Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

Atmospheric chemistry of hydrogen fluoride

Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500 m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.     

Atmospheric stabilization and the timing of carbon mitigation

Stabilization of atmospheric CO₂ concentrations below a pre-industrial doubling (~550 ppm) is a commonly cited target in climate policy assessment. When the rate at which future emissions can fall is assumed to be fixed, the peak atmospheric concentration – or the stabilization “frontier” – is an increasing and convex function of the length of postponement. Here we find that a decline in emissions of 1% year^?1 beginning today would place the frontier near 475 ppm and that when mitigation is postponed, options disappear (on average) at the rate of ~9 ppm year^?1, meaning that delays of more than a decade will likely preclude stabilization below a doubling. When constraints on the future decline rate of emissions are relaxed, a particular atmospheric target can be realized in many ways, with scenarios that allow longer postponement of emissions reductions requiring greater increases in the intensity of future mitigation. However, the marginal rate of substitution between future mitigation and present delay becomes prohibitively large when the balance is shifted too far toward the future, meaning that some amount of postponement cannot be fully offset by simply increasing the intensity of future mitigation. Consequently, these results suggest that a practical transition path to a given stabilization target in the most commonly cited range can allow, at most, one or two decades of delay.     

Atmospheric response to deep-sea injections of fossil-fuel carbon dioxide

The possibility of controlling atmospheric carbon dioxide accumulation and attendant climatic effects from fossil-fuel burning by diverting a fraction of the combustion product and injecting it into the deep-ocean, as proposed by Marchetti, is analyzed using an atmosphere/mixed layer/diffusive deep-ocean model for the carbon cycle. The model includes the nonlinear buffering of CO₂ at the air/sea interface, and considers the long term trends associated with consuming an assumed fossil-fuel reserve equivalent to 7.09 × 10¹⁵ kg carbon as a logistic function of time as in the projections of Siegenthaler and Oeschger, except that atmospheric carbon dioxide levels are computed for five alternate strategies: (a) 100% injected into atmosphere, (b) 50% injected at oceanic depth of 1500 m and 50% into atmosphere, (c) 50% injected at sea floor (4000 m) and 50% into atmosphere, (d) 100% at 1500 m depth and (e) 100% at sea floor. Since no carbon leaves the system, all runs approached the same post-fossil fuel equilibrium after several thousand years, C _a - 1150 ppm, almost four times the pre-fossil fuel value (- 300 ppm). But the transient response of these cases showed a marked variation ranging from a peak overshoot value of 2800 ppm in the year 2130 for 100% atmospheric injection to a slight decrease to the pre-fossil fuel 300 ppm lasting till 2300 with a subsequent slow approach to equilibrium for the 100% deep-ocean injection. The implications of these results for an oceanic injection strategy to mitigate the climatic impact of fossil-fuel CO₂ is discussed, as are the ingredients of a second generation carbon cycle model for carrying out such forecasts on an engineering design basis.     

Atmospheric chemistry of the monoterpene reaction products nopinone,camphenilone, and 4-acetyl-1-methylcyclohexene

Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO₃ radicals and O₃ have been measured at 296±2 K. The rate constants (cm³ molecule^–1 s^–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10^–11; camphenilone, (5.15±1.44)×10^–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10^–10; for reaction with the NO₃ radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10^–11; and for reaction with O₃: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10^–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.     

Pacific Atmospheric Sulfur Experiment (PASE): dynamics and chemistry of the south Pacific tropical trade wind regime

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157º, 20?? W, 2º 52?? N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6?C12º south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3?C15 ms^?1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth??s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (??300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO₂ has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO₂ conversion efficiency of 60?C73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO₂, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO.     

Atmospheric carbon dioxide variations at coastal site, Shibukawa, in Seto Inland Sea, Japan

Summary Four years of measurements (1980–83) of carbon dioxide at the northern coast site, Shibukawa, are presented. The data reveal well defined diurnal and seasonal variations. The amplitude of the daily carbon dioxide variation is about 30 ppm during the colder season (January–March; November–December), and about 60 ppm during the warmer season (April–October). The seasonal variation of daily minimum concentration of carbon dioxide has a maximum in the middle of summer (July–September) and a minimum in the winter months. This variation does not correspond to that expected from vegetation activity. The summer peak in carbon dioxide concentration seems to be inherent features at the coast site, Shibukawa; it is probably due to less activity of the vertical mixing under stable stratification of the air layer prevailing throughout the day. The year-to-year comparison of minimums in the winter months reveals an average annual increase of the carbon dioxide content of 6 ppm/year, which is much greater than 1.5 ppm/year observed in the troposphere over Japan [1]. This indicates that the carbon dioxide concentration and its variations at Shibukawa station represent the local scale values rather than the large scale one. The horizontal distribution of carbon dioxide concentration, measured over sea surface near Shibukawa station, also suggests the existence of many patches of high concentration of carbon dioxide due to the local point sources related to the human activity such as ships and industries distributed at the coast site.

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Variationen des atmosphärischen CO₂ bei Shibukawa im Küstengebiet des Inlandsees Seto in Japan

Zusammenfassung Es werden Ergebnisse über Tages- und Jahresgänge von vierjährigen Messungen (1980–83) des CO₂ bei Shibukawa an der nördlichen Küste des Sees vorgelegt. Die Amplitude des Tagesganges beträgt in der kalten Jahreszeit ungefähr 30 ppm und in der warmen Jahreszeit ungefähr 60 ppm. Im Jahresgang des täglichen Minimums des CO₂ fällt das Maximum auf den Sommer und das Minimum auf Wintermonate. Dies entspricht nicht der aus der Aktvität der Vegetation zu erwartenden Variation. Das Sommermaximum scheint eine Besonderheit der Lage von Shibukawa an der Küste zu sein und ist wahrscheinlich auf die zu geringe vertikale Durchmischung bei der tagsüber dort vorherrschenden stabilen Schichtung zurückzuführen. Der Vergleich der Minima der Wintermonate von Jahr zu Jahr läßt eine Zunahme um 6 ppm pro Jahr erkennen, die bedeutend größer ist als die Zunahme um 1,5 ppm pro Jahr in der Troposphäre über Japan [ 1 ]. Dies weist darauf hin, daß die CO₂-Konzentration und ihre Variationen in Shibukawa eher lokale als großräumige Werte darstellen.Die über der Seeoberfläche in der Nähe von Shibukawa gemessene Verteilung der CO₂-Konzentrationen zeigt viele Stellen mit hoher CO₂-Konzentration, die auf lokale Punktquellen menschlicher Aktivität wie auf Schiffe und auf an der Küste verteilte Industrien hinweisen.

     

大气涛动

<正>大气涛动的研究至今已有百年以上的历史。19世纪末,当人们开始绘制月平均海平面气压图时,就发现了"大气活动中心",即相对稳定的高压区或低压区。有些低压及高压终年存在,被称为永久性活动中心,如北大西洋上的冰岛低压和亚述尔高压、北太平洋上的阿留申     

Tropospheric ozone chemistry. The impact of cloud chemistry

The effect of clouds and cloud chemistry on tropospheric ozone chemistry is tested out in a two-dimensional channel model covering a latitudinal band from 30 to 60° N. Three different methods describing how clouds affect gaseous species are applied, and the results are compared. The three methods are:

?A first order parameterization scheme for the removal of sulphur and other soluble gases by liquid droplets.

?A parameterization scheme for SO₂, O₃, and H₂O₂ removal is constructed. The scheme is based on the solubility of gases in liquid droplets, cycling times of air masses between clouds and cloud free areas and on the chemical interaction of SO₂ with H₂O₂ and O₃ in the liquid phase.

?Gas-aqueous-phase interactions and aqueous-phase chemical reactions are included in the reaction scheme for a number of components in areas where clouds are present.

In all three methods, a full gas-phase chemistry scheme is used. Particular emphasis is given to the study of how the ozone and hydrogen peroxide levels are affected. Significant changes in the distributions are found when aqueous-phase chemical reactions are included. The result is loss of ozone in the aqueous phase, with pronounced reductions in ozone levels in the middle and lower troposphere. Ozone levels are reduced by 10 to 30% with the largest reductions in the remote middle troposphere, bringing the values in better agreement with observations. Changes in H₂O₂ are harder to predict. Although, in one case study, hydrogen peroxide is produced within the aqueous phase, concentrations are mostly comparable or even lower than in the other cases. Hydrogen peroxide levels are, however, shown to be very pH sensitive. pH values around 5 seem to favour high H₂O₂ levels. High H₂O₂ concentrations may be found particularly in the upper part of the clouds under favourable conditions.     

Global Atmospheric Watch

CAMSisresponsibleforthescientific/technicalsupporttotheGAW(GlobalAtmosphereWatch).monitoringprogramincludingoneGAWbaselinestation(ChinaGlobalAtmosphereWatchBaselinelObservatory-CGAWBO),threeGAWregionalstationsandanational-wideacidrainmonitoringnetworkofI86sites.Inthesestations,thelong-termcomprehensiveatmosphericmonitoringofCO=,CO,CH',Ozone.(totalandsurface),SO=,precipitation(acidrain)chemistry,aerosolchemistry,solarradiation,meteorologicallelements,etc.isconducted.Themajorprogre…     

大气边界层和大气环境研究进展

大气边界层物理和大气环境是大气科学的重要领域,中国科学院大气物理研究所自成立以来在这一研究领域取导了丰硕的成果.作者重点介绍最近十多年来在大气边界层探测、大气边界层结构特征、大气湍流理论、城市和区域大气污染预测预报模式研究等方面取得的重要进展,并对大气边界层和大气环境研究的未来发展作了展望.     

大陆大气本底基准研究

国家社会公益类研究重点项目“大陆大气本底基准研究”2006年8月通过由国家科技部基础司组织的验收。验收专家组认为项目观测数据资料、数据质量的总体水平达到国际先进水平，对瓦里关山NOy的观测和本底地区气溶胶理化特性方面有价值的发现。     

Reduction of Multiphase Atmospheric Chemistry

The aim of this article is to investigate the dynamical behaviour ofmultiphase atmospheric chemical mechanisms. Reducing procedures areapplied to a multiphase chemical box model including gas-phasereactions, aqueous-phase reactions and interfacial mass transfer. The lumping of species is computed in an automatic wayusing an efficient algorithm (apla). The computed lumped species arerelated to the fast behaviour of chemical and microphysical processessuch as Chapman cycle, ionic dissociations within the cloud drops andinterfacial Henry's equilibria. Depending on some parameters (liquidwater content, droplet radius) mixed lumped species (including both phases) may also becomputed. We show the existence of hierarchical reduced models due to the existence ofmultiple timescales. We use a special algorithm (dan2) in order tosolve the reduced models. Such models are accurate and the relative errorremains under the threshold of 1%. The speed-up is up to a factor 5comparedwith a fully implicit method (Gear) for the same accuracy. The key pointis that it provides a good qualitative understanding for the behaviourof the kinetic scheme.     

广义大气密度函数

把大气密度函数的定义从几何空间扩大到相空间(如压力温度等),引入了广义大气密度函数概念,讨论了这个函数的计算方法和积分特点,给出了两个简单的广义大气密度函数实例,还讨论了相空间中的大气方程组问题。     

Some Aspects of Atmospheric Dispersion in the Stratified Atmospheric Boundary Layer over Homogeneous Terrain

The ability to simulate atmospheric dispersion with models developed for applied use under stable atmospheric stability conditions is discussed. The paper is based on model simulations of three experimental data sets reported in the literature. The Hanford data set covered weakly stable conditions, the Prairie Grass experiments covered both weakly stable and very stable atmospheric conditions, and the Lillestrøm experiment was carried out during very stable conditions. Simulations of these experiments reported in the literature for eight different models are discussed. Applied models based on the Gaussian plume model concept with the spread parameters described in terms of the Pasquill stability classification or Monin–Obukhov similarity relationships are used. Other model types are Lagrangian particle models which also are parameterized in terms of Monin–Obukhov similarity relationships. The applied models describe adequately the dispersion process in a weakly stable atmosphere, but fail during very stable atmospheric conditions. This suggests that Monin–Obukhov similarity theory is an adequate tool for the parameterization of the input parameters to atmospheric dispersion models during weakly stable conditions, but that more detailed parameterisations including other physical processes than those covered by the Monin–Obukhov theory should be developed for the very stable atmosphere.