In-situ Measurements of Tropospheric Hydroxyl Radicals by Folded Long-Path Laser Absorption During the Field Campaign POPCORN   总被引：1，自引：0，他引：1  

Uwe Brandenburger  Theo Brauers  Hans-Peter Dorn  Martin Hausmann  Dieter H. Ehhalt 《Journal of Atmospheric Chemistry》1998,31(1-2):181-204

Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.  相似文献   

Gaseous and Particulate Oxidized and Reduced Nitrogen Species in the Atmospheric Boundary Layer in Scandinavia in Spring     

Asgeir Sorteberg  Øystein Hov  Sverre Solberg  Kjetil Tørseth  Hans Areskoug  Martin Ferm  Kit Granby  Heikki Lättilä  Karin Persson  David Simpson 《Journal of Atmospheric Chemistry》1998,30(2):241-271

Observations of the concentration of several nitrogen containing compounds at five rural Scandinavian sites during March–June 1993 are reported. Total nitrate (NO ₃ ^- + HNO₃) and total ammonium (NH ₄ ⁺ + NH₃) were measured by denuder and filter pack. In general the methods agree well. At all sites the particulate fraction dominated, with the largest fraction of NO ₃ ^- and the lowest of NH ₄ ⁺ at the sites which were closest to the emission sources. The fraction of NO ₃ ^- of total nitrate increased with increasing NO₂ concentrations, indicating that the nighttime conversion of NO₂ to NO ₃ ^- is an important route of formation for NO ₃ ^- . A positive correlation was found between HNO₃ and O₃ in June at all sites, while no correlation was found early in the spring. Model calculations were made with a lagrangian boundary layer photooxidant model for the whole period, and compared to the measured concentrations. The calculated ratio between mean observed and modelled daily maximum concentrations of ozone over the measurement period were within +/–10% at all sites. The models ability to describe the daily ozone maximum concentration was satisfactory with an average deviation of 19–22% from the observed concentrations. HNO₃ was underestimated by over 50% at all sites except the one closest to the emission sources. The correlation between modelled and observed concentrations was generally best for the sites with shortest transport distance from the sources of emission.  相似文献   

Kornerupine parageneses in whiteschists and other magnesian rocks: is kornerupine + talc a high-pressure assemblage equivalent to tourmaline + orthoamphibole?     

Edward S. Grew  Nikolai N. Pertsev  Stanislav Vrána  Martin G. Yates  Charles K. Shearer  Michael Wiedenbeck 《Contributions to Mineralogy and Petrology》1998,131(1):22-38

Kornerupine, (□,Fe,Mg)(Mg,Fe,Al)₉(Si,Al,B)₅ (O,OH,F)₂₂, has been reported with talc in rocks from six localities worldwide, but only at Chilapila Hill in the Lufilian Arc, Zambia do textural relationships imply that kornerupine (Krn) equilibrated with talc (Tlc) during a prograde metamorphic event at T≈ 640 °C, P≈ 13 kbar; a prograde Krn + Tlc assemblage has also been reported from Mautia Hill, Tanzania (P ≤ 13 kbar). In order to estimate possible constraints on the stability range for the kornerupine + talc paragenesis in nature, we constructed a P-T diagram in the model system MgO-Al₂O₃-SiO₂-H₂O (MASH) for seven phases quartz (Qtz), B-free kornerupine sensu stricto, anthophyllite (Ath), chlorite (Chl), cordierite (Crd), kyanite (Ky), and talc. The minimum pressure for Krn + Tlc + Ky stability in MASH is close to that for Ky + Tlc stability, i.e., 6–8 kbar, at T≤ 780 °C. However, in the natural system, B₂O₃ and Na₂O are major constituents in Krn and orthoamphibole (Oam), respectively, and dravitic tourmaline (Tur) is widespread. The critical assemblage alternative to Krn + Tlc in nature is Tur + Oam. The upper pressure limit of Tur + Ath is determined by the upper pressure for anthophyllite: 7.7–10.5 kbar at 682–794 °C in the MgO-SiO₂-H₂O system (Chernosky et al. 1985, Am Mineral 70:223–236), and is undoubtedly higher in the presence of Na₂O, CaO, and Al₂O₃. At three of the six localities, talc is a retrograde phase; nonetheless, it possibly equilibrated with kornerupine on the retrograde path or during a later metamorphic event at P-T conditions appropriate for Ky + Tlc. At the sixth locality (Mulvoj, southwestern Pamir Mountains, Tajikistan), Krn is found in the same thin section as talc and kyanite and all three minerals formed during a prograde metamorphic event at T≥ 650 °C, P near 7 kbar. However, Krn is restricted to a lens 4 to 6 mm thick of phlogopite + anthophyllite + Tur and it does not touch either talc or kyanite. A reaction relating the Mulvoj and Chilapila Hill (Krn + Tlc + Ky + Qtz + Tur) parageneses is calculated from compositions in the Mulvoj rock to be 0.40Tur + 2.55Ath + 1.33H₂O + 0.27F = Krn + 2.16Tlc + 0.36B₂O₃ + 0.02Rutile + 0.19Na₂O + 0.17CaO. Given the difference in metamorphic pressures estimated for Mulvoj and Chilapila Hill, Krn + Tlc is inferred to be favored by increasing pressure as well as by low Na₂O and CaO contents. Some FeO, F, Fe₂O₃, and BeO are present in measurable amounts in at least one of the phases in the Mulvoj and Chilapila Hill whiteschists (e.g., Krn contains 0.24–0.67 wt% BeO), but the effect of these constituents is subordinate to that of Na₂O, CaO and B₂O₃. The Krn + Tlc could be a more important assemblage in B-bearing whiteschists than has been reported to date, particularly at pressures where orthoamphibole is no longer stable. Received: 21 April 1997 / Accepted: 13 October 1997  相似文献   

Open system alkaline magmatism in northern Kenya: evidence from U-series disequilibria and radiogenic isotopes   总被引：4，自引：0，他引：4  

Stuart Black  Ray Macdonald  Barbara A. Barreiro  Peter N. Dunkley  Martin Smith 《Contributions to Mineralogy and Petrology》1998,131(4):364-378

U-series activity ratios, Sr-Nd-Pb isotopic ratios and major and trace element compositions have been determined on young basalts (<10 ka) and trachytes from the volcano Emuruangogolak in the Kenya Rift Valley. The basalts are mildly alkaline and are associated with small volumes of hawaiite. The mafic rocks are characterised by high (²³⁰Th/²³²Th) (≥1.06) with low (²³⁸U/²³⁰Th) ratios (≤0.72). They have variable incompatible trace element ratios (e.g. Zr/Nb, Ba/Zr), indicating that they represent a number of magmatic lineages. The trachytes, which comprise both comenditic and pantelleritic varieties, have significantly lower (²³⁰Th/²³²Th) ratios than the basalts, with clear differences between pantelleritic and comenditic types. The (²³⁸U/²³⁰Th) ratios in the pantellerites range from less, to greater, than 1. The variations in composition and isotopic diversity must represent different sources for the trachytes. Internal isochrons for the trachytes give U-Th ages of 14 to 40 ka, similar to single crystal laser fusion ⁴⁰Ar/³⁹Ar ages from sanidine phenocrysts (16–38 ka) for the same rocks. Post-crystallisation residence times of the trachytes were very short, implying relatively rapid movement of trachyte from magma chamber to the surface. Variations in the initial (²³⁰Th/²³²Th)₀ ratios (0.69–1.14) of both basalts and trachytes indicate that Emuruangogolak has erupted a large range of isotopically diverse magmas over a very short period of time (38 ka), from conduits closely spaced around the summit of the volcano. Received: 29 May 1996 / Accepted: 24 November 1997  相似文献   

Effect of artificial maturation on carbazole distributions, as revealed by the hydrous pyrolysis of an organic-sulphur-rich source rock (Ghareb Formation, Jordan)     

Heather Clegg  Brian Horsfield  Heinz Wilkes  Jaap Sinninghe Damst  Martin P. Koopmans 《Organic Geochemistry》1998,29(8):1953-1960

Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% R_r and for Posidonia Shale at >0.88% R_r). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C₁- and C₂-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C₂-carbazoles, are not easy to interpret.  相似文献   

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis     

Anke Putschew  Christine Schaeffer-Reiss  Philippe Schaeffer  Martin P Koopmans  Jan W de Leeuw  Michael D Lewan  Jaap S Sinninghe Damsté  James R Maxwell 《Organic Geochemistry》1998,29(8):1875-1890

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.  相似文献   

Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures     

Eva R. Myers  Volker Heine  Martin T. Dove 《Physics and Chemistry of Minerals》1998,25(6):457-464

The main driving force behind Al/Si ordering in tetrahedral framework aluminosilicates is nearest-neighbour Al/Al avoidance. Computer simulation is used to explore the direct consequences of such Al/Al avoidance. The main result is that the order-disorder transition temperature T _c falls dramatically as the concentration x of Al in the structure is reduced, and if the only interactions are those associated with nearest-neighbour Al/Al avoidance, T _c becomes zero for x less than some critical value x _c , where x _c =0.31 for the feldspar framework and x _c =0.34 for cordierite. Also a large degree of short range order is found above T _c . Both results differ radically from the standard Bragg-Williams model. Plots of entropy and enthalpy of ordering are given as functions of x and T, which may be used to interpret experimental data or for extrapolation into ranges of x and T inaccessible to experiment. Received: 14 May 1997 / Revised, accepted: 2 June 1997  相似文献   

Venus-intercepting meteoroid streams     

Martin Beech 《Monthly notices of the Royal Astronomical Society》1998,294(2):259-264

This study is motivated by the possibility of determining the large-body meteoroid flux at the orbit of Venus. Towards this end, we attempt to estimate the times at which enhanced meteoric activity might be observed in the planet's atmosphere. While a number of meteoroid streams are identified as satisfying common Earth and Venus intercept conditions, it is not clear from the Earth-observed data if these streams contain large-body meteoroids. A subset of the Taurid Complex objects may produce fireball-rich meteor showers on Venus. A total of 11 short-period, periodic comets and 46 near-Earth asteroids approach the orbit of Venus to within 0.1 au, and these objects may have associated meteoroid streams. Comets 27P/Crommelin and 7P/Pons–Winnecke are identified as candidate parents to possible periodic meteor showers at the orbit of Venus.  相似文献   

The Parkes Southern Pulsar Survey — III. Timing of long-period pulsars     

D'Amico  Stappers  Bailes  Martin  Bell  Lyne  & Manchester 《Monthly notices of the Royal Astronomical Society》1998,297(1):28-40

The Parkes survey of the entire southern sky for millisecond and other low-luminosity pulsars has now been completed. The survey system and initial results were described by Manchester et al. and the final results and population studies are described by Lyne et al. A total of 298 pulsars were detected, including 101 new discoveries of which 17 were millisecond pulsars. Here we report on timing observations at Parkes and Jodrell Bank of the 84 long-period (non-millisecond) pulsars discovered in the survey, including timing solutions for 78 of them. Pulse profiles and arrival times were obtained at several different frequencies over intervals of more than a year, yielding a position, period, period derivative and dispersion measure for each pulsar. Pulse profiles at frequencies near 400 MHz and 600 or 1400 MHz are presented for most of the observed pulsars. Significant timing noise was detected for five pulsars and a glitch was observed in the period of PSR J1123–6259.  相似文献   

Star formation in the circumnuclear environment of NGC 1068     

Richard I. Davies  Hajime Sugai  & Martin J. Ward 《Monthly notices of the Royal Astronomical Society》1998,300(2):388-396

We present near-infrared emission-line images of the circumnuclear ring in NGC 1068. We have measured the Brγ fluxes in a number of star-forming complexes and derived the extinction for each of these by comparison with Hα. We investigate the star-forming histories of these regions and find that a short burst of star formation occurred coevally throughout the ring within the last 30–40 Myr, and perhaps as recently as 4–7 Myr ago. The 1–0 S(1) flux and S(1)/Brγ ratios indicate that as well as fluorescence, shock-excited H₂ emission contributes to the total flux. There is excess H₂ flux to the north-west where the ionization cone crosses the ring, and we show that it is possible that the non-stellar continuum from the Seyfert nucleus which produces the high-excitation lines could also be causing fluorescence at the edges of molecular clouds in the ring. The nuclear 1–0 S(1) is more extended than previously realized but only along the bar's major axis, and we consider mechanisms for its excitation.  相似文献