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1.
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. 相似文献
2.
Major reactive species of ambient volatile organic compounds (VOCs) and their sources in Beijing 总被引：1，自引：0，他引：1
Volatile organic compounds (VOCs) are important precursors of atmospheric chemical processes. As a whole mixture, the ambient VOCs show very strong chemical reactivity. Based on OH radical loss rates in the air, the chemical reactivity of VOCs in Beijing was calculated. The results revealed that alkenes, accounting for only about 15% in the mixing ratio of VOCs, provide nearly 75% of the reactivity of ambient VOCs and the C4 to C5 alkenes were the major reactive species among the alkenes. The study of emission characteristics of various VOCs sources indicated that these alkenes are mainly from vehicle exhaust and gasoline evaporation. The reduction of alkene species in these two sources will be effective in photochemical pollution control in Beijing. 相似文献
3.
在青海湖不同盐度的四孔近代沉积物岩芯（Ｑ－１６Ａ，ＱＨ，ＱＥ和ＱＧ）（图１）抽提物支链和环烷烃组分中检出了非常丰富的Ｃ20，Ｃ25和Ｃ30高度支链类异戊二烯烯烃（ｈｉｇｈｌｙｂｒａｎｃｈｅｄｉｓｏｐｒｅｎｏｉｄａｌｋｅｎｅｓ），简称ＨＢＩ烯烃。这是在我国近代湖泊沉积物发现这类化合物的首次详细报导。由于Ｃ20，Ｃ25和Ｃ30ＨＢＩ烯烃比正构烷烃具有较强的抵抗生物降解的能力（ＲｏｂｓｏｎａｎｄＲｏｗｌａｎｄ，１９８８ｂ），因此，它们广泛分布于各种近代环境中，如湖泊、海洋和高盐环境的近代沉积物中（ＲｏｗｌａｎｄａｎｄＲｏｂｓｏｎ，１９９０）。并且，具有１～６个双键的Ｃ20，Ｃ25和Ｃ30烯烃经常是现代沉积物中丰富的烃类。最近在印度洋现代沉积物中又发现了一个新的具有７个双键的Ｃ35ＨＢＩ烯烃（Ｈｏｅｆｓｅｔａｌ，１９９５）。全饱和的Ｃ20（Ｉ，附图）、Ｃ25（Ⅱ，附图）和Ｃ30（Ⅲ，附图）ＨＢＩ烷烃已通过标样的合成确切地确定了它们的结构。在青海湖ＱＧ孔（尕海，咸水）和ＱＥ孔（耳海，淡水）抽提物中发现了Ｃ20单烯（１号峰，图２ａ）。Ｃ25烯烃（２号峰，图２ａ、２ｂ）和Ｃ30烯烃（主要是３号和８号峰，图２ａ、２ｂ）存在于所有四孔沉积物中。 相似文献
4.
The design and performance of a smog chamber for the study of photochemical reactions under simulated environmental conditions is described. The chamber is thermostated for aerosol experiments, and it comprises a gas chromatographic sample enrichment system suitable for monitoring hydrocarbons at the ppbv level. By irradiating NO
x
/alkane-mixtures rate constants for the reaction of OH radicals with n-alkanes are determined from n-pentane to n-hexadecane to be (k±2)/10–12 cm3 s–1=4.29±0.16, 6.2±0.6, 7.52 (reference value), 8.8±0.3, 10.2±0.3, 11.7±0.4, 13.7±0.3, 15.1±0.5, 17.5±0.6, 19.3±0.7, 22.3±1.0, and 25.0±1.3, respectively at 312 K. Rate constants, (k±2)/10–17 cm3 s–1, for the reaction of ozone with trans-2-butene (21.2±1.0), cis-3-methylpentene-(2) (47.2±1.7), cyclopentene (62.4±3.5), cyclohexene (7.8±0.5), cycloheptene (28.3±1.5), -pinene (8.6±1.3), and -pinene (1.4±0.2) are determined in the dark at 297 K using cis-2-butene (13.0) as reference standard. 相似文献
5.
Shark Bay is an 8000 sq. km shallow marine embayment on the western coast of Western Australia. The waters exhibit a well established salinity gradient from oceanic to hypersaline. The chemical assemblage of sediment hydrocarbons along the salinity gradient may be classified into two distinct chemogeographic types. Firstly, oceanic sediments contain n-alkanes and a suite of highly branched and branched/cyclic C25 alkenes. Hypersaline sediments are characterised by a high relative abundance of a C25H50 alkene together with an analogous C20H40 alkene and its parent C20H42 alkene (2,6,10-trimethyl-7-(3-methylbutyl)-dodecane). A pair of alkanes C21H42 and C22H44 increase in concentration and relative abundance with depth. The hydrocarbons of the hypersaline basins are found in only trace amounts in oceanic sediments. These chemical signals are overlain by further input indicative of the immediate biotic community. 相似文献
6.
Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology and Ecology 总被引：50，自引：0，他引：50
This overview compiles the actual knowledge of the biogenic emissions of some volatile organic compounds (VOCs), i.e., isoprene, terpenes, alkanes, alkenes, alcohols, esters, carbonyls, and acids. We discuss VOC biosynthesis, emission inventories, relations between emission and plant physiology as well as temperature and radiation, and ecophysiological functions. For isoprene and monoterpenes, an extended summary of standard emission factors, with data related to the plant genus and species, is included. The data compilation shows that we have quite a substantial knowledge of the emission of isoprene and monoterpenes, including emission rates, emission regulation, and biosynthesis. The situation is worse in the case of numerous other compounds (other VOCs or OVOCs) being emitted by the biosphere. This is reflected in the insufficient knowledge of emission rates and biological functions. Except for the terpenoids, only a limited number of studies of OVOCs are available; data are summarized for alkanes, alkenes, carbonyls, alcohols, acids, and esters. In addition to closing these gaps of knowledge, one of the major objectives for future VOC research is improving our knowledge of the fate of organic carbon in the atmosphere, ending up in oxidation products and/or as aerosol particles. 相似文献
7.
As part of a geochemical study of C25 and C30 biogenic alkenes in estuarine environments, distributions of these compounds in detritus and sediments collected from a New England salt marsh (Round Swamp on Conanicut Island in Narragansett Bay, Rhode Island) have been determined. The alkene assemblages detected, consisting primarily of four acyclic C25 dienes and trienes and a C30 bicyclic diene, qualitatively resemble those previously reported for other sediments in which anoxic conditions were prevalent. These similarities exist despite significant differences in the principal sources of sedimentary organic matter, suggesting that the occurrence of these specific alkenes is more likely associated with an in situ process common to anoxic environments than with a direct input from a specific source. Size fractionation (> 840 μm and < 840 μm to 1·2 μm) of marsh detritus revealed that the larger size fraction, consisting primarily of decaying Spartina debris, contains significant amounts of alkenes. This result, together with alkene subsurface profiles which show high surface concentrations decreasing to near-background levels by 20 cm, suggest that anaerobic bacteria are mediating in situ production of these compounds. Previous studies of bacterial hydrocarbons have not reported the presence of these C25 and C30 alkenes, although similar compounds have been isolated from several species of methanogenic bacteria. However, attempts to induce alkene synthesis by decomposing Spartina anaerobically in the laboratory were unsuccessful. In light of this result, the exact source of alkenes in marsh sediments remains uncertain. The absence from marsh sediments of other C25 alkenes whose sedimentary distributions had been previously correlated with the presence of marine (planktonic) organic matter implies the existence of different origins for structurally related constituents of this hydrocarbon series. 相似文献
8.
塔里木盆地侏罗系煤岩热模拟生物标志化合物特征研究 总被引：9，自引：0，他引：9
通过对塔里木盆地侏罗系煤岩热模拟实验研究,其结果表明生物标志化合物的组成不仅受其母质的控制,而且还受热成熟度和生油岩的岩性影响。这与生油岩中生物标志化合物先质在不同演化阶段释放出不同碳数生物标志化合物的强度有关。同时,在烃源岩热演化过程中时,不能仅依靠OEP值作为热成熟度的判识指标;正构烷烃峰型在整个热演化过程中呈现出双峰型,前驼峰的主峰碳主要集中在nC16-nC18,而后驼峰则随着模拟温度的升高逐渐增大;煤岩的ΣC21-/ΣC22+值与热模拟温度之间呈现出规律性变化;原始煤岩的Pr/Ph值随热模拟温度由250℃～550℃升高,总体呈逐渐降低的趋势。 相似文献
9.
Jaap S. Sinninghe Damst Stefan Schouten W. Irene C. Rijpstra Ellen C. Hopmans Harry Peletier Winfried W. C. Gieskes Jan A. J. Geenevasen 《Organic Geochemistry》1999,30(12):918
2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)-pentadeca-2,5E,9E,13-tetraene I possessing a C25 highly branched isoprenoid skeleton has been isolated from the marine diatom Rhizosolenia setigera and identified by 1H and 13C NMR spectroscopy. 相似文献
10.
E. J. Wraige S. T. Belt C. A. Lewis D. A. Cooke J. -M. Robert G. Mass S. J. Rowland 《Organic Geochemistry》1997,27(7-8)
The highly branched isoprenoid (HBI) alkenes of three batch cultures of the diatom Haslea ostrearia have been examined and the occurrence of C25 tri-, tetra- and pentaenes confirmed. Growth of cultures outside at ambient temperature, under natural sunlight, in May (6 days) and June (10 days) 1995 and monitoring of HBI concentrations in samples collected daily and stored frozen, revealed that in May greater concentrations of HBIs (ca 6500 fg cell−1) were produced than in June and at a much earlier stage of growth. Furthermore, in May the HBIs were more unsaturated (predominantly a tetraene rather than a triene). The reasons for these differences are at present unknown and future investigations of the effect of irradiance, temperature, salinity and other environmental variables are required. Such experiments may allow the various HBI distributions in the alga and in sediments to be better understood and, like some other polyunsaturated lipids, HBI alkenes may become useful environmental and palaeoenvironmental indicators. Two previously unreported alkenes, 2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)pentadec-2,5,9,13-ene (GC retention index, 2201DB-1) and 2,6,10,14-tetramethyl-7-(3-methylene pent-4-enyl)pentadec-2,5,9,13-ene (GC RI, 2248DB-1) from a batch culture of Haslea ostrearia grown in October/November 1993 and stored frozen for over a year, have also been isolated and characterised by 13C and 1H NMR, epoxide derivatisation and mass spectrometry. Such structural characterisation studies of HBI alkenes should also aid our understanding of the geochemical fate of these widely distributed hydrocarbons. 相似文献