Simulated Sensitivity of Ozone Generation to Precursors in Beijing during a High O3 Episode

This study uses the WRF-Chem model combined with the empirical kinetic modeling method (EKMA curve) to study the compound pollution event in Beijing that happened in 13-23 May 2017. Sensitivity tests are conducted to analyze ozone sensitivity to its precursors, and to develop emission reduction measures. The results suggest that the model can accurately simulate the compound pollution process of photochemistry and haze. When VOCs and NOx were reduced by the same proportion, the effect of O3 reduction at peak time was more obvious, and the effect during daytime was more significant than at night. The degree of change in ozone was peak time > daytime average. When reducing or increasing the ratio of precursors by 25％ at the same time, the effect of reducing 25％ VOCs on the average ozone concentration reduction was most significant. The degree of change in ozone decreased with increasing altitude, the location of the ozone maximum change shifted westward, and its range narrowed. As the altitude increases, the VOCs-limited zone decreases, VOCs sensitivity decreases, NOx sensitivity increases. The controlled area changed from near-surface VOCs-limited to high-altitude NOx-limited. Upon examining the EKMA curve, we have found that suburban and urban are sensitive to VOCs. The sensitivity tests indicate that when VOCs in suburban are reduced about 60％, the O3-1h concentration could reach the standard, and when VOCs of the urban decreased by about 50％, the O3-1h concentration could reach the standard. Thus, these findings could provide references for the control of compound air pollution in Beijing.     

中国地区臭氧前体物对地面臭氧的影响

利用GEOS-Chem模式的数值试验结果,研究中国地区NOx和两类VOCs对O3质量浓度分布及其化学机理的影响。研究表明,NOx的减少会使得中国西部O3质量浓度显著降低,但在冬季NOx的减少会使得东北、华北地区O3质量浓度上升。而京津唐地区由于VOCs/NOx比值偏低,不能通过单一减少NOx来控制O3质量浓度。VOCs排放的减少会使得我国东部地区O3质量浓度大幅减少,其中人为VOCs的减少能降低我国东部地面O3质量浓度,而生物VOCs的减少只能在夏秋季有效减少我国东部地区35°N以南区域的地面O3质量浓度。控制地面O3质量浓度时,中国西部主要考虑NOx的减排,东部35°N以北主要考虑AVOCs的减排,而30~35°N应同时考虑AVOCs和BVOCs的减排,在30°N以南的地区,则需要全面考虑NOx和VOCs的减排。     

Smog Chamber Study on the Ozone Formation Potential of Acetaldehyde

Acetaldehyde is one of the important VOC species of O3 precursors in the atmospheric environment. The influences of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the formation of O3 are studied in smog chamber experiments, and the MCM v3.3.1 mechanism of acetaldehyde is modified based on the experimental results. In low-RH conditions (RH= 11.6％±1.1％), the O3 concentration at 6 h increases first and then decreases with the increase of RCN, and the RCN at the inflection point of O3 concentrations is 3.2. In high-RH experiments (RH = 78.8％±1.0％), variation of the O3 concentration at 6 h with RCN is similar to that in low-RH experiments, but the RCN at the inflection point is 2.8. RH has no significant effect on the O3 concentrations under low RCN (< 3), whereas it has a negative effect under high RCN (> 3). Compared with the experimental results, original MCM v3.3.1 greatly underestimates the O3 concentrations. Addition of both the photolysis process of peroxyacetyl nitrate and the photolysis process of HNO3 on the reactor surface into the original MCM can reduce the difference between the simulated O3 concentrations and the experimental results at 6 h from 24％-35％ and 17％-49％ to 6％-26％ and 10％-42％ under low- and high-RH conditions, respectively. The maximum incremental reactivity (MIR) of acetaldehyde simulated with the modified MCM is 4.0 ppb ppb-1 without considering the effect of other VOCs.     

ROx Budgets and O3 Formation during Summertime at Xianghe Suburban Site in the North China Plain

Photochemical smog characterized by high concentrations of ozone (O3) is a serious air pollution issue in the North China Plain (NCP) region, especially in summer and autumn. For this study, measurements of O3, nitrogen oxides (NOx), volatile organic compounds (VOCs), carbon monoxide (CO), nitrous acid (HONO), and a number of key physical parameters were taken at a suburban site, Xianghe, in the NCP region during the summer of 2018 in order to better understand the photochemical processes leading to O3 formation and find an optimal way to control O3 pollution. Here, the radical chemistry and O3 photochemical budget based on measurement data from 1-23 July using a chemical box model is investigated. The daytime (0600-1800 LST) average production rate of the primary radicals referred to as ROx (OH + HO2+ RO2) is 3.9 ppbv h-1. HONO photolysis is the largest primary ROx source (41％). Reaction of NO2 + OH is the largest contributor to radical termination (41％), followed by reactions of RO2 + NO2 (26％). The average diurnal maximum O3 production and loss rates are 32.9 ppbv h-1 and 4.3 ppbv h-1, respectively. Sensitivity tests without the HONO constraint lead to decreases in daytime average primary ROx production by 55％ and O3 photochemical production by 42％, highlighting the importance of accurate HONO measurements when quantifying the ROx budget and O3 photochemical production. Considering heterogeneous reactions of trace gases and radicals on aerosols, aerosol uptake of HO2 contributes 11％ to ROx sink, and the daytime average O3 photochemical production decreases by 14％. The O3-NOx-VOCs sensitivity shows that the O3 production at Xianghe during the investigation period is mainly controlled by VOCs.     

长三角工业区夏季近地层臭氧和颗粒物污染相互关系研究

利用2013年5月15日到8月31日南京江北工业区（长三角典型工业区）同步的观测资料分析了近地层臭氧（O₃）和细颗粒物（PM_2.5）、气溶胶光学厚度（AOD）的变化特征及相互间的关系,并结合光化学箱模式分析了AOD对近地层O₃生成的影响。结果表明,观测期间PM_2.5平均质量浓度为56.2±20.1 μg m-3;AOD（500 nm）均值为1.4±0.9;波长指数α（440~870 nm）均值为1.0±0.3。PM_2.5质量浓度24 h均值超国家二级标准20.2%,超标时AOD均值增加14.7%,α平均值增加23.9%,O₃体积分数均值减少12.3%。O₃超国家二级标准10.1%,超标时段AOD增加34.9%,α变化不显著。高温低湿条件下,O₃日变化峰值（y）和PM_2.5质量浓度（x）存在较高的线性相关。相对湿度＜60%时,两者拟合曲线为y＝0.97x+43.96（拟合度R2=0.60）,温度＞32°C时,两者拟合方程为y＝1.24x+30.61（R2＝0.64）。夏季长三角工业区呈现高浓度O₃与高浓度PM_2.5叠加的大气复合污染。O₃日变化峰值和AOD变化呈显著负相关。模拟结果显示,O₃日变化峰值（y）和AOD（x）呈现极高的负相关[y＝－34.28x+181.62,R2 = 0.93或y＝220.62·exp (－x/3.17)－19.50,R2＝0.99]。     

Spectral reflectance in an urban area a case study for Tokyo

The spectral reflectance of the surface in an urbanized area was estimated through airborne measurements of the spectral upward flux of visible radiation in the range 475–750 nm. Atmospheric effects due to Rayleigh and Mie scattering were accounted for by using optical parameters to solve the radiative transfer equation. The values for these parameters were derived from measurements of the particle number concentration and size distribution.The results clearly show a difference in reflectance between urban and suburban areas. The difference in spectral reflectance decreases from the suburban to the urban area.In a metropolitan area, the surface reflectance generally decreases with urban development, and the global upward flux of visible radiation has a similar tendency. This trend supports the idea of a decrease in reflectance due to the modification of the surface structure.     

近地面臭氧研究进展

近地面臭氧是空气中氮氧化物和挥发性有机物发生光化学反应的产物,其浓度与气象条件密切相关。晴天少云、紫外辐射较强、温度较高、相对湿度较低以及风速较小的天气,均有利于臭氧的生成,其中紫外辐射是产生臭氧最关键的因素。臭氧前体物（氮氧化物和挥发性有机物）的浓度及其比值是影响近地面臭氧浓度的另外三个重要因素。我国大多数城市的O3处于VOC控制区,即NOx浓度的增加会引起O3浓度的降低,而VOCs浓度的增加则会使其浓度升高。因而VOC源解析问题成为近年来O3研究的一个热点问题。同时,由于气溶胶可以直接吸收、散射太阳紫外辐射、短波辐射以及大气长波辐射,因此气溶胶的存在会影响大气中光化学反应的进程,从而影响臭氧的光化学生成,气溶胶对近地面臭氧的影响已成为目前大气环境的前沿课题。     

南京北郊冬季大气SO2、NO2和O3的变化特征

利用差分吸收光谱仪DOAS（differential optical absorption spectroscopy）,对2007年11月—2008年1月南京北郊大气SO2、NO2和O3进行了观测。结合Parsivel降水粒子谱仪和自动气象站的资料,对冬季大气污染气体的浓度变化规律及降水和风速风向对其的影响进行了分析。结果表明,南京北郊大气SO2浓度较高,呈明显双峰特征,分别在12时（北京时,下同）和00时达最大,受附近排放源的影响最大,东风及南风时比静风时SO2浓度更高。降水对SO2湿清除效果明显,清除系数平均为0.168 h-1。NO2气体呈明显单峰特征,在18时达最高值。南京北郊是NO2源区之一,主要受附近高速公路汽车尾气排放源的影响。静风时NO2浓度最高。O3浓度受NO2的影响较明显。O3日变化呈单峰特征,在15时达最大值,静风时O3浓度最低。降水对O3的间接影响较明显,在降水时,白天由于太阳辐射较弱,O3浓度降低;夜晚NO浓度较低,使得O3浓度升高。     

Influence of Atmospheric Particulate Matter on Ozone in Nanjing,China:Observational Study and Mechanistic Analysis

Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m~(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m~(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.     

应用查表法模拟区域对流层O3、Nox分布和演化的研究

应用STEM-II气相光化学模式探讨了影响对流层O3、NOx气相光化学转化率的各物理、化学因子。表明在我国多数地区光化学污染物特征(NMHC/NOx较高)下,光辐射强度、温度、初始O3浓度和NOx浓度是影响O3、NOx气相光化学转化率的主要因子。将以上因子分档组合,计算并建立了各种情况下O3、NOx气相光化学转化率的查算表,并将之用于模拟区域O3、NOx的演化和分布。结果表明,与光化学模式直接耦合计算法相比,该方法既能显著缩短计算时间,又能基本反映大气化学反应的非线性过程,并与直接耦合法符合得较好。     

Summertime Surface N_2O Concentration Observed on Fildes Peninsula Antarctica:Correlation with Total Atmospheric O_3 and Solar Activity

Three-year summertime surface atmospheric N2O concentrations were observed for the first time on the Fildes Peninsula, maritime Antarctica, and the relationships among the N2O concentration, total atmospheric O3 amount, and sunspot number were analyzed. Solar activity had an important effect on surface N2O concentration and total O3 amount, and increases of sunspot number were followed by decreases in the N2O concentration and total O3 amount. A corresponding relationship exists between the N2O concentration and total atmospheric O3, and ozone destruction was preceded by N2O reduction. We propose that the extended solar activity in the Antarctic summer reduces the stratospheric N2O by converting it into NOx, increases the diffusion of N2O from the troposphere to the stratosphere, decreases the surface atmospheric N2O, and depletes O3 via the chemical reaction between O3 and NOx. Our observation results are consistent with the theory of solar activity regarding the formation of the Antarctic O3 hole.     

Summertime Surface N2O Concentration Observed on FildesPeninsula Antarctica： Correlation with TotalAtmospheric O3 and Solar Activity

Three-year summertime surface atmospheric N2O concentrations were observed for the first timeon the Fildes Peninsula, maritime Antarctica, and the relationships among the N2O concentration, totalatmospheric O3 amount, and sunspot number were analyzed. Solar activity had an important effecton surface N20 concentration and total O3 amount, and increases of sunspot number were followed bydecreases in the N2O concentration and total O3 amount. A corresponding relationship exists betweenthe N2O concentration and total atmospheric O3, and ozone destruction was preceded by N2O reduction.We propose that the extended solar activity in the Antarctic summer reduces the stratospheric N2O byconverting it into NOx, increases the diffusion of N2O from the troposphere to the stratosphere, decreasesthe surface atmospheric N2O, and depletes O3 via the chemical reaction between O3 and NOx. Ourobservation results are consistent with the theory of solar activity regarding the formation of the AntarcticO3 hole.     

Evaluation of the use of photochemical indicators to assess ozone—NOx—VOC sensitivity in the Southwestern Iberian Peninsula

Understanding the chemical links between ozone (O₃) and its two main precursors, nitrogen oxides (NOx) and volatile organic compounds (VOC), is important for designing effective photochemical smog reduction strategies. This chemical relationship will determine which precursor (NOx or VOC) emission reduction will be more effective for decreasing the ozone formation. Under certain conditions, ozone levels decrease as a result of a reduction in NOx emissions but do not respond significantly to changes in VOC emissions (NOx-sensitive condition), while under other conditions ozone concentrations decrease in response to reductions in VOCs and may even increase when NOx emissions are reduced (VOC-sensitive conditions). Indicator species can be used to assess the sensitivity of ozone to changes in the emissions of its precursors. These indicators are species or species ratios involved in ozone photochemistry which reflect the primary chemical process through which the ozone was formed. In this work we use the MM5-CAMx model system to explore the behaviour of various indicator species during two meteorological situations featuring different atmospheric conditions in a complex terrain area. The results show that indicators based on nitrogen compounds (i.e,. NOy and NOz) are suitable for defining the transition range from VOC- to NOx-sensitive chemistry, and that despite the uncertainties associated with the use of chemical indicators, the ratios O₃/NOy and O₃/NOz may provide a simple and useful way to summarize the response of ozone to changes in NOx and VOC emissions in Southwestern Spain.     

南京及周边黑碳气溶胶对臭氧影响的观测分析和数值模拟

利用南京地面站点2016—2017年黑碳气溶胶(Black Carbon, BC)和臭氧(O_3)逐小时观测资料,对比分析了不同季节BC与近地面O_3的关系。结果表明,高BC(高于平均值)影响下的O_3质量浓度值明显比低BC(低于平均值)影响下的O_3质量浓度值低,这种抑制作用在秋冬季明显高于春夏季,且BC与O_3的负相关性在秋冬季显著高于春夏季,而PM_(2.5)与O_3的负相关性不显著。利用WRF-Chem模式,对2017年12月个例开展BC反馈效应对O_3影响的数值模拟,结果再次证实BC对O_3存在负反馈影响。其影响机制是:BC可通过抑制边界层发展,使近地面NO_x积聚,从而减少臭氧的化学生成(VOCs控制区);BC可通过抑制边界层垂直湍流交换,减少边界层上部高O_3向下的湍流输送,从而减少近地面O_3;BC可通过减小近地面风速,减少O_3的平流输入,从而减少地面O_3。不同个例的主要控制因子不同。     

南京市紫外线辐射强度的变化及影响因子

利用南京市2005-02—2009-01共4 a的紫外线辐射观测资料,分析了到达地面的紫外线辐射强度的变化特征,并探讨了云、污染物浓度和雾、霾天气等对紫外线辐射强度的影响。结果表明,低云量对紫外线强度的衰减更明显,最大达58.15%,蔽光性云层对紫外线辐射强度的衰减可达71%～80%;紫外线辐射强度与污染物浓度呈负相关,其中与NO2的相关性最好,为-0.39;晴空条件下,严重霾对紫外线辐射强度的衰减率可达20%以上,浓雾对紫外线辐射强度的衰减接近50%。     

耦合气溶胶气候模式FGOALS-f3-L模拟青藏高原地区气溶胶特性

基于新耦合气溶胶气候模式FGOALS-f3-L模拟分析了2002-2011年青藏高原地区气溶胶时空分布特征.结果表明:青藏高原地区,沙尘,硫酸盐,碳质气溶胶(包括黑碳,有机碳和混合碳)地表质量浓度分别占比为53.6％,32.2％,14.2％;在拉萨站点,模拟的气溶胶地表质量浓度被低估,尤其是黑碳和有机碳气溶胶;模拟的气溶胶光学厚度(AOD)时空分布与卫星观测结果较为一致,均方根误差和偏差分别为0.081和0.036;由于模式中沙尘排放参数化的不确定性,模式对AOD的模拟效果在夏季和秋季优于春季.     

南京北郊冬季大气S0_2、N0_2和0_3的变化特征

利用差分吸收光谱仪DOAS(differential optical absorption spectroscopy),对2007年11月-2008年1月南京北郊大气SO_2、NO_2和O_3进行了观测.结合Parsivel降水粒子谱仪和自动气象站的资料,对冬季大气污染气体的浓度变化规律及降水和风速风向对其的影响进行了分析.结果表明,南京北郊大气SO_2浓度较高,呈明显双峰特征,分别在12时(北京时,下同)和00时达最大,受附近排放源的影响最大,东风及南风时比静风时SO_2浓度更高.降水对SO_2湿清除效果明显,清除系数平均为0.168h~(-1).NO_2气体呈明显单峰特征,在18时达最高值.南京北郊是NO_2源区之一,主要受附近高速公路汽车尾气排放源的影响.静风时NO_2浓度最高.O_3浓度受NO_2的影响较明显.O_3日变化呈单峰特征,在15时达最大值,静风时O_3浓度最低.降水对O_3的间接影响较明显,在降水时,白天由于太阳辐射较弱,O_3浓度降低;夜晚NO浓度较低,使得O_3浓度升高.     

南京细颗粒物对城市热岛强度的影响

随着城市化和工业化进程的加快,南京城市热岛效应显著,细颗粒物污染加剧,对大气环境、气候变化和人体健康产生重要影响.本文基于观测资料,分析了南京市不同颗粒物浓度水平下城市热岛强度的变化特征;利用光学特性模型OPAC（optical properties of aerosols and clouds model）和辐射传输模型TUV（troposphere ultraviolet-visible model）估计了气溶胶的光学厚度及辐射强迫;定量分析了细颗粒物对城市热岛强度的影响及其可能机制.结果表明：南京城市热岛强度范围为-0.51.3K,冬季强于夏季.细颗粒物质量浓度范围为32 135 μg/m3,冬季高于夏季,城区和郊区差别不大;当大气中细颗粒物质量浓度较高时,城市热岛强度相对较弱;南京城郊气溶胶光学厚度变化范围为0.28 1.01,在地面产生的辐射强迫达-3.88-4.72 W＆#183;m-2;由于城区和郊区下垫面、人为热、细颗粒物浓度水平的差异,造成城郊近地面降温的不同,导致细颗粒物对城市热岛强度的削弱,夏季减弱0.1K,冬季减弱0.2K.     

地面臭氧的变化规律和计算方法的初步研究Ⅰ.紫外波段

通过对广州鼎湖山近地面O3、NOx、太阳辐射、气象参数等项目的观测和理论分析,研究了地面O3与NOx等微量气体及太阳辐射的变化规律,详细讨论了紫外波段、不同天气条件地面O3与NOx,光化学反应、气溶胶、光化辐射等之间复杂的关系.用光能量传输与守恒的观点来考虑大气中与紫外辐射有关的主要过程,并以此来研究大气光化学过程中所遵循的能量规律,建立了一个简单、实用、省时的统计模式,用于计算地面O3浓度.结果表明,不同情况下计算值与观测值均吻合较好.     

Numerical Simulation to Evaluate the Effects of Upward Lightning Discharges on Thunderstorm Electrical Parameters

A theoretical discussion of the discharge effects of upward lightning simulated with a fine-resolution 2D thunderstorm model is performed in this paper,and the results reveal that the estimates of the total induced charge on the upward lightning discharge channels range from 0.67 to 118.8 C,and the average value is 19.0 C,while the ratio of the induced charge on the leader channels to the total opposite-polarity charge in the discharge region ranges from 5.9%to 47.3%,with an average value of 14.7%.Moreover,the average value of the space electrostatic energy consumed by upward lightning is 1.06×10^9 J.The above values are lower than those related to intracloud lightning discharges.The density of the deposited opposite-polarity charge is comparable in magnitude to that of the preexisting charge in the discharge area,and the deposition of these opposite-polarity charges rapidly destroys the original space potential well in the discharge area and greatly reduces the space electric field strength.In addition,these opposite-polarity charges are redistributed with the development of thunderstorms.The space charge redistribution caused by lightning discharges partly accounts for the complexity of the charge structures in a thunderstorm,and the complexity gradually decreases with the charge neutralization process.