光化学臭氧日变化特征与其前体物关系的探讨

应用大气光化学模式研究了日最大臭氧体积分数及其出现时刻与其前体物NMHC、NOx体积分数及NMHC／NOx比值的关系。结果表明，影响日最大臭氧体积分数（ψ03max）脊线位置（EKMA图，Empirical Kinetic Modeling Approach）的关键因子是NMHC成份组成比例；日臭氧体积分数达到最大值需要的时间（τ03max）与NMHC／NOx比值及NMHC成份组成比例有关，与NMHC、NOx体积分数关系不大。此外，利用该结果解释了近20a北京日最大臭氧体积分数出现时刻具有不断提前的变化趋势的原因。     

A Possible Photochemical Link Between Stratospheric and Near-Surface Ozone on Swiss Mountain Sites in Late Winter

Record high near-surface ozone concentrations at two elevated sites (Chaumont, 1140 m asl, and Rigi, 1030 m asl) in Switzerland were observed simultaneously with extremely low total ozone during a fair weather period in mid-February 1993. An analysis of ozone, temperature, humidity, and wind profiles suggests that the surface ozone peaks were most possibly generated within the region in a layer between about 1000 and 1500 m asl. Mean diurnal cycles of ozone concentration during the period shows a strong increase from late morning to late afternoon at Chaumont and at the same time a decrease at the high alpine site Jungfraujoch (3580 m asl). The different diurnal ozone cycles can both be explained photochemically by taking into account the large difference in NOx concentrations (about two orders of magnitude) between the sites. Photochemical processes are also indicated by the diurnal cycles of NO2 and NO concentration. As a strong photochemical activity is not expected in mid-February at 47°N, we hypothesize that the extremely low total ozone played a role. Total ozone controls the amount of UV-B radiation reaching the troposphere and thus influences photochemical processes. Using a radiation model, we calculated an increase in ozone photolysis at Chaumont and Jungfraujoch of 73% and 83%, respectively, on the day with the lowest total ozone (243 DU) compared to average February conditions (335 DU). It is suggested that total ozone changes have the potential to stimulate photochemistry sufficiently to produce the observed surface ozone peaks at Chaumont and Rigi of 61 and 64 ppbv, respectively. A fog layer just below Chaumont during these days probably also influenced photochemistry, but on a smaller spatial scale. Our empirical results on the influence of changing UV radiation on tropospheric photochemistry are in close agreement with model studies of other groups. Although this case study represents unique conditions, a distinct anticorrelation between near-surface ozone at Chaumont and total ozone also appears in other years (1992–1997) when selecting fair weather days in mid-February. However, other influences cannot be excluded. The selected days provide evidence of a significant photochemical source of ozone in the mid-latitude lower troposphere in late winter.     

Meteorological Aspects, Ozone, and Solar Radiation Measurements During POPCORN 1994

Meteorological data, ozone mixing ratios, and photolysis frequencies for the period August 2 to August 24, 1994, are presented and discussed in support of the field campaign POPCORN (Photochemistry of Plant Emitted Compounds and OH Radicals in Northeastern Germany). Measurements of temperature, ozone, and wind speed at different heights are used to evaluate micro-meteorological parameters. The observations provide information about local influences on the air mass composition. The analysis of radio sonde data of nearby stations provides the height of the planetary boundary layer.     

地面臭氧光化学过程规律的初步研究

给出了1996年夏季在广东肇庆鼎湖山对光化辐射、地面O3、NO、NO2浓度的观测结果,对影响地面O3、NO、NO2的主要因子进行了分析。晴天,地面O3、NO、NO2浓度有明显的日变化;阴天,它们的日变化比较复杂。晴天和阴天,在lnQUVB/m和lnQvis/m(其中QUVB为紫外B辐射,Qvis为可见光辐射,m为大气质量)与地面O3、NO,NO2浓度、整层大气水汽含量(q1、q2、q3、q4)之间存在着很好的相关关系。利用得到的关系式计算了地面O3浓度,在紫外和可见光波段,计算值与观测值符合得都比较好。     

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。     

紫外差分吸收激光雷达测量平流层臭氧

我们研制了一台紫外差分吸收（UV-DIAL）激光雷达,用于18～45 km高度的平流层臭氧垂直廓线的长期监测。位于合肥的这一激光雷达于1996年8月全面建成并投入常规运行。本文将给出该激光雷达系统的结构和平流层臭氧测量数据处理。给出的一些测量结果和与其他手段测量结果的对比表明,该激光雷达对平流层臭氧能够进行可靠的测量。     

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.     

A Study of Ozone Laminae Using Diabatic Trajectories, Contour Advection and Photochemical Trajectory Model Simulations.

In this paper, we show that the rate of ozone loss in both polar and mid-latitudes, derived from ozonesonde and satellite data, has almost the same vertical distribution (although opposite sense) to that of ozone laminae abundance. Ozone laminae appear in the lower stratosphere soon after the polar vortex is established in autumn, increase in number throughout the winter and reach a maximum abundance in late winter or spring. We indicate a possible coupling between mid-winter, sudden stratospheric warmings (when the vortex is weakened or disrupted) and the abundance of ozone laminae using a 23-year record of ozonesonde data from the World Ozone Data Center in Canada combined with monthly-mean January polar temperatures at 30 hPa.Results are presented from an experiment conducted during the winter of 1994/95, in phase II of the Second European Stratospheric And Mid-latitude Experiment (SESAME), in which 93 ozone-enhanced laminae of polar origin observed by ozonesondes at different time and locations are linked by diabatic trajectories, enabling them to be probed twice or more. It is shown that, in general, ozone concentrations inside laminae fall progressively with time, mixing irreversibly with mid-latitude air on time-scales of a few weeks. A particular set of laminae which advected across Europe during mid February 1995 are examined in detail. These laminae were observed almost simultaneously at seven ozonesonde stations, providing information on their spatial scales. The development of these laminae has been modelled using the Contour Advection algorithm of Norton (1994), adding support to the concept that many laminae are extrusions of vortex air. Finally, a photochemical trajectory model is used to show that, if the air in the laminae is chemically activated, it will impact on mid-latitude ozone concentrations. An estimate is made of the potential number of ozone molecules lost each winter via this mechanism.     

FY-3星紫外臭氧总量探测仪(TOU)监测大气臭氧及吸收性气溶胶

FY-3卫星上搭载的紫外臭氧总量探测仪(Total Ozone Unit,TOU)是我国首台自主研制的用于全球臭氧总量监测的仪器,自2008年5月至今已有3台仪器搭载在气象卫星(FY-3A/FY-3B/FY-3C)上成功发射并在轨运行。TOU利用紫外波段进行臭氧总量反演,以获得全球臭氧的分布及其变化。2013年,针对我国灰霾、沙尘等气溶胶污染事件频发的环境问题,TOU紫外探测数据被成功用于吸收性气溶胶指数(AAI)的反演,之后TOU被用于我国吸收性气溶胶污染事件的监测,为沙尘、灰霾等的预报提供监测数据。对TOU的数据和产品的质量和应用进行了介绍,包括L1B数据、臭氧总量产品及AAI指数。在此基础上,根据现有仪器的不足,对后续仪器的发展方向进行了阐述。     

Photochemical Effects in the Heterogeneous Reaction of Soot with Ozone at Low Concentrations

The soot-ozone reaction at low concentrations (ppm O₃) hasbeen examined todetermine any influence of solar radiation on its products and kinetics. Theeffect of simulatedsolar radiation is to change the product distribution towardsCO₂(g), CO (g) and H₂O(g) at theexpense of soot surface functional groups formation. Little effect on theextent or rate ofdiminution of O₃ through this rapid reaction is observed. Theinitial rate laws for formation ofall products remain the same under simulated solar radiation, with changes inthe rate constants(and thus in the relative importance of mechanistic pathways) responsible forthe differingproduct distributions. Decarboxylation of soot surface functionalities hasbeen shown to be onepossible mechanism underlying these effects. Atmospheric soot, particularlythat emitted nearthe tropopause by increasing numbers of subsonic and supersonic aircraft, mayplay a role inozone depletion; the rapid diminution of ozone in soot's presence isunaffected by solarradiation.     

On the Importance of Reliable Background Concentrations of Ozone for Regional Scale Photochemical Modelling

Ozone throughout the troposphere is subject of significant temporal and spatial variability due to photochemical production in the planetary boundary layer and free troposphere, stratospheric intrusions, convective events and long range transport. However, high resolving observations of ozone in the troposphere are generally rare today. That is of special disadvantage for limited area models, which represent mathematically a differential equation system with an initial and boundary problem. As ozone concentrations usually increase from the earth surface to the stratosphere, a proper choice of the background ozone concentrations is necessary to reproduce or even predict the amount and distribution of ozone in a specific region of interest.In this paper the impact of background concentrations of ozone on regional scale model results is analysed during a summer smog episode over Europe. For this purpose ozone is artificially partitioned into individual categories. For each category, transport and chemical transformation is calculated separately. Initial and boundary concentrations of ozone dominate total ozone concentrations increasingly with height. But also in the planetary boundary layer they contribute with more than 30% to thetotal ozone changes and are therefore far from being negligible. Moderately modified assumptions of background ozone concentrations reveal an uncertainty of near surface ozone concentrations of 5–15%depending on the weather situation.     

北极楚克奇海上空臭氧垂直变化的探测与分析

1999年夏季,中国首次组织北极地区科学考察.分析此次考察中楚克奇海海域上空获得的大气结构和臭氧探空资料,结合臭氧总量观测光谱仪(TOMS)臭氧总量和NCEP大气环流资料,指出:考察期间楚克奇海海域上空臭氧总量与13 km以下臭氧含量关系密切,而在20 km附近最大臭氧浓度处的臭氧变化与大气臭氧总量关系较差,表明整层臭氧总量的变化主要受低层大气臭氧变化的影响.大气臭氧总量呈高-低-高变化,对流层顶高度呈低-高-低变化,分析500hPa高度场表明:考察期间的天气系统可能是造成局地臭氧变化的主要原因.     

Determination of Dominant Pathways in Chemical Reaction Systems: An Algorithm and Its Application to Stratospheric Chemistry

The analysis of complex chemical reaction systems is frequently complicatedbecause of the coexistence of fast cyclic reaction sequences and slower pathways that yield a net production or destruction of a certain species of interest.An algorithm for the determination of both these types of reaction sequences (in a given reaction system) is presented. Under the assumption that reaction rates are known, it finds the mostimportant pathways by solving a linear optimization problem for each of them.This algorithm may be used as a tool for the interpretation of chemical model runs.For illustration, it is applied to examples in stratospheric chemistry, including the determination of catalytic ozone destruction cycles.     

A Review of Atmospheric Chemistry Research in China: Photochemical Smog, Haze Pollution, and Gas-Aerosol Interactions

In this paper we present a review of atmospheric chemistry research in China over the period 2006-2010, focusing on tropospheric ozone, aerosol chemistry, and the interactions between trace gases and aerosols in the polluted areas of China. Over the past decade, China has suffered severe photochemical smog and haze pollution, especially in North China, the Yangtze River Delta, and the Pearl River Delta. Much scientific work on atmospheric chemistry and physics has been done to address this large-scale, complex environmental problem. Intensive field experiments, satellite data analyses, and model simulations have shown that air pollution is significantly changing the chemical and physical characters of the natural atmosphere over these parts of China. In addition to strong emissions of primary pollutants, photochemical and heterogeneous reactions play key roles in the formation of complex pollution. More in-depth research is recommended to reveal the formation mechanism of photochemical smog and haze pollution and their climatic effects at the urban, regional, and global scales.     

Validation of Ground-Based Visible Measurements of Total Ozone by Comparison with Dobson and Brewer Spectrophotometers

Comparisons of total column ozone measurements from Dobson, Brewer and SAOZ instruments are presented for the period 1990 to 1995 at seven stations covering the mid- and the high northern latitudes, as well as the Antarctic region. The main purpose of these comparisons is to assess, by reference to the well established Dobson network, the accuracy of the zenith-sky visible spectroscopy for the measurement of total ozone. The strengths and present limitations of this latter technique are investigated. As a general result, the different instruments are found to agree within a few percent at all stations, the best agreement being obtained at mid-latitudes. On average, for the mid-latitudes, SAOZ O₃ measurements are approximately 2% higher than Dobson ones, with a scatter of about 5%. At higher latitudes, both scatter and systematic deviation tend to increase. In all cases, the relative differences between SAOZ and Dobson or Brewer column ozone are characterised by a significant seasonal signal, the amplitude of which increases from about 2.5% at mid-latitude to a maximum of 7.5% at Faraday, Antarctica. Although it introduces a significant contribution to the seasonality at high latitude, the temperature sensitivity of the O₃ absorption coefficients of the Dobson and Brewer instruments is shown to be too small to account for the observed SAOZ/Dobson differences. Except for Faraday, these differences can however be largely reduced if SAOZ AMFs are calculated with realistic climatological profiles of ozone, pressure and temperature. Other sources of uncertainties that might affect the comparison are investigated. Evidence is found that the differences in the air masses sampled by the SAOZ and the other instruments contribute significantly to the scatter, and the impact of the tropospheric clouds on SAOZ measurements is displayed.     

A New Index Developed for Fast Diagnosis of Meteorological Roles in Ground-Level Ozone Variations

China experienced worsening ground-level ozone(O₂) pollution from 2013 to 2019. In this study, meteorological parameters, including surface temperature(T₂), solar radiation(SW), and wind speed(WS), were classified into two aspects,(1) Photochemical Reaction Condition(PRC = T₂× SW) and(2) Physical Dispersion Capacity(PDC = WS). In this way, a Meteorology Synthetic Index(MSI = PRC/PDC) was developed for the quantification of meteorology-induced ground-level O₂pollution. The positive linear relationship between the 90 th percentile of MDA8(maximum daily 8-h average) O₂concentration and MSI determined that the contribution of meteorological changes to ground-level O-3 varied on a latitudinal gradient, decreasing from ~40% in southern China to 10%–20% in northern China. Favorable photochemical reaction conditions were more important for ground-level O₂pollution. This study proposes a universally applicable index for fast diagnosis of meteorological roles in ground-level O₂variability, which enables the assessment of the observed effects of precursor emissions reductions that can be used for designing future control policies.     

Stable Carbon Isotope Ratios and the Photochemical Age of Atmospheric Volatile Organic Compounds

Abstract

The dependence of ozone formation on the mixing ratios of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) has been widely studied. In addition to the atmospheric levels of VOCs and NO_x, the extent of photochemical processing of VOCs has a strong impact on ozone levels. Although methods for measuring atmospheric mixing ratios of VOCs and NO_x are well established and results of those measurements are widely available, determination of the extent of photochemical processing of VOCs, known as photochemical age (PCA), is difficult. In this article a recently developed methodology for the determination of PCA for individual compounds based on the change in their stable carbon isotope composition is used to investigate the dependence between ozone and VOC or NO_x mixing ratios at a rural site in Ontario, Canada, during fall and winter. The results show that under these conditions the variability in VOC mixing ratios is predominantly a result of the varying impact of local emissions and not a result of changes in the extent of atmospheric processing. This explains why the mixing ratio of ozone shows no systematic dependence on the mixing ratios of VOCs or NO_x in this environment and at this time of the year.     

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.     

Segregation and Interpretation of Ozone and Carbon Monoxide Measurements by Air Mass Origin at the TOR Station Mace Head, Ireland from 1987 to 1995

Three independent methods have been used to sort the ozone, carbonmonoxide, and other radiatively important trace gases measured at Mace Head,Ireland, and thereby distinguish clean air masses transported over the NorthAtlantic from the more polluted air masses which have recently travelledfrom the European continent. Over the period April 1987–June 1995 theNorthern Hemisphere surface ozone baseline concentrations exhibited a meanconcentration of 34.8 ppb, with a small positive trend (+0.19 ppbyr^-1), while the corresponding trend in air originating fromthe polluted European areas was negative (–0.39 ppbyr^-1). Carbon monoxide measurements from March 1990 toDecember 1994 showed negative trends for both the unpolluted (–0.17ppb yr^-1) and polluted data (–13.6 ppbyr^-1). Overall the continent of Europe was shown to be a smallnet sink of 2.6 ppb for all occasions when European air was transported tothe North Atlantic.     

Observations of Streamers in the Troposphere and Stratosphere Using Ozone Lidar

We describe here a DIAL lidar system for atmospheric ozone measurements atAberystwyth, Wales, together witha method for deriving a stratospheric ozone profile from a single laserwavelength. Lidar measurements are used todepict the passage of three mesoscale ozone disturbances in the troposphereand stratosphere. In the troposphere, twosmall fold-like structures are shown beneath and at the edge of streamers ofhigh potential vorticity in ECMWFanalyses. MST radar measurements at the same time show that one of these foldswas actively turbulent, causingmixing of stratospheric and tropospheric air. In the stratosphere, a streamerof low-latitude air drawn into a filamentby a breaking Rossby wave event was observed crossing the lidar site.