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11.
A full-dimensional quantum dynamics simulation of a hydrogen atom reacting with methane on an accurate ab initio potential energy surface is reported. Based on first-principles theory, thermal rate constants are predicted with an accuracy comparable to (or even exceeding) experimental precision. The theoretical prediction is within the range of the significantly varied experimental rate constants reported by different groups. This level of accuracy has previously been achieved only for smaller, three-or four-atom reactive systems. Comparison with classical transition state theory confirms the importance of quantum mechanical tunneling for the rate constant below 400 kelvin. 相似文献
12.
13.
Wozny C Kivi A Lehmann TN Dehnicke C Heinemann U Behr J 《Science (New York, N.Y.)》2003,301(5632):463; author reply 463
14.
Keller HU Jorda L Küppers M Gutierrez PJ Hviid SF Knollenberg J Lara LM Sierks H Barbieri C Lamy P Rickman H Rodrigo R 《Science (New York, N.Y.)》2005,310(5746):281-283
The OSIRIS cameras (optical, spectroscopic, and infrared remote imaging system) onboard the European Space Agency's Rosetta spacecraft observed comet 9P/Tempel 1 for 17 days continuously around the time of NASA's Deep Impact mission. The cyanide-to-water production ratio was slightly enhanced in the impact cloud, compared with that of normal comet activity. Dust particles were flowing outward in the coma at >160 meters per second, accelerated by the gas. The slope of the brightness increase showed a dip about 200 seconds after the impact. Dust Afrho values before and long after the impact confirm the slight decrease of cometary activity. The dust-to-water mass ratio was much larger than 1. 相似文献
15.
Spatial variability of humus layer (O layer) thicknesses can have important impacts upon soil water dynamics, nutrient storage and availability, as well as plant growth. The purpose of the present study was to elucidate the impact of forest‐transformation practices on the spatial variability of O layer thicknesses. The study focused on the Kahlenberg forest area (NE Germany) with stands of Scots pine (Pinus sylvestris) and European beech (Fagus sylvatica) of different age structures that form a transformation chronosequence from pure Scots pine stands towards pure European beech stands. Topsoil profiles including both, the O layer and the uppermost humic mineral soil horizon were excavated at intervals of 0.4 m along 15–20 m long transects, and spatial variability of O layer thicknesses was quantified by variogram analysis. The correlation lengths of total O layer thickness increased in the sequence consisting of pure pine stand (3.1 m) → older mixed stand (3.7 m) → pure beech stand (4.5 m), with the exception of the younger mixed stand, for which no correlation lengths of total O layer thickness could be determined. The degree of spatial correlation, i.e., the percentage of the total variance which can be described by variograms, was highest for the two monospecies stands, whereas this percentage was distinctly lower for the two mixed stands. A similar minimum for the two mixed stands was observed for the correlation lengths of the Oh horizon. These results suggest that the spatial structures of forest‐transformation stands may be interpreted in terms of a disturbance (in the form of the underplanting of beech trees). After this disturbance, the forest ecosystem requires at least 100 y to again reach relative equilibrium. These findings are in line with the results of other soil‐related investigations at these sites. 相似文献
16.
Soils under intensive cultivation have altered due to water erosion. This study was conducted to determine whether soil organic matter (SOM) composition of the colluvial source (Ap horizons) differs from the colluvial sink (M horizons). The SOM of a sandy Catena with erodic Cambisols and colluvic soils (Colluvisols) in Schleswig-Holstein, Northwest Germany, was investigated. A wet chemical analysis was combined with CPMAS 13C-NMR spectroscopy. In one case a significant correlation between the SOM composition of the Ap horizon of the erodic Cambisol and the M horizon of the Colluvisol was high (r2 = 0.904-), whereas the correlation for the other set was much weaker (r2 = 0.640*). Two possible paths of pedogenesis are discussed. About 70% of the SOM of the colluvial source is decomposed during translocation or after deposition. A selective preservation or new formation of humins in the M material is probable. These humins contain, obviously, large amounts of polysaccharides, which were not detected by the wet chemical analysis. Further investigations of colluvic and erodic soils are necessary in order to specify the SOM quality and its possible modification due to soil translocation and accumulation. 相似文献
17.
Jun M Shao Y Ho CT Koetter U Lech S 《Journal of agricultural and food chemistry》2003,51(21):6340-6346
The degradation profile of glucosamine bulk form stressed at 100 degrees C for 2 h in an aqueous solution was studied. Column chromatography of acetylated product mixture led to isolation of two pure compounds (1b and 2b) and a mixture of at least three isomers (3b). 1a and 2a were identified as 5-(hydroxymethyl)-2-furaldehyde (5-HMF) and 2-(tetrahydroxybutyl)-5-(3',4'-dihydroxy-1'-trans-butenyl)pyrazine, respectively, by utilizing a variety of analytical techniques, such as GC-MS, LC-MS, on-line UV spectrum, (1)H and (13)C NMR, and DEPT, as well as (1)H-(1)H COSY. 3a was identified as 2-(tetrahydroxybutyl)-5-(2',3',4'-trihydroxybutyl)pyrazine, commonly known as deoxyfructosazine. In addition, glucosamine solid dosage form was exposed to 40 degrees C/75% relative humility for 10 weeks. Methanol extract of glucosamine solid dosage form was analyzed after acetylation by LC-MS, resulting in degradants 3b and 4b. 3a and 4a were, therefore, determined as deoxyfructosazine and 2,5-bis(tetrahydroxybutyl)pyrazine (fructosazine), respectively. Furthermore, the mechanisms of formation of identified degradation products are proposed and briefly discussed. 相似文献
18.
Kappelmeyer Uwe Kuschk Peter Stottmeister Ulrich 《Water, air, and soil pollution》2003,147(1-4):317-330
Chemodenitrification is of importance in both soils and the treatment of some types of wastewater. During model experiments,the impact of various conditions, such as pH and especially artificial humic matter and oxygen on this process was studied to build upkinetic models. The chemodenitrification rate decreased due to the ongoingautoxidation/polymerization of hydroquinone to artificial humic matterfrom 11.02 μg (L h)-1 after 7 days autoxidation to 5.38 μg (L h)-1 after 14 days at pH 4 under aerobic conditionsand an initial nitrite concentration of 250 μg L-1. At the same pH,with the same nitrite concentration, and in the presence of Roth humic matter(2 mg L-1) under aerobic conditions, the chemodenitrification rate was0.73 μg (L h)-1, whereas under anaerobic conditions itwas considerably higher (2.88 μg (L h)-1). In anothermodel experiment, it was shown that the amount of nitrite incorporated into the artificial humic matter was less then 1%. Further, it was found that the main reaction product of chemodenitrification is NO. 相似文献
19.
In Schleswig-Holstein, F.R.G., two typical soil associations from loamy boulder marl and loamy pleistocene sands were mapped and ecologically characterized in order to show the necessity of an adequate classification of Colluvic Cumulic Anthrosols (Colluvisols). More than 50% of the original soils have been altered by erosion. The depth of the colluvic wM horizon ranges between 10 cm and more than 100 cm. The amounts of soil organic matter and plant available nutrients are much higher in the Colluvisols than in the haplic soils. Soil classification does not deal with all these aspects with regard to mapping of colluvic soils. In the German soil classification adequate and ecologically significant definitions and instructions of the nomenclature of colluvic soils are not available. Therefore, a proposal is presented to classify colluvic soils. In addition the threshold value of 0.6% soil organic matter in sandy parent material is too low in order to distinguish a Bv from a M horizon; 1.0% would be a more acceptable value. It would be necessary to investigate yield on erodic, non-erodic and colluvic soils in order to determine the effect of erosion and accumulation on crop yield. 相似文献
20.
Sewenig S Bullinger D Hener U Mosandl A 《Journal of agricultural and food chemistry》2005,53(4):838-844
A new coupling system of GC-GC, connected via a Multi Column Switching Device MCS2 for measuring isotope ratios, is introduced. By means of several standard substances the precise and accurate measurement of isotopic values is proved. First applications concerning the authentication of raspberry aroma compounds are established. Consequently, the combination of constant flow multidimensional gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry (MDGC-C/P-IRMS) is applied to the authenticity assessment of (E)-alpha(beta)-ionone from six different raspberry cultivars. Furthermore, 12 commercially available raspberry products and samples of (E)-alpha(beta)-ionone, some declared to be natural, are investigated. delta(2)Eta(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values of (E)-alpha(beta)-ionone are determined, and characteristic authenticity ranges were concluded from raspberries by correlation of both delta(2)Eta(V)(-)(SMOW) and delta(13)C( V)(-)(PDB) values. The results are correlated with the determination of enantiomeric purities of (E)-alpha-ionone, using stir bar sorptive extraction enantio-multidimensional gas chromatography mass spectrometry (SBSE-enantio-MDGC-MS). 相似文献