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.     

Natural and anthropogenic C2 to C6 hydrocarbons in the central-eastern Venezuelan atmosphere during the rainy season

The levels of low molecular weight hydrocarbons were measured at pristine sites and rural locations affected by hydrocarbon emissions from oil and gas producing fields in Venezuela. At the clean sites, lower concentrations of C₂ to C₆ alkanes were observed, whereas, in comparison with remotes sites, very much higher levels were measured at the polluted sites. Alkenes present relatively high concentrations, with isoprene being the most abundant, all over the study region. The main sources of alkenes are likely to be natural, mainly from vegetation. The levels of alkanes recorded at the clean sites and the alkene levels found everywhere in the region are in agreement with the values reported for other clean sites in the tropics. The increase of ozone production capacity due to the anthropogenic emissions of alkanes from oil and gas fields was estimated. Due to the presence in the atmosphere of important amounts of naturally emitted isoprene, ethene and propene, which makes a substantial contribution to the reactivity of the hydrocarbon mixture, a small increase (<5%) was estimated to occur in the capacity of the ozone production at a regional scale during the rainy season.     

Accuracy of ozonesonde measurements in the troposphere

Measurements of atmospheric ozone at concentrations typical of the free troposphere have been compared for ECC sondes and a UV-absorption photometer, using a Bendix chemiluminescent analyser as a transfer standard. Comparisons were conducted in the laboratory and in the tropospheric part of the atmosphere. It was found that the measurements agreed to within 4% provided that the background current for the ECC sonde was measured before exposure to ozone in the preparation procedure, and was assumed to be constant throughout the sonde flight. These results confirm those of earlier experiments and mean that the methods currently used to correct for the background current in the troposphere need to be revised.     

Collection and analysis of atmospheric ozone samples

Anomalies found in the isotope ratios of ozone are traceable to the ozone formation process. Metastable electronic states may be responsible for the preferred production of the heavy molecules. While laboratory isotope data and first tropospheric results agree well in the magnitude of isotope enrichments, stratospheric measurements show often higher values. Only through the collection of ozone samples can sufficiently large amounts of gas be obtained to analyze the three isotopes ⁴⁸O₃, ⁴⁹O₃, and ⁵⁰O₃. Collector systems have been developed and successfully operated in the troposphere and in the stratosphere. They will play in the future an important role in atmospheric oxygen isotope studies.     

Boundary-layer ozone depletion as seen in the Norwegian Arctic in spring

Several years of measurements of ozone, hydrocarbons, sulphate and meteorological parameters from Spitsbergen in the Norwegian Arctic are presented. Most of the measurements were taken on the Zeppelin Mountain at an altitude of 474 m a.s.l. The focus is the episodes of ozone depletion in the lower troposphere in spring, which are studied in a climatological way. Episodes of very low ozone concentrations are a common feature on the Zeppelin Mountain in spring. The low ozone episodes were observed from late March to the beginning of June. When the effect of transport direction was subtracted, the frequenty of the low ozone episodes was found to peak in the beginning of May, possibly reflecting the seasonal cycle in the actual depletion process. Analyses based on trajectory calculations show that most of the episodes occurred when the air masses were transported from W-N. Ozone soundings show that the ozone depletion may extend from the surface and up to 3–4 km altitude. The episodes were associated with a cold boundary layer beneath a thermally stable layer, suppressing mixing with the free troposphere. The concentration of several individual hydrocarbons was much lower during episodes of low ozone than for the average conditions. The change in concentration ratio between the hydrocarbons was in qualitative agreement with oxidation of hydrocarbons by Br and Cl atoms rather than by OH radicals.     

MEASUREMENTS AND MODEL SIMULATIONS OF SURFACE OZONE VARIATIONS AT DIFFERENT BACKGROUND CONCENTRATIONS OF THE PRECURSORS

Ozone photochemical production and loss in very different environments at Waliguan baselinestation and Lin'an background station were simulated by using the measurement data and photo-chemical box model.The results show that net ozone photochemical production rate is negative,about 0.5 ppb/d,at Waliguan baseline sation,because of very low precursor concentrations.Butat Lin'an background station,the net photochemical ozone production is positive,about 2—3 ppb/h.which is very closed with the measurement at Lin'an.That means ozone production was con-trolled by photochemical reactions at Lin'an background station,because of the higher precursorconcentrations.The net destruction rate,at Waliguan Mt.,is not large,so that future increase inanthropogenic emission of reactive nitrogen will lead to larger production rates of steady-state O_3concentration.     

大气臭氧与气溶胶垂直分布的高空气球探测

本文给出了1993年9月12日利用高空科学气球在河北省香河地区探测到的大气臭氧和气溶胶的垂直分布。结果发现:(1) 大气臭氧的数密度在整个对流层较低(～10[12]mol/cm3)，并从地面到对流层顶略有下降；对流层顶以上开始快速增加，极值层高度在～24 km，其值为4.78×10[12]mol/cm3；臭氧分压有类似的分布特征，极值146×10[-4]Pa，位于同一高度；(2) 在平流层低层，臭氧分压有一个次极值62×10[-4]Pa，位于15～16 km；(3) 0～30 km大气气溶胶数密度呈现出三个峰值:143，8和1.1 个/cm[3]，分别位于近地面、5 km和21 km；（4）气溶胶的数密度谱在对流层为双模态；在平流层，次峰消失。同时，我们还与其他观测结果作了比较分析。     

中层大气行星波在臭氧的季节和年际变化中输运作用的数值研究──Ⅰ．常定流的情况

本文构造了一个３４层球坐标原始方程波－流相互耦合谱模式，利用此模式从拉格朗日平均环流的观点研究了在常定流下行星波对臭氧的输运作用。研究结果表明，行星波对臭氧的输运有明显的季节变化，在北半球冬季，由于行星波上传到平流层而大大增强了中高纬地区向极地向下的Ｏ３输运；并且还表明，热带纬向风的ＱＢＯ不仅通过影响东、西风切变而引起热带Ｏ３分布的年际变化，而且通过影响行星波的传播引起了行星波对Ｏ３输运的年际变化，这表现为当热带纬向风处于东风位相时，中高纬地区行星波对Ｏ３的输运比西风位相时强。     

A modeling study of effective radiative forcing and climate response due to tropospheric ozone

This study simulates the effective radiative forcing(ERF) of tropospheric ozone from 1850 to 2013 and its effects on global climate using an aerosol–climate coupled model, BCC AGCM2.0.1 CUACE/Aero, in combination with OMI(Ozone Monitoring Instrument) satellite ozone data. According to the OMI observations, the global annual mean tropospheric column ozone(TCO) was 33.9 DU in 2013, and the largest TCO was distributed in the belts between 30°N and 45°N and at approximately 30°S; the annual mean TCO was higher in the Northern Hemisphere than that in the Southern Hemisphere;and in boreal summer and autumn, the global mean TCO was higher than in winter and spring. The simulated ERF due to the change in tropospheric ozone concentration from 1850 to 2013 was 0.46 W m~(-2), thereby causing an increase in the global annual mean surface temperature by 0.36℃, and precipitation by 0.02 mm d~(-1)(the increase of surface temperature had a significance level above 95%). The surface temperature was increased more obviously over the high latitudes in both hemispheres, with the maximum exceeding 1.4?C in Siberia. There were opposite changes in precipitation near the equator,with an increase of 0.5 mm d~(-1)near the Hawaiian Islands and a decrease of about-0.6 mm d~(-1)near the middle of the Indian Ocean.     

2008年冬季北京上空上对流层/下平流层臭氧的异常特征

利用国产GPSO3臭氧探空系统观测的大气臭氧探空资料和NCEP再分析资料,结合对天气形势、大气环流背景、高空位涡变化及对流层顶高度扰动的分析,深入研究了2008年冬季北京地区10~14 km高度范围内持续出现的臭氧次峰值及大气臭氧含量异常现象。结果表明:在2008年我国南方雪灾这一特殊时期,引起臭氧垂直分布持续出现次峰值现象及臭氧含量异常的主要原因是平流层空气强烈下沉运动及其与对流层的交换作用,而引起这种下沉运动及平流层-对流层交换则是由于该阶段特殊的天气背景,乌拉尔阻塞高压长时间维持,贝加尔湖到巴尔喀什湖一带横槽稳定存在,里海以东切断低压长期维持,造成冷空气长时间、稳定地南下影响北京上空臭氧的垂直分布。加之副热带急流的出现,北京正处于其入口区左侧,其上空有强烈的辐合下沉运动,有利于平流层空气向下输送。此次臭氧次峰值及臭氧含量异常的现象很好地说明,在冷空气天气过程的影响下,北京地区上空的平流层空气运动及其与对流层的交换十分活跃。