Two-dimensional modelling of some CFC replacement compounds

The Cambridge 2-D Eulerian model has been used to study the potential atmospheric distributions and lifetimes of a number of CFC replacement compounds and their degradation products. The study has focused on HFC 134a and HCFCs 123, 141b and 142b and the major products formed by their atmospheric degradation. The loss of these compounds and their products by hydroxyl radical attack, photolysis and in-cloud hydrolysis have been investigated. The study has shown that HCFCs 141b and 142b have sufficiently long lifetimes to enter the stratosphere in significant quantities, where degradation leads to an increase in the total stratospheric chlorine concentration. The study has also highlighted areas where further experimental work would be valuable, in particular characterisation of the product channels for the degradation reactions and determination of the removal rates of the products in the aqueous phase.     

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.     

Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

单站GPS遥感水汽含量范围的确定及结果分析

随着GPS技术的日益成熟和研究的不断深入,GPS的定位精度得到了大幅度的提高,为其在测绘、交通、林业资源、石油勘探、精细农业等行业的应用提供了更广阔的空间。GPS气象学(GPS/Meteorology简称GPS/MET)的诞生改善了原有大气监测技术的局限性,极大的提高了气象监测的时空分辨率,但是在将这项技术由试验阶段向推广普及应用的过程中,单站地基GPS监测的有效范围以及水汽解的精度一直为广大气象学家们所忽略,本文在对以往GPS气象数据收集和整理的基础上,根据理论计算和实际验算,得出了一些有益的结论。     

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.     

Retrieval of the Change of Precipitable Water Vapor by GPS Technique

The feasibility of GPS precipitable water vapor (PWV) is discussed based on the comparison of Radiosonde and GPS PWV where the correlation coefficient is 0.94 and the RMS is 4.0 mm. PWV change in the C...     

拱星OH脉泽辐射频谱的双峰结构和多重分离的膨胀拱星壳

对一些OH／IR星的拱星OH脉泽的观测结果表明,在双峰结构谱线轮廓上常常可以发现一些小峰叠加在双峰上,即在谱线轮廓的双峰结构中的每个峰是由几个小峰叠加而成的．从脉泽的辐射转移方程和拱星包层的速度结构出发,研究拱星OH脉泽辐射频谱的轮廓特征,提出多重分离的膨胀拱星亮模型,很好地解释了双峰结构的奇特观测现象．     

Intercomparison of Tropospheric OH Measurements by Different Laser Techniques during the POPCORN Campaign 1994

In-situ OH measurements by laser-induced fluorescence (LIF) spectroscopy and folded long-path differential optical absorption spectroscopy (DOAS) were carried out in a rural environment in North-East Germany as part of the field experiment POPCORN in August 1994. The large set of OH data obtained allowed an intercomparison of both techniques based on relative diurnal profiles and simultaneously measured absolute concentrations. Most of the time the two OH instruments encountered the same air and agreed well in the measured relative diurnal variations. Only on a few occasions the measurements significantly disagreed due to a perturbation of the DOAS measurements by a local OH source in the north-western wind sector. Excluding data from this wind direction, the statistical analysis of 137 data pairs yields a correlation coefficient of r = 0.90 and a weighted linear fit with a slope of 1.09 ± 0.12. The correlations are carefully analyzed. The comparison of both instruments is discussed in the light of newly published effective absorption cross-sections for H2O and O2 that affect the calibration of LIF.     

A Three-year Study of Nonmethane Hydrocarbons in Surface Air over Saxony (Germany)

Measurements of the nonmethane hydrocarbon (NMHC) mixing ratio over a period of 42 months were carried out for the first time in the air of a research station situated in the former East Germany during the SANA project. Apart from four species, all other species analysed showed a statistically significant downward trend at the 95% significance level. The decrease of the hydrocarbon concentrations was superimposed by seasonal variations. A drop of about 40% of the annual mean values from 1993 to 1995 was observed. This development reflects the dramatic changes in traffic, industry, power economy, and agriculture in Saxony after the reunification of Germany. The remove of two-stroke engined cars is reflected in NMHC mixing ratio changes, as is the removal of obsolete chemical plants. Generally it was not possible to relate causes and effects of a single event, but in some cases major changes in concentrations and NMHC ratios occurred coincidentally with the disappearance of a specific emission source.