First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

北京奥运会期间CBM-Z化学机制的模拟应用

利用CBM-Z化学机制模拟了中国科学院大气物理研究所气象塔站在北京奥运会期间高臭氧时段O3浓度的日变化,评估了气象条件、北京奥运会加强控制措施以及O3前体物浓度对近地面O3生成的影响。结果表明:(1)CBM-Z化学机制较好地模拟了北京奥运会期间典型时段气象塔站O3、NO、NO2日变化特征。(2)有利于局地高臭氧事件发生的气象条件非常相似;北京奥运会加强控制措施的实施显著减少了NOx及VOCs的排放量,导致近地面O3浓度的明显下降。(3)奥运会期间VOCs和CO是影响气象塔站O3生成量的关键因素。     

Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

长江三角洲地区对流层臭氧的变化趋势

Analysis of tropospheric ozone residual (TOR) data from satellite measurements indicates an increasing trend of tropospheric ozone over the Yangtze Delta region of China. The increasing trend can be derived both from the annual mean TOR and from the monthly mean TOR except for January and March. The increase rate of the decadal mean TOR was 0.82 DU during 1978-2000. The impact of this long-term trend on the climate and atmospheric oxidizing capacity over the region should be further studied. Data comparison shows a significant correlation between the TOR and surface ozone data collected at Lin'an background station in the Yangtze Delta region, suggesting an internal connection between both quantities.     

An Algorithm for the Determination of All Significant Pathways in Chemical Reaction Systems

When the output of a complex chemical model is analysed, a typical topic isthe determination of pathways, i.e., reaction sequences, that produce ordestroy a chemical species of interest.A representative example is the investigation of catalytic ozone destruction cycles in the stratosphere.An algorithm for the automatic determination of pathways in any given reactionsystem is presented. Under the assumption that reaction rates are known, it finds all significant pathways, i.e., all pathways with a rate above a prescribed threshold.The algorithm forms pathways step by step, starting from single reactions.The chemical species in the system are consecutively considered as `branching points'.For every branching-point species, each pathway producing it is connected witheach pathway consuming it.Rates proportional to `branching probabilities' are calculated.Pathways with a rate that is smaller than a prescribed threshold arediscarded.If a newly formed pathway contains sub-pathways, e.g., null cycles, it is split into these simpler pathways.In order to demonstrate the performance of the algorithm, it has been applied to the determination of catalytic ozone destruction cycles and methaneoxidation pathways in the stratosphere.     

Atmospheric Circulation Changes in Response to an Observed Stratospheric Zonal Ozone Anomaly

Abstract

In a sensitivity study, the influence of an observed stratospheric zonal ozone anomaly on the atmospheric circulation was investigated using the Fifth Generation European Centre Hamburg Model (ECHAM5) which is a general circulation model. The model was run from 1960 to 1999 (40 years) with a mean seasonal cycle of zonally symmetric ozone. In order to isolate the induced dynamical influence of the observed zonally asymmetric part of the three-dimensional stratospheric ozone, a second run was performed for the boreal extratropics using prescribed monthly means from the 40-year reanalysis dataset from the European Centre for Medium-range Weather Forecasts (ERA-40). The main findings are the interdecadal westward shift of the polar vortex at about 65°N and a significant increase in the number of stratospheric sudden warmings during the 1980–99 period. Under the action of zonally asymmetric ozone a decrease in the Arctic Oscillation was identified between the mid-1980s and the mid-1990s. The lag correlation between the mean Arctic Oscillation at the surface and the daily stratospheric northern annular mode increased in mid-winter. Furthermore, we examined the influence of the stratospheric zonal ozone anomaly on Rossby wave breaking in the upper troposphere and found a significant westward shift of poleward Rossby wave breaking events over western Europe in the winter. By this we show that the stratospheric zonal ozone anomaly has a strong influence on the tropospheric circulation as a result of enhanced dynamical coupling processes.     

Total ozone response to major geomagnetic storms and changes in meteorological situations

Summary The total ozone response to strong major geomagnetic storms (A_p≥60) in winter along the 50° N latitudinal circle is studied. The results add to the recent results of Laštovička et al. (1992) obtained for European middle latitudes (∼50°N) and to the results of Mlch (1994). A significant response of total ozone is only observed in winter under high solar activity/E-phase of QBO conditions (E-max) and seems to be caused by geomagnetic storm-induced changes of atmospheric dynamics. There are two sectors along latitude 50°N, which are sensitive to forcing by geomagnetic storms both in total ozone and the troposphere — north-eastern Atlantic-European and eastern Siberia-Aleutian sectors. The total ozone response under E-max conditions manifests itself mainly as a large decrease in the longitudinal variation of ozone after the storm, which means an increase of ozone in Europe. The observed effects in total ozone consist in redistribution, not production or loss of ozone.     

青藏高原环境气象研究进展

近十年来,青藏高原环境气象研究进展迅速,无论是观测研究还是理论研究方面均有新的发现。周秀骥和邹捍等先后发现夏季青藏高原上空的臭氧低值中心并提出了产生这种低值中心的可能原因。高登义等利用１９７５年以来对珠穆朗玛峰北坡水环境的监测资料,分析研究后发现,１９９０￣１９９１年爆发的中东战争油田燃烧曾污染了珠峰地区的水环境,带来珠峰北坡绒布河水十三种化学元素含量的剧烈增加,比其前后各年增加了５￣７倍。     

北京地区臭氧垂直分布的演变趋势与特征的研究——卫星SBUV资料与地面遥感对比分析

利用地面遥感O₃垂直分布的逆转方法〈C〉测量出的北京上空O₃剖面资料,对雨云7号卫星的SBUV系统测量的同地区的O₃垂直分布数据进行了订正.对订正后的长达8年（1979-1986年）的完整的SBUV资料进行了较为仔细的分析,得出了这一时期内的O₃垂直分布长期演变呈下降趋势.并在上层O₃含量的季节变化特征和周期振荡等方面,有新的发现,得出一些有意义的结果.