风场资料(包括水平风速、风向、垂直风速、大气折射率结构常数C■)配合其他气象要素在分析两个污染阶段污染物的累积及扩散、输送中可以发挥重要的作用,即当成都地区水平风场风速较小且风向多变时,此时受静稳型天气控制,污染物浓度会快速累积增长,而当出现较强的东北风时,可能会有沙尘污染物的输入,应注意沙尘天气的提前预警.垂直风场中垂直速度和大气折射率结构常数C■的变化往往影响着污染物浓度的变化,由于风廓线雷达具有较高的时间分辨率,因此,对污染天气过程的变化有一定的指示意义.②结合局地环流指数和边界层通风量,重新定义了一种适合成都地区风场特征的通风指数:有效通风量(EVI),从而表明第一阶段污染的主要原因是成都地区由静稳型天气控制,边界层内风场对污染物的稀释扩散能力差,导致污染物累积.③通过后向轨迹模拟并结合PM_(2.5)浓度数据进行聚类分析,认为第二阶段污染主要是东北方向携带有大量沙尘污染物的气团输送到成都地区导致的,与源于西北地区沙尘天气的沙尘输送密切相关.