Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Global climatic change – the latest scientific understanding

IPCCs statement in its 1995 report (IPCC 1996) that a human influence was discernible in global climate has been widely quoted but often misunderstood. The character of the evidence underpinning this detection statement is explained so that its strengths and weaknesses can be better understood and the subtleties of its message better appreciated. To demonstrate the close linkage between the government-approved summary and the underlying chapters of the IPCC report the detailed evolution of the detection statement from first draft through to the form finally approved by the IPCC is described.     

Ozone production due to emissions from vegetation burning

Ozone has been observed in elevated concentrations by satellites over areas previously believed to be background. There is meteorological evidence, that these ozone plumes found over the Atlantic Ocean originate from vegetation fires on the African continent.In a previous study (DECAFE-88), we have investigated ozone and assumed precursor compounds over African tropical forest regions. Our measurements revealed large photosmog layers at altitudes from 1.5 to 4 km. Both chemical and meteorological evidence point to savanna fires up to several thousand km upwind as sources.Here we describe ozone mixing ratios observed over western Africa and compare ozone production ratios from different field measurement campaigns related to vegetation burning. We find that air masses containing photosmog ingredients require several days to develop their oxidation potential, similar to what is known from air polluted by emissions from fossil fuel burning. Finally, we estimate the global ozone production due to vegetation fires and conclude that this source is comparable in strength to the stratospheric input.     

A note on the determination of ozone concentrations from radio-meteor duration distributions.

Hajduk, et al (1992) have drawn attention to a possible source of error in our earlier analysis of visual and radar observations of shower meteors from which we calculated the ozone concentration at meteor heights. We have considered their main criticism that the features of our data which we used to calculate the ozone concentration may have been due to the constraint that our meteors had to be observed by both methods. We have shown that observations collected from radar-only systems show very similar characteristics and that these can be analysed without recourse to visual data to produce very similar results to those from our original analysis. Presented at theInternational Conference on Meteoroids 23 – 31 August 1994 in Bratislava.Submitted to Earth, Moon and Planets     

Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l^-1 and from 1.4 to 11.3 nmol m^-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m^-2 d^-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m^-2 d^-1, respectively.     

Carbon, sulfur and O2 across the Permian–Triassic boundary

A model for the carbon and sulfur cycles across the Permian–Triassic boundary has been constructed from carbon and sulfur isotopic data. Results indicate a drop in global organic matter burial, the formation of an anoxic deep ocean, and a large drop in atmospheric oxygen over the time span 270 to 240 Ma. Much of these changes were probably due to a drop in terrestrial productivity and preservation and an increase in global aridity.     

Rodent paleofaunas as indicators of climatic change in Europe during the last 125,000 years

This paper presents a quantitative reconstruction of the European late Pleistocene paleoclimate based on 72 rodent assemblages of five sequences from France, Germany and Bulgaria, covering the last interglacial-glacial cycle. They show a pattern of severe changes in temperature, with reduced precipitation during the coldest periods. A tentative correlation between the isotopic and palynological records and the paleotemperature changes is shown. These changes are consistent with variations in atmospheric circulation patterns in response to an expanding-retracting Fennoscandian ice-sheet. They can be attributed to the enhancement-weakening of the Scandinavian-Polar anticyclone and its associated dry winds, the south-north shifting of the North Atlantic Polar Front, and the varying supply of moist air from the Atlantic. Qualitative paleoenvironmental analysis shows broadleaved-deciduous forests in France and Bulgaria during most of the studied period. Taiga and tundra appeared in eastern France during the lower Würm. The German sequence indicates the presence of coniferous forests. These results are broadly consistent with other paleobiological records (mammalian, avian and insect faunas, isotopic record in dental tissue, palynology). The main discrepancies with the paleoclimate inferred from the palynological record are found during the coldest periods and are probably due to the interaction between vegetation, climate, and atmospheric CO₂ levels.     

大气边界层湍流温度序列的信息熵分析

利用大气边界层内近地面的大气湍流温度时间序列，运用功率谱分析、信息熵分析等方法，分析了大气边界层内近地面的大气湍流特点，并对稳定层和不稳定层的大气湍流进行了对比。结果表明，信息熵和功率谱指数是区别稳定层结和不稳定层结大气边界层湍流特征的指标，对造成两者之间的差别做出了对应的解释。     

论江西省大气成分观测与服务系统建设

在介绍国内外大气成分观测与研究进展的基础上，对建设江西省大气成分观测与服务系统的必要性和可行性进行了科学的分析，并从系统建设的原则、目标、内容、技术路线、监测方案，以及系统研究的主要内容和提供的产品等方面，对拟建的江西省大气成分观测与服务系统进行了全面的阐述。研究结果认为，随着江西经济建设的快速发展，建设江西省大气成分观测与服务系统，有利于了解和掌握江西大气物质成分分布特征及变化情况；有利于提高江西天气气候预报预测准确率，提升江西气象公共服务的能力和水平；可为预防大气化学灾害和控制区域大气环境质量，提供科学的决策依据，具有显著的社会、经济效益和生态效益。     

夏季青藏高原加热和北半球环流年际变化的相关分析

利用 195 8～ 1997年NCEP/NCAR再分析数据集中加热率和环流资料 ,采用相关分析和对比分析相结合的方法 ,诊断和分析了夏季青藏高原的非绝热加热与北半球环流系统的年际变化的联系。分析结果表明 :夏季青藏高原的加热强 (弱 )的年份 ,高原及邻近地区的上升运动、下层辐合及上层辐散均增强 (减弱 ) ,使高原加热对周边地区低层暖湿空气的抽吸效应和对高层大气向周边地区的排放作用加强 (减弱 )。从而影响着高原和周边地区的环流以及亚洲季风区大尺度环流系统。而且高原的加热强迫能够激发产生一支沿亚欧大陆东部海岸向东北方向传播的Rossby波列 ,其频散效应可影响到更远的东太平洋以至北美地区的大气环流