Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

On the growth of maars and diatremes and its relevance to the formation of tuff rings

Small and large maars exist associated with small and large diatremes, respectively, their subsurface feeder structures. The problem of size and growth of maar-diatreme volcanoes is discussed from a phreatomagmatic point of view from field data, some geophysical data, and short-lived historic maar eruptions. A hydrostatic pressure barrier of usually about 20–30 bars is assumed to control the maximum depth level of explosive magma/groundwater interactions. Similar to the situation in submarine and subglacial volcanism, initial maar-forming water vapour explosions are therefore assumed to occur at shallow depth and to produce a small maar with a shallow diatreme. Because of limited availability of groundwater and ejection of groundwater in the form of steam, the confining pressure barrier is displaced downward. Consequently, water vapour explosions can take place at consecutively deeper levels with the result that the diatreme penetrates downward and grows in size. Since maars are collapse craters resulting from ejection of wallrocks fragmented by water vapour explosions at the level of the diatreme root zone, downward penetration of a diatreme not only results in increase in size of a diatreme but also in increase in size of the overlying maar. As availability of groundwater in limited amounts controls formation of diatremes and their downward penetration, lack of groundwater enables magma to rise within a diatreme and to form a scoria cone or lava lake within the maar, as is frequently found in volcanic fields such as the Eifel area in Germany. In contrast, availability of large amounts of water in near surface environments such as shallow marine, lake, water-rich coastal plains, or water-rich fluviatile gravel beds prevents formation of maars and deep diatremes but causes formation of tuff rings.     

External ballistic of volcanic explosions

In order to determine the kinetic energy of an explosion it is necessary to know the initial velocities of ejected fragments. Calculations of initial velocities made earlier with few exceptions did not take into account the resistance of the air and therefore, greatly underestimated the initial velocities, and consequently the energy of the explosions. A solution of the inverse problem of ballistics which takes into account air resistance makes it possible to find precise values of initial velocities of ejection, determined from the distance of ejected fragments and their ballistic coefficients. The method makes it possible to determine the kinetic energy of explosions for eruptions which were not directly observed. It is shown that the velocity field in volcanic explosions is not spherical,i.e. the velocities of ejection of fragments differ markedly in different directions. Accordingly, the maximum distance of ejection of fragments depends not only on the initial angle of ejection, but also on the character of distribution of initial velocities and the ballistic coefficients of the fragments. For fragments with diameters of 40 cm to 2 m the maximum distance of ejection is realized in the case of angles of ejection of 30–36°. For smaller fragments the optimal angles of ejection are still smaller. The ballistics of explosive eruptions of the volcanoes Asama, Arenal, and Shiveluch are considered.     

Chemical composition of lunar meteorites and the lunar crust

The paper presents the first analyses of major and trace elements in 19 lunar meteorites newly found in Oman. These and literature data were used to assay the composition of highland, mare, and transitional (highland-mare interface) regions of the lunar surface. The databank used in the research comprises data on 44 meteorites weighing 11 kg in total, which likely represent 26 individual falls. Our data demonstrate that the lunar highland crust should be richer in Ca and Al but poorer in mafic and incompatible elements than it was thought based on studying lunar samples and the first orbital data. The Ir concentration in the highland crust and the analysis of lunar crater population suggest that most lunar impactites were formed by a single major impact event, which predetermined the geochemical characteristics of these rocks. Lunar mare regions should be dominated by low-Ti basalts, which are, however, enriched in LREEs compared to those sampled by lunar missions. The typical material of mare-highland interface zones can contain KREEP and magnesian VLT basalts. The composition of the lunar highland crust deduced from the chemistry of lunar meteorites does not contradict the model of the lunar magma ocean, but the average composition of lunar mare meteorites is inconsistent with this concept and suggests assimilation of KREEP material by basaltic magmas. The newly obtained evaluations of the composition of the highland crust confirm that the Moon can be enriched in refractory elements and depleted in volatile and siderophile elements.     

Foreign meteoritic material of howardites and polymict eucrites

Howardites and polymict eucrites are fragments of regolith breccias ejected from the surface of a differentiated (eucritic) parent body, perhaps, of the asteroid Vesta. The first data are presented demonstrating that howardites contain, along with foreign fragments of carbonaceous chondrites, also fragments of ordinary chondrites, enstatite meteorites, ureilites, and mesosiderites. The proportions of these types of foreign meteoritic fragments in howardites and polymict eucrites are the same as in the population of cosmic dust particles obtained from Antarctic and Greenland ice. The concentrations of siderophile elements in howardites and polymict eucrites are not correlated with the contents of foreign meteoritic particles. It is reasonable to believe that cosmogenic siderophile elements are concentrated in howardites and polymict eucrites mostly in submicrometer-sized particles that cannot be examined mineralogically. The analysis of the crater population of the asteroid Vesta indicates that the flux of chondritic material to the surface of this asteroid should have been three orders of magnitude higher than the modern meteoritic flux and have been comparable with the flux to the moon’s surface during its intense meteoritic bombardment. This provides support for the earlier idea about a higher meteoritic activity in the solar system as a whole at approximately 4 Ga. The lithification of the regolith (into regolith breccia) of the asteroid Vesta occurred then under the effect of thermal metamorphism in the blanket of crater ejecta. Thus, meteorite fragments included in howardites provide record of the qualitative composition of the ancient meteorite flux, which was analogous to that of the modern flux at the Earth surface.     

The Spatial Characteristics of a Line and Their Application to Line Simplification

This paper discusses the spatial knowledge related to a line,and the characteristic points of lines is detected.According to the requirements of line generalization,new algorithms for identifying characteristic line points are presented.These characteristic points are used to improve the algorithms of line generalization.An algorithm for identifying bends is shown.In this paper,improved algorithms based on those by Douglas-Peucker,Visvalingam and Whyatt are shown.In this test,the progressive process of line generalization is emphasized.     

Collapse structures in the Permian of the Saar-Nahe area,Southwest Germany

Volcanic breccias near an intrusive rhyolite dome in the Permian Saar-Nahe trough of southwest Germany have been identified as complex pipe-like subsidence-structures occupying the site and immediate neighbourhood of explosive volcanoes.At the Rödern, at first fine-grained, well-bedded and later coarser-grained and poorly bedded pyroclastic materials were deposited on top of a lava flow that formed the regional surface. Collapse along a ringfault with differential subsidence of 500 to 700 m produced a saucer-shaped structure in which steeply dipping pyroclastic beds still overlie the lava flow on which they were originally deposited. In the actual feeder, large blocks of country-rock subsided individually prior to wholesale subsidence of the entire feeder-content. Intrusion of a high alumina quartz tholeiite into the pyroclastic beds terminated the activity.The Hirschberg structure has essentially the same history, but is more fragmented. Subsidences vary between 150 and 260 m. Intrusion of petrographically and chemically similar basalt took place mainly near the margin of the ringfault.Three smaller structures also contain bedded pyroclastic deposits that subsided approximately 600, 1100, and 1400 m. The surface expressions of these five collapse structures are assumed to have been small collapse-calderas with diameters of several 100 m. to 1.5 km.

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Zusammenfassung Vulkanische Brekzien im Rotliegenden der Umgebung des Donnersberges in der Saar-Nahe-Senke/Pfalz liegen in Einbruchsstrukturen vor, die den ursprünglichen Schlot und seine unmittelbare Umgebung einnehmen.Am Rödern wurden ehemals auf einer Olivin-Basalt-Lava feinkörnige und spÄter grobkörnige Pyroclastica abgelagert. Einbruch an einem Ringbruch und differentielle Absenkung zwischen 500 und 700 m führte zur Anlage der trichterförmigen Struktur der geschichteten Pyroclastica. Trotz der Absenkung liegen sie immer noch mit ungestörtem Kontakt, jedoch nun steil einfallend, dem mitabgesenkten Olivin-Basalt auf.Am ursprünglichen Schlot ist Absenkung einzelner gro\er Nebengesteinsschollen und nachfolgend des gesamten Schlotinhaltes festzustellen. Die vulkanische AktivitÄt wurde durch Intrusion eines high-alumina Quarz-Tholeiites abgeschlossen.Der Hirschberg weist im wesentlichen die gleiche Struktur und Entwicklungsgeschichte auf, ist jedoch in mehrere Schollen untergliedert. Die BetrÄge der differentiellen Absenkung liegen zwischen 150 und 260 m. Infolge der Zerblockung innerhalb des Ringbruches intrudierte Basalt vorwiegend im Bereich der Verwerfungen, also am Ringbruch und zwischen einzelnen Schollen.Drei kleinere Strukturen enthalten ebenfalls geschichtete Pyroclastica und weisen maximale AbsenkungsbetrÄge von 600, 1100 und 1400 m auf.Im Bereich der ursprünglichen ErdoberflÄche müssen infolge der Einbrüche tiefe Krater vorgelegen haben, die als kleine Einbruchscalderen bezeichnet werden können.

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Résumé Aux alentours du «Donnersberg» dans la «Saar-Nahe-Senke» (Palatinat, Sudouest de l'Allemagne) des brèches volcaniques du Permien inférieur sont conservées à l'intérieur de structures d'effondrement. Celles-ci se trouvent au lieu mÊme de la cheminée originale et à ses alentours immédiats.Une de ces structures, le «Rödern», est caractérisée par des dépÔts pyroclastiques — fins à la base et plus grenus vers le sommet — couvrant des laves basaltiques à olivine. L'effondrement à l'intérieur d'une faille annulaire et une subsidence différentielle de 500 à 700 m ont eu comme résultat une structure rappelant un entonnoir. Les dépÔts pyroclastiques stratifiés reposent, quoiqu'avec un pendage fort, toujours en superposition normale et non faillés sur les basaltes à olivine qui eux aussi ont été affectés par la subsidence.A la cheminée mÊme on constate l'affaissement de grands panneaux de roches encaissantes suivi de l'effondrement de tout le remplissage de cheminée. L'activité s'achève par des venues d'une «high-alumina Quarz-Tholeiite».Le «Hirschberg», dont la structure et l'évolution ressemblent à celles du «Rödern», est caractérisé par une fragmentation du bloc effondré. L'affaissement de différents panneaux varie entre 150 et 260 m. Suite à la fragmentation de nouvelles venues basaltiques prennent place, soit le long de la faille annulaire, soit le long des failles entre les differents panneaux.Des dépÔts pyroclastiques stratifiés sont conservés encore dans trois autres structures plus petites. L'affaissement à l'intérieur de ces structures est de 600, 1100 et 1400 m au maximumQuant à la morphologie de la région après l'effondrement, on peut supposer qu'elle était caractérisée par l'existence de cratères profonds (caldères d'effondrement).

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, Donnersberg ( -, ) , . - Rödern - , . - 500–700 , . , .- , . . - Hirschberg, , , . 150–260 . , . . . - ; 600, 1100 1400 . - , , , , .

     

Origin and crystallization history of Permian tholeiites from the Saar-Nahe trough,SW Germany

The Hirschberg and Rödern diatremes, within the Permian Saar-Nahe trough, SW Germany, are composed chiefly of basaltic tuffs, with associated small intrusions of K-rich tholeiites. Several tholeiite bodies carry 2–20 mm crystals of magnesian clinopyroxene and orthopyroxene, the latter containing up to 5.5% Al₂O₃ and often extensively resorbed and rimmed by fine-grained olivine and clinopyroxene. Experimental duplication of these pyroxenes has been achieved under conditions of Pload=6–10 kb, T=1280–1080° C and 2–4 wt.-% H₂O, confirming that they represent a rare occurence of high pressure phenocrysts in tholeiitic basalts.These conditions of pyroxene crystallization also place constraints on processes of magma generation, indicating that the tholeiites originated by partial melting of unusually hydrous peridotite mantle (0.4–0.8% H₂O) beneath a relatively thin continental crust (maximum thickness approximately 30 km). Water present in the mantle at the site of magma generation may have been derived from the dehydration of oceanic lithosphere prior to the formation of the Saar-Nahe trough. This lithosphere probably underwent subduction at the margin of the Palaeozoic European continent during the Hercynian cycle of sedimentation, andesitic volcanism and folding. The termination of this cycle was followed by a period of basin-range type tensional faulting, leading to the formation of the Permian basins of present-day Central Europe, and widespread bimodal basalt/rhyolite volcanism.