An overview of emissions of SO2 and NOx and the long-range transport of oxidized sulfur and nitrogen pollutants in East Asia

The long-range transport of oxidized sulfur(sulfur dioxide(SO_2) and sulfate) and oxidized nitrogen(nitrogen oxides(NO_x ) and nitrate) in East Asia is an area of increasing scientific interest and political concern. This paper reviews various published papers, including ground- and satellite-based observations and numerical simulations. The aim is to assess the status of the anthropogenic emissions of SO_2 and NO_x and the long-range transport of oxidized S and N pollutants over source and downwind region. China has dominated the emissions of SO_2 and NO_x in East Asia and urgently needs to strengthen the control of their emissions, especially NO_x emissions. Oxidized S and N pollutants emitted from China are transported to Korea and Japan, due to persistent westerly winds, in winter and spring.However, the total contributions of China to S and N pollutants across Korea and Japan were not found to be dominant over longer time scales(e.g., a year). The source–receptor relationships for oxidized S and N pollutants in East Asia varied widely among the different studies. This is because:(1) the nonlinear effects of atmospheric chemistry and deposition processes were not well considered, when calculating the source–receptor relationships;(2) different meteorological and emission data inputs and solution schemes for key physical and chemical processes were used; and(3) different temporal and spatial scales were employed. Therefore, simulations using the same input fields and similar model configurations would be of benefit, to further evaluate the source–receptor relationships of the oxidized S and N pollutants.     

Hydrogen peroxide levels in Los Angeles: A screening-level evaluation

The major factors affecting the diurnal variation of gaseous hydrogen peroxide were studied using a one-dimensional vertical gas-phase chemistry/transport screening model. The model which included diurnal variations of the inversion layer, surface emissions, dry deposition of air pollutants, and meteorological conditions such as solar radiation, temperature, relative humidity and wind speed, was used to evaluate the influence of the ratio of NMHC/NO_x, the emission rates of NO_x and NMHC, the deposition velocity of H₂O₂, and the height of inversion layer on the ground level gaseous H₂O₂ concentrations. The model was found to yield reasonable agreement with field data from the Carbonaceous Species Methods Comparison Study at Glendora, California, in 11–21 August 1986. Specifically, model predictions and field results all indicated that during clear skies, ambient H₂O₂ concentration was highest at about early afternoon when O₃ concentration was highest and NO_x was lowest. It was concluded that the predicted gaseous H₂O₂ concentration is most sensitive to the emission rate of NO_x and the ratio of NHMC/NO_x, but it is less sensitive to the deposition velocity, height of inversion layer, and the emission rate of NMHC.     

The stem-II acid deposition and photochemical oxidant model—II. A diagnostic analysis of mesoscale acid deposition

The MesoSTEM model is used to analyse data obtained during the Mesoscale Acid Deposition Study. The Mesoscale Acid Deposition Study was designed to investigate acid deposition on the urban-suburban scale by sampling well defined frontal storms around the city of Philadelphia using a surface based network. The MesoSTEM model was developed to provide diagnostic analysis of these data. The mesoSTEM model is a combination of the Mesoscale Atmospheric Simulation System (MASS) predictive mesoscale dynamic meteorological model and the STEM-II model, a three-dimensional Eulerian acid deposition model. The MesoSTEM model is described in this paper and applied to the analysis of the 2 May 1985 storm. Elevated sulfate and nitrate deposition is predicted downwind of the major source areas and nitrate deposition exceeds that for sulfate. However, much of the NO_x and SO_x emitted on the mesoscale escapes the storm and becomes available for long-range transport and subsequent deposition.     

Studying high ozone concentrations by using the Danish Eulerian model

The long-range transport of air pollutants (LRTAP) over Europe is studied by a mathematical model based on a system of partial differential equations (PDEs). The number of PDEs is equal to the number of species studied and the model contains 35 species at present. Among the species are NO, NO₂, NO₃⁻, HNO₃, NH₃, NH₄⁺, O₃, PAN, SO₂, SO₄²⁻ and may hydrocarbons. Most of the 70 chemical reactions involved in the model are nonlinear (including here many photochemical reactions).The model requires large sets of input data. Emissions of SO₂, NO_x, NH₃ and both natural and anthropogenic volatile organic compounds (VOC) are needed in the model. The meteorological data consist of fields of wind velocities, precipitation, surface temperatures, temperatures of the boundary layer, relative humidities and cloud cover, which are read in the beginning of every 6-h interval. Both daytime and nighttime mixing heights are used in the model.Many of the species in the model vary on a diurnal basis. An investigation of the main mechanisms that determine the diurnal variation of the ozone concentrations is performed. One of the important conditions that is necessary if one wants to represent correctly the diurnal variations of the concentrations is to have access to meteorological data that vary diurnally. This is especially true for the temperature and the mixing height.The use of modern numerical algorithms (which are combined with vectorization of the most time-consuming numerical procedures) allows one to perform long-term runs with the model on several high-speed computers. Results obtained in runs with meteorological data for July 1985 and August–October 1989 are discussed. The computed concentrations and depositions are compared with measurements taken at stations located in different European countries. The agreement between calculated concentrations and measurements is reasonably good.Results obtained with several scenarios, in which the NO_x emission and/or the anthropogenic VOC emissions are varied, are presented. Several main conclusions are drawn by studying the results obtained during the comparisons. Some plans for future development of the models are discussed.     

Calculation of long term averaged ground level ozone concentrations

Seasonal averaged ground level concentrations for O₃ have been calculated for The Netherlands by means of a two-layer Lagrangian long-range transport (LRT) model. The model includes emissions, nonlinear atmospheric chemistry, dry deposition, exchange between boundary layer (BL) and free troposphere (FT) and fumigation between a mixed layer and an aged smog layer. Concentrations of primary and secondary pollutants in the FT are obtained from a two-dimensional global model developed by Isaksen.In the reference calculation the modelled concentrations of Ox (sum of O₃ and NO₂) and O₃ are in fair agreement with measurements. The NO_x (sum of NO and NO₂) and NO₂ concentrations are under-estimated by the model but there is a good temporal correlation between calculated and measured concentrations. Validation of other components involved in the chemical scheme is hardly possible due to the paucity of measured data. It can only be stated that the results presented in this paper are not in disagreement with measured or modelled data presented in the literature.In a number of sensitivity runs the influence of European anthropogenic emissions of NO_x and volatile organic compounds (VOC) has been investigated. The calculations indicate that the influence of European emissions on the growing season, daytime averaged (May–September, 10–17 h) O₃ concentrations in The Netherlands is small. For European reductions in the order of tens of per cents a VOC emission reduction is more effective than a NO_x emission reduction in lowering the O₃ concentrations. For strong reductions (about 70%) VOC and NO_x are equally effective. The effects of the modelled underprediction of NO_x concentrations on the production of O₃ on a European scale are probably small. On a local scale the effects are more pronounced due to the NO/O₃ titration (photostationary equilibrium). Therefore, an empirical correction is applied on the modelled O₃ concentrations. After this correction, it is shown that daytime O₃ levels during the growing season increase when European NO_x emissions are reduced (2.0–7.7.% increase at 50% NO_x emission reduction). A reduction in VOC emission leads to decreasing O₃ levels (9% reduction for 40% VOC emission reduction, 16% reduction for 70% VOC emission reduction). For a combined reduction of both VOC and NO_x slightly decreasing ground level O₃ concentrations are expected.     

京津冀污染物跨界输送通量模拟

发展了关键影响因子加权人为源分配方法(WKIF),增添了依赖于气象条件和下垫面类型的生物源,动态更新了气象场和浓度场的边界条件.然后利用WRF-CAMx模式定量给出了四季北京、天津和河北大气边界层中PM2.5、O3、CO、SO2、NO2和NO跨界输送通量和北京净输入或输出通量.结果表明WKIF方法合理反映了中小城市人为源的空间分布特征,模式重要输入参量、初值与边界条件的改进显著改善了WRF-CAMx模式对京津冀地区6个观测站点近地面NOx、O3和PM2.5浓度的模拟.北京向天津冬、春季主要通过西北方向,夏、秋季主要经过偏西方向输入NO、NO2、SO2、CO、O3、PM2.5,输送通量夏季均最小,冬季均最大,且四季北京向天津输入的CO、O3、PM2.5通量显著高于NO、NO2、SO2通量.河北的污染物冬、春季主要通过西北方向,夏季主要经由偏南方向,秋季主要途径偏西方向进入北京;四季北京向河北输入NO和NO2,但跨界输送通量小于20t·d-1;四季河北向北京输入的CO、O3、PM2.5通量远高于北京向河北输送的NO、NO2通量,明显大于北京向河北输送的SO2通量,且河北向北京输入CO、O3、PM2.5通量夏季均最小,冬季均最大;四季北京大气边界层中NO、NO2、SO2最大净输出通量小于50t.d-1,CO、O3、PM2.5净输入或输出通量分别为111～2309、567～6244、715～1778t·d-1.这些定量结果为京津冀区域污染源调控对策的制定提供了科学依据.     

Analysis of RADM gas concentration predictions using OSCAR and NEROS monitoring data

The ability of the Regional Acid Deposition Model (RADM) to produce realistic atmospheric trace gas concentration patterns for a variety of atmospheric conditions is explored by comparing model results with surface monitoring data. Two frontal storm system episodes, monitored in 1981 as part of the Oxidation and Scavenging Characteristics of Aptil Rains (OSCAR) experiment, and one relatively dry high-pressure-system case from the 1979 Northeast Regional Oxidant Study (NEROS) were studied. The temporal and spatial variations of SO₂, O₃ and N species monitored at selected locations throughout the eastern U.S. and Canada are compared to the corresponding RADM grid-average predictions. The analysis is complicated by the fact that grid averages are nor necessarily representative of point measurements when the measurements are strongly influenced by local subgrid-scale phenomena. The comparison database also is limited by gaps in the hourly monitoring data and ambiguity in the N species measurements. To reduce these difficulties, observational sites located in rural and suburban areas which are less influenced by large emission sources were chosen for the comparisons, sharp hourly spikes in the observational data were omitted from the analysis and nitrogen species comparisons were limited to special observations where the measurement ambiguities were less pronounced. Spatial distributions of SO₂ and O₃ daytime (10 a.m.–4 p.m.) and night-time (10 p.m.–4 a.m.) RADM concentration averages were compared to the observational averages to confirm that the model and data concentration patterns agreed over the domain. Intercomparisons of individual grid-point pair comparisons were facilitated using fractional differences, which are defined as the difference in the observations and predictions divided by the sum of the observations and predictions. Predictions and observations showed similar patterns of high and low concentrations throughout the region for all three of the events for the daytime comparisons; the lower night-time agreement improved when night-time stability adjustments were applied to the model predictions. Summarizing over all of the individual grid-point, day-total comparisons for all three events, it was found that, for O₃, all of the pairs were in agreement to better than a factor of two and 50% of them were in agreement to a factor of 1.1 or better; for SO₂, 88% of the pairs were in agreement to better than a factor of two and 25% of the pairs were in agreement to a factor of 1.1 or better. Predicted N species concentrations in the 1–4 and 5–7 ppb ranges for two OSCAR cases were comparable to the levels measured at a rural Indiana site during the OSCAR I and OSCAR IV events. Predictions of NEROS NO_x in the 3–11 ppb range were comparable with the concentrations measured at a rural Pennsylvania site for a summer 1986 case meteorologically similar to the 1979 NEROS I event. In general, higher agreement is associated with well-mixed conditions in areas where local characteristics of the observational site more closely resemble the grid-average characteristics.     

长江三角洲夏季一次典型臭氧污染过程的模拟

利用WRF/Chem空气质量模式对长江三角洲夏季一次典型臭氧(O3)污染过程的时空分布特征和物理化学机制进行了数值模拟研究.结果表明,模式能够合理地再现这次长江三角洲夏季典型O3污染过程的时空分布特征和演变规律.2013年8月10~18日,长江三角洲主要受副热带高压影响,晴天、高温和小风的气象条件有利于光化学污染的形成.模拟结果表明,长江三角洲地区气象场、地理位置、区域输送和化学生成都对O3的时空分布有影响.敏感性实验表明,上海O3浓度在海洋性气流影响下较低,但上海排放源对长江三角洲O3浓度时空分布的影响较为显著;南京近地面高浓度O3主要贡献为化学生成(烯烃和芳香烃)和高层O3的垂直输送,杭州和苏州近地面高浓度O3主要来源于物理过程.在O3生成速率最大时(11~13h)对O3前体物减排,对长江三角洲15:00的O3峰值浓度影响较为明显.     

A case study of ozone production in a rural area of central ontario

An O₃ episode observed at Dorset, a rural site in central Ontario, during a stagnant high pressure period of the intensive Eulerian Model Evaluation Field Study (EMEFS), in the summer of 1988, is simulated using a photochemical box model with a two-layer treatment. In the model analysis, natural hydrocarbon chemistry is simulated based on an isoprene-only scenario. Sensitivity tests indicate that local isoprene emissions are an important contributor to local O₃ production, relative to anthropogenic hydrocarbons (AHCs), during the event.The model calculated isoprene contribution to the local O₃ production, defined as the ratio of the O₃ amount formed in the absence of AHCs to that in the presence of AHCs, is characterized by a strong NO_x dependence. A minimum value (∼50%) of the contribution was found at a NO_x level of ∼ 6 ppbv for the representative hydrocarbon composition during the episode. At this NO_x level, O₃ production was strongly influenced by the presence of AHCs. At significantly higher or lower NO_x levels, isoprene is more important than AHCs in the local O₃ production.     

缺失烟囱参数估算及其应用对空气质量模拟结果的改进

针对源清单中部分点源烟囱参数缺失而采用源排放模型SMOKE(Sparse Matrix Operator Kernel Emissions)默认的烟囱参数对空气质量模型模拟结果造成的不利影响,综合考虑气象观测数据、空气质量监测数据、源排放强度以及相关标准和规范对烟囱设计的要求,分别基于最大落地浓度法和基于统计方法对2009年珠三角地区源清单中缺失烟囱参数点源的烟囱参数进行了估算,并将估算烟囱参数用在WRF/SMOKE-PRD/CMAQ空气质量模型系统分析其对模型模拟的改善情况.相比于采用SMOKE默认烟囱参数,基于最大落地浓度估算烟囱参数对NO2、NOx、SO2、PM10及O3的模拟结果均具有一定改善作用,而基于统计方法估算烟囱参数仅对SO2、O3的模拟结果有所提高.结果表明,使用基于最大落地浓度法估算得到的烟囱参数更为合理,使污染物的垂直排放分配更加合理,可以应用于空气质量模型输入源清单中缺失烟囱参数点源的估算,从而一定程度上改善空气质量模型的模拟效果.     

A study of Taipei ozone problem

A high level of ozone has been a serious problem in Taipei. At one station there were concentrations of hourly O₃ 127 and 60 time > 120 ppbv in 1986 and 1987, respectively. The diurnal O₃ variation is mainly governed by a single-peaked (SP) pattern with a major peak near noontime, and a double-peaked (DP) pattern with a primary peak near noontime and a secondary peak in the early morning. The analyses of observed NO_x, NO₂ and NMHC distributions suggest that the photochemical production of ozone is responsible for the primary peak but not the secondary peak. In January, DP occurs more frequently than SP, while in June the SP pattern dominates. Analyses of the surface meteorological data suggest that a unique localized circulation may be responsible for the occurrence of the secondary peak of the DP pattern. A simplified quasi-three-dimensional model is developed to analyze the effect of land-sea breeze on the temporal and spatial variation of O₃.     

Modelling the role of nitrogen oxides,hydrocarbons and carbon monoxide in the global formation of tropospheric oxidants

A new zonally averaged two-dimensional chemical and transport model of the lower atmosphere has been used to study the budgets of photochemical oxidants on a global scale in the troposphere. The sensitivities of these budgets to controls on the emissions of NO_x, CO and hydrocarbons from a variety of sources have also been considered. The species studied include O₃, PAN, H₂O₂ and organic peroxides, as well as the global budget of the hydroxyl radical. The results show the relative impacts of emissions from natural and from man-made sources. Overall, some 75% of the turnover of tropospheric ozone results from in situ chemical production, with only 25% having its origins in the stratosphere. The respective fractions for chemical loss and dry deposition are similar. Of the ozone formed in situ, approximately one-third is formed from natural emissions, and two-thirds from man-made emissions. Over half of this man-made contribution is due to industrial society, with much of the rest being caused by biomass burning and methane emitted from paddy fields. Although reducing emissions of NO_x is the most effective way of controlling tropospheric O₃, this also increases the inventories of peroxides and the rate of increase in the concentration of methane, due to a reduction in the inventory of the OH radical. It is, therefore, necessary to control the emissions of a wide range of species in order to reduce the budget of all photochemical oxidants without adversely perturbing the budget of CH₄.     

夏季城市大气O3浓度影响因素及其相关关系

利用2003年夏季济南市区近地面大气O₃、相关前体物和气象因素等观测数据,研究了O₃浓度的分布特征及时间变化规律,分析了7月份O₃与NO、NO₂和CO等前体物及太阳辐射和气温气象条件的相关性.结果表明,济南市区夏季O₃污染比较严重,观测期间各污染物O₃、NO、NO₂、NO_x和CO浓度都相对较高,昼间O₃与各前体物的浓度呈较好的负相关关系,与太阳辐射具有非常明显的相关性,而与气温的相关性不明显.根据以上分析结果,利用回归分析方法,建立了昼间O₃浓度与前体物、气象因子之间的相关模式,结果表明O₃浓度的计算值与观测值符合性较好.     

Evaluation of a number of chemical mechanisms for their application in models describing the formation of photochemical ozone in Europe

A series of 24 chemical mechanisms from the literature are compared against each other using harmonized emissions, photolysis rate coefficients for simple inorganic chemistry and life cycle data for ozone, PAN and H₂O₂. The evaluation sought to understand the impact of parameterizing hydrocarbon oxidation on the peak concentrations of photochemically-generated secondary pollutants. Only seven of the 24 chemical mechanisms gave peak concentrations of ozone, PAN and H₂O₂ simultaneously in their respective central ranges. PAN and H₂O₂ were generally calculated with a much lower precision compared to ozone. Only 11 mechanisms out of 24 gave responses to both 50% hydrocarbons and NO_x emissions controls in their respective central bands. The lack of coordinated ozone, PAN and hydrogen peroxide measurements across Europe currently limits the adequacy of model comparisons and hence the confidence which may be placed in assessments of likely impacts of future control strategies.     

北京城区夏季O3化学生成过程

选取2007年7月1日—8月31日中的21个晴空日,利用观测资料和光化学箱模式计算了北京城区测点的O₃生成速率G(O₃)和O₃生成效率OPE.结果表明,21个晴空日中G(O₃)日最高小时值分布在(18~82)×10^-9h^-1之间;在O₃污染和非污染日G(O₃)最高值的平均水平无显著差异,且与O_x浓度之间不存在一致的对应关系,表明O₃化学生成过程不能全面解释地面O₃浓度的累积,物理传输过程对测点O₃实测浓度有显著作用;各个化学过程对G(O₃)的贡献率对比结果显示,HO₂ 在 NO向NO₂的转化中贡献最大;OPE值分布在2.8~5.8之间,总体水平为4.1±0.1;OPE值与NO_x浓度之间为非线性关系,OPE值随NO_x浓度的增加而减少,表明消减测点附近VOCs排放能有效降低O₃浓度.     

基于随机森林的北京城区臭氧敏感性分析

明确臭氧（O₃）与前体物的非线性关系是O₃防控措施制定的基础和关键.基于北京城区站点2020年4~9月O₃、挥发性有机物（VOCs）、氮氧化物（NO_x）和气象要素在线观测,分析了O₃及其前体物污染特征,利用随机森林（RF）模型结合SHAP值探究了影响O₃的关键因素,并通过多情景分析探讨了O₃-VOCs-NO_x敏感性.相关性分析结果显示O₃小时浓度与温度（T）呈显著正相关,与TVOCs和NO_x呈显著负相关;但从每日结果来看,O₃与T、TVOCs和NO_x均呈显著正相关.RF模型模拟的O₃浓度与实测值吻合较好,进一步计算了各个特征变量的SHAP值,结果显示T和NO_x对O₃影响最高,但前者是正向影响,而后者是负向影响.以观测期间O₃污染天的NO_x和VOCs平均值为基础情景,设置了对应不同NO_x和VOCs的多种情景,并利用RF模型计算不同情景下的O₃,得到O₃等值线（EKMA曲线）,结果显示北京城区O₃-VOCs-NO_x敏感性处于VOCs控制区,与基于观测的盒子模型（OBM）得到的结果一致,这说明RF模型可以用作O₃-VOCs-NO_x敏感性分析的一种补充方法.     

2013年10月长株潭城市群一次持续性空气污染过程特征分析

2013年10月21~31日长株潭城市群经历了一次持续性空气污染过程.利用地面空气质量监测资料、地面气象资料及探空资料综合分析了此次污染过程与大气环流、边界层气象条件之间的相互关系,并利用卫星遥感火点监测资料和HYSPLIT4模式,分析了此次过程大气污染物的来源及输送路径.结果表明,过程前期(21~26日),污染物缓慢积累,过程后期(27~31日),PM2.5、CO、NO2等焚烧特征污染物浓度急剧升高,秸秆焚烧污染物的长距离输送是后期空气污染加重的主要原因.火点监测和后向轨迹分析表明,过程前期气流主要流经长株潭城市群东北方向的安徽、湖北等地,流经地区火点分布较少,后期气流主要流经长株潭城市群东南方向的江西等地,流经地区火点分布较多.高压均压场背景环流导致的稳定大气层结、南北冷暖气流对峙造成的地面静小风,是长株潭城市群污染过程发展、维持和加强的重要条件,污染物长距离输送对长株潭城市群区域空气质量有重要影响.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.