A captive-air irradiation study of the response of nitric acid and peroxyacetyl nitrate to ozone control strategies in Los Angeles

Outdoor smog chamber experiments were used to study the sensitivity of the yields of two important nitrogen-containing pollutants, nitric acid (HNO₃) and peroxyacetyl nitrate (PAN) to changes in nonmethane hydrocarbon (HC) and nitrogen oxide (NO_x) concentrations in Los Angeles. The experiments were conducted at two sites in the Los Angeles Basin using eight chambers filled with morning Los Angeles air on 33 days. At least one chamber was unchanged and served as a control, while the initial HC and/or NO_x concentrations were changed by 25–50% in up to seven chambers to simulate O₃ control strategies and to broaden the range of HC - NO_x conditions studied. Empirical models that predict the maximum yields of HNO₃ and PAN were used to determine the response of these pollutants to three possible ozone control strategies. All three strategies (reductions in HC, NO_x or both HC and NO_x) reduced PAN while only NO_x reductions decreased HNO₃. However, reducing NO_x increased the HC reductions required to attain lower O₃ levels. Thus, there is a conflict between the O₃ and HNO₃ control strategies.     

The evaluation of some photochemical smog reaction mechanisms—I. Temperature and initial composition effects

Four popular photochemical reaction mechanisms, Caltech, CB-III, CB-XR and CB-IV, are evaluated using a major, newly available set of outdoor smog chamber data. The smog chamber experiments were carried out under conditions representative of urban air. Sixteen experiments with various temperature and initial HC/NO_x ratios are used to test model performance. In general the four photochemical smog models are found to give results in good agreement with experiment, particularly at moderate temperatures (15–25°C) and HC/NO_x ratios of 7–16 and when the initial organic composition included gasoline vapour, synthetic exhaust and solvents. At higher temperatures (30–45°C) and at lower HC/NO_x ratios (<5) the agreement is not as good. For HC/NO_x = 3.5 the CB-XR and CB-IV mechanisms underestimate the final O₃ concentration by up to 82%. When solvent emissions are omitted from the initial composition the Caltech and CB-III models overestimate the final O₃ concentration by up to 59%.     

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.     

VOC emission caps constrained by air quality targets based on response surface model: A case study in the Pearl River Delta Region, China

Because of the recent growth in ground-level ozone and increased emission of volatile organic compounds (VOCs), VOC emission control has become a major concern in China. In response, emission caps to control VOC have been stipulated in recent policies, but few of them were constrained by the co-control target of PM_2.5 and ozone, and discussed the factor that influence the emission cap formulation. Herein, we proposed a framework for quantification of VOC emission caps constrained by targets for PM_2.5 and ozone via a new response surface modeling (RSM) technique, achieving 50% computational cost savings of the quantification. In the Pearl River Delta (PRD) region, the VOC emission caps constrained by air quality targets varied greatly with the NO_x emission reduction level. If control measures in the surrounding areas of the PRD region were not considered, there could be two feasible strategies for VOC emission caps to meet air quality targets (160 µg/m³ for the maximum 8-hr-average 90th-percentile (MDA8-90%) ozone and 25 µg/m³ for the annual average of PM_2.5): a moderate VOC emission cap with <20% NOx emission reductions or a notable VOC emission cap with >60% NO_x emission reductions. If the ozone concentration target were reduced to 155 µg/m³, deep NO_x emission reductions is the only feasible ozone control measure in PRD. Optimization of seasonal VOC emission caps based on the Monte Carlo simulation could allow us to gain higher ozone benefits or greater VOC emission reductions. If VOC emissions were further reduced in autumn, MDA8-90% ozone could be lowered by 0.3-1.5 µg/m³, equaling the ozone benefits of 10% VOC emission reduction measures. The method for VOC emission cap quantification and optimization proposed in this study could provide scientific guidance for coordinated control of regional PM_2.5 and O₃ pollution in China.     

基于响应曲面法的臭氧生成敏感性分析

准确判断臭氧(O₃)生成敏感性对O₃污染成因分析和防控对策的制定至关重要.首次利用响应曲面方法设计最优试验方案,基于盒子模式模拟结果,快速量化O₃对其前体物变化的响应.结果表明,CO对O₃有正贡献,NO_x和VOCs与O₃呈现显著非线性关系,当φ(VOCs)与[φ(NO_x)-13.75]比值大于4.17时,为NO_x控制区,小于4.17时,为VOCs控制区;烯烃为影响O₃生成的关键VOCs组分,当φ(烯烃)与[φ(NO_x)-15]比值小于1.10且φ(烯烃)<35×10^-9时,烯烃有利于O₃的生成.响应曲面法在多因素和其交互作用对O₃生成影响的研究中取得了良好效果,为高效判断O₃敏感性提供了新的思路和方法.     

Comparison of H2O2 and O3 content in atmospheric samples in the San Bernardino mountains,Southern California

Concentrations of atmospheric H₂O₂ were measured in air, rain, cloud and dew samples in forested areas of the San Bernardino Mountains, southern California, from spring through fall of 1987–1990 O₃ measurements in air were also conducted for comparison. Typical ranges of H₂O₂ concentrations measured were 1–3 ppb in air, 10–90 μM in rain and cloud water, and < μM in dew. The results show that gas-phase H₂O₂ concentrations were slightly higher at nighttime than at daytime or nearly constant throughout a 24-hr period, whereas O₃ concentrations were highest during the afternoon, when polluted air masses from Los Angeles carried by daily sea breezes reached the mountain region. Afternoon concentrations of gaseous H₂O₂ and O₃ in the mountain region were compared with those measured in Los Angeles urban sites to elucidate the regional variation of these oxidants. The results show that ambient concentrations of H₂O₂ and O₃ were about 50–100% higher at the mountains sites than at the Los Angeles sites.     

30年来中国民航运输行业的大气污染物排放

民航是我国重要的交通运输方式之一,但我国民航运输行业的大气污染物排放问题报道较少.根据中国民航统计部门逐年统计数据,采用基于燃料消耗量的排放因子法,估算了1980～2009年中国民航飞机的大气污染物排放量,并分析了大气污染物排放强度及其变化.结果表明,30年来中国民航飞机SO2、CO、NOx和HC排放量逐年增多,分别由1980年的0.031、0.189、0.225和0.314万t增至2009年的1.183、7.298、8.705和12.159万t,排放量年均增加分别为0.039 7、0.245、0.292和0.408万t.SO2、CO、NOx和HC的排放强度呈降低趋势,其值分别由1980年的0.624、3.806、4.53和6.322 g.(t.km)-1降至2009年的0.275、1.697、2.025和2.828 g.(t.km)-1.中国民航运输行业所排放的SO2、CO、NOx占全国总排放量的比重很低,与其他行业排放量相比,中国民航运输行业所排放的大气污染物量也较小.     

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.     

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.     

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.     

臭氧污染动态源贡献分析方法及应用初探

论文创新提出了基于RSM/CMAQ臭氧污染动态源贡献分析方法,并以佛山市顺德区2014年10月为例,分析了不同区域的人为可控源NO_x和VOCs减排情景下(10%、70%和100%)对本地O_3浓度变化的量化贡献.研究结果表明顺德区O_3的人为可控比例约43%,且受区域排放影响非常明显,主导上风向广州排放源总贡献(14%)超过顺德本地贡献(7%).VOCs的减排可有效削减顺德区O_3浓度,当减排力度较小时(12%),若仅控制区域NO_x排放将导致顺德区O_3浓度上升,随着减排力度的加大,区域NO_x的削减贡献会反超VOCs.RSM/CMAQ动态源贡献分析方法可为空气质量管理提供科学决策依据.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

VOCs源强不确定性对臭氧生成及污染防治影响的模拟分析

本文基于三维区域空气质量模式WRF-Chem,通过修改模式化学模块,量化输出过程量和诊断量,提供了一种定量分析挥发性有机化合物(VOCs)源强不确定性对O3生成影响的方法.为无法定量计算VOCs源强导致的臭氧生成率[P(O3)]偏差,以及由此对O3体积分数分布和污染控制相关联的VOCs敏感区和NOx 敏感区分布的误判提供了方法参考.采用标准统计参数对WRF-Chem模式的气象场与污染场模拟性能进行了评估,相关指标均优于前人结果.以INTEX-B(intercontinental chemical transport experiment-phase B)人为源、FINNv1(fire inventory from NCAR version 1)生物质燃烧源和 MEGAN(model of emissions of gases and aerosols from nature)生物源作为基准源,并以卫星观测数据作为约束,对排放源进行改进,评估了源改进前后臭氧生成率[P(O3)]、O3体积分数和O3控制敏感区指标(Ln/Q)的变化情况.仅人为VOCs(AVOCs)源增加68％后,P(O3)模拟峰值增升比例达13％～82％,以北京观测站点为例,P(O3)模拟月均峰值增加42％(22.5×10-9 h-1).对P(03)形成贡献比例最大的主要化学反应是HO2+NO(占比约68％),AVOCs源增加68％后,该反应贡献比例下降至65％.在改进源下,P(O3)普遍增加达到2×10-9～4×10-9h-O3各季节增幅较大的区域均主要集中在京津冀、长三角和珠三角中心城市及周边区域,与我国大型城市区基本都是VOCs敏感区的结论一致.整体而言,VOCs源强改进后,Nox敏感区O3体积分数增加幅度不大,不超过4×10-9,而部分VOCs敏感区增幅超过20 x10-9.VOCs源强的不确定性会影响O3形成过程中Nox和VOCs敏感区的判断,特别是VOCs源强明显低估会夸大VOCs敏感区的范围,从而降低O3调控对策的有效性.     

On-board measurements of gaseous pollutant emission characteristics under real driving conditions from light-duty diesel vehicles in Chinese cities

A total of 15 light-duty diesel vehicles(LDDVs) were tested with the goal of understanding the emission factors of real-world vehicles by conducting on-board emission measurements. The emission characteristics of hydrocarbons(HC) and nitrogen oxides(NOx) at different speeds, chemical species profiles and ozone formation potential(OFP) of volatile organic compounds(VOCs) emitted from diesel vehicles with different emission standards were analyzed. The results demonstrated that emission reductions of HC and NOxhad been achieved as the control technology became more rigorous from Stage I to Stage IV. It was also found that the HC and NOxemissions and percentage of O2 dropped with the increase of speed, while the percentage of CO2 increased. The abundance of alkanes was significantly higher in diesel vehicle emissions, approximately accounting for 41.1%–45.2%, followed by aromatics and alkenes. The most abundant species were propene,ethane, n-decane, n-undecane, and n-dodecane. The maximum incremental reactivity(MIR)method was adopted to evaluate the contributions of individual VOCs to OFP. The results indicated that the largest contributors to O3 production were alkenes and aromatics, which accounted for 87.7%–91.5%. Propene, ethene, 1,2,4-trimethylbenzene, 1-butene, and1,2,3-trimethylbenzene were the top five VOC species based on their OFP, and accounted for 54.0%-64.8% of the total OFP. The threshold dilution factor was applied to analyze the possibility of VOC stench pollution. The majority of stench components emitted from vehicle exhaust were aromatics, especially p-diethylbenzene, propylbenzene, m-ethyltoluene, and p-ethyltoluene.     

City-specific vehicle emission control strategies to achieve stringent emission reduction targets in China's Yangtze River Delta region

The Yangtze River Delta (YRD) region is one of the most prosperous and densely populated regions in China and is facing tremendous pressure to mitigate vehicle emissions and improve air quality. Our assessment has revealed that mitigating vehicle emissions of NOx would be more difficult than reducing the emissions of other major vehicular pollutants (e.g., CO, HC and PM_2.5) in the YRD region. Even in Shanghai, where the emission control implemented are more stringent than in Jiangsu and Zhejiang, we observed little to no reduction in NOx emissions from 2000 to 2010. Emission–reduction targets for HC, NOx and PM_2.5 are determined using a response surface modeling tool for better air quality. We design city-specific emission control strategies for three vehicle-populated cities in the YRD region: Shanghai and Nanjing and Wuxi in Jiangsu. Our results indicate that even if stringent emission control consisting of the Euro 6/VI standards, the limitation of vehicle population and usage, and the scrappage of older vehicles is applied, Nanjing and Wuxi will not be able to meet the NOx emissions target by 2020. Therefore, additional control measures are proposed for Nanjing and Wuxi to further mitigate NOx emissions from heavy-duty diesel vehicles.     

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.     

Ground-high altitude joint detection of ozone and nitrogen oxides in urban areas of Beijing

Based on observational data of ozone(O3) and nitrogen oxide(NOx) mixing ratios on the ground and at high altitude in urban areas of Beijing during a period of six days in November 2011,the temporal and spatial characteristics of mixing ratios were analyzed.The major findings include:urban O3 mixing ratios are low and NOx mixing ratios are always high near the road in November.Vertical variations of the gases are significantly different in and above the planetary boundary layer.The mixing ratio of O3 is negatively correlated with that of NOx and they are positively correlated with air temperature,which is the main factor directly causing vertical variation of O3 and NOx mixing ratios at 600-2100m altitude.The NOx mixing ratios elevated during the heating period,while the O3 mixing ratios decreased:these phenomena are more significant at high altitudes compared to lower altitudes.During November,air masses in the urban areas of Beijing are brought by northwesterly winds,which transport O3 and NOx at low mixing ratios.Due to Beijing’s natural geographical location,northwest air currents are beneficial to the dilution and dispersion of pollutants,which can result in lower O3 and NOx background values in the Beijing urban area.     

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.     

深圳市2022年春季新冠疫情管控期间空气质量分析

短期减排是我国城市应对大气污染事件的重要应急管控手段,但短期减排的效益尚未得到完善分析.2022年3月14～20日,广东省深圳市为抑制新冠疫情传播实施了全市管控,为评估短期减排对华南城市春季空气质量的影响提供独特机会.结合深圳市高精度环境空气质量监测与气象观测等多源数据,分析了深圳市管控期间前后的空气质量变化.此次管控前和管控期中均有部分日期天气形势静稳,局地污染水平主要反映本地排放,有利于分析本地减排的影响.观测与WRF-GC区域化学模拟都表明,与珠三角周边城市相比,深圳市管控期间由于市内交通源排放显著减少,深圳市二氧化氮(NO₂)浓度降低(-26±9.5)%,可吸入颗粒物(PM₁₀)浓度降低(-28±6.4)%,细颗粒物(PM_2.5)浓度降低(-20±8.2)%,但臭氧(O₃)浓度无显著变化[(-1.0±6.5)%].TROPOMI卫星观测的甲醛和二氧化氮柱浓度数据对比表明,2022年春季珠三角臭氧光化学主要受挥发性有机物(VOCs)浓度控制,对氮氧化物浓度降低不敏感,反而可能因氮氧化物对臭氧滴...     

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.