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31.
Richard Winterhalter Peter Neeb Dirk Grossmann Antje Kolloff Osamu Horie Geert Moortgat 《Journal of Atmospheric Chemistry》2000,35(2):165-197
Gas phase ozonolysis of -pinene was performedin a 570 l static reactor at 730 Torr and 296 K insynthetic air and the products were analysed by acombination of gas phase FTIR spectroscopy, HPLC andIC analyses of gas phase and aerosol samples,respectively. The reaction mechanism was investigatedby adding HCHO, HCOOH and H2O as Criegeeintermediate scavenger and cyclohexane as OH radicalscavenger. Main identified products (yields inparentheses) in the presence of cyclohexane as OHradical scavenger were HCHO (0.65 ± 0.04),nopinone (0.16 ± 0.04), 3-hydroxy-nopinone (0.15± 0.05), CO2 (0.20 ± 0.04), CO (0.030± 0.002), HCOOH (0.020 ± 0.002), the secondaryozonide of -pinene (0.16 ± 0.05), andcis-pinic acid (0.02 ± 0.01). The decompositionof the primary ozonide was found to yieldpredominantly the excited C9-Criegee intermediateand HCHO (0.84 ± 0.04) and to a minor extent theexcited CH2OO intermediate and nopinone (0.16± 0.04). Roughly 40% of the excitedC9-Criegee intermediate becomes stabilised andcould be shown to react with HCHO, HCOOH and H2O. The atmospherically important reaction of thestabilised C9-Criegee intermediate with H2Owas found to result in a nopinone increase of (0.35± 0.05) and in the formation of H2O2(0.24 ± 0.03). Based on the observed products,the unimolecular decomposition/isomerisationchannels of the C9-Criegee intermediate arediscussed in terms of the hydroperoxide and esterchannels. Subsequent reactions of the nopinonylradical, formed in the hydroperoxide channel, lead tomajor products like 3-hydroxy-nopinone but also tominor products like cis-pinic acid. A mechanismfor the formation of this dicarboxylic acid isproposed and its possible role in aerosol formationprocesses discussed. 相似文献
32.
Alexander Müller Dirk Flottmann Wolfgang Schulz Wolfram Seitz Walter H. Weber 《洁净——土壤、空气、水》2007,35(4):329-338
The development of instrumental analytics such as the LC-MS/MS has made it possible to quickly determine many component concentrations in a single chromatogram. However, the validation of such multi-methods needs new strategies for robustness and optimization. Statistical execution of analytical tests is one tool that can be utilized to meet this requirement. A Central Composite Design (CCD) was utilized for the validation of an LC-MS/MS multi-method for 84 analytes. The experimental design includes six design variables and two non-design variables (response variables). Concentration, ionization temperature, dwell time, gradient, flow (of eluent), and spraying/curtain gas (continuous design variables) were varied on five different levels; the whole design encompassed 91 runs. To investigate the robustness of a LC-MS/MS method both peak sensitivity and chromatographic separation had to be verified. Therefore, two non-design variables were necessary. The distribution of the peaks over analysis time was applied to describe the quality of the chromatographic separation. The sensitivity was described with the signal to noise ratio (S/N). The evaluation of the measured data was accomplished with the Analysis of Variance (ANOVA) and the Response Surface Methodology (RSM). Three main effects (concentration, ionization temperature, dwell time) and no significant interaction effect were found for the response variable “S/N”. The variables of concentration, ionization temperature, and dwell time had no significant effects for the response variable “S/N”. The ANOVA of the response variable chromatographic separation abandoned no significant effects as well. Therefore, robustness of the method can be guaranteed for all non significant design variables. 相似文献
33.
The solubility of KFe(CrO4)2·2H2O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO4)2·2H2O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log KSP for the reaction
相似文献
34.
Matthias Zillmer Boris Kashtan & Dirk Gajewski 《Geophysical Journal International》1998,132(3):643-653
Wave propagation in weakly anisotropic inhomogeneous media is studied by the quasi-isotropic approximation of ray theory. The approach is based on the ray-tracing and dynamic ray-tracing differential equations for an isotropic background medium. In addition, it requires the integration of a system of two complex coupled differential equations along the isotropic ray.
The interference of the qS waves is described by traveltime and polarization corrections of interacting isotropic S waves. For qP waves the approach leads to a correction of the traveltime of the P wave in the isotropic background medium.
Seismograms and particle-motion diagrams obtained from numerical computations are presented for models with different strengths of anisotropy.
The equivalence of the quasi-isotropic approximation and the quasi-shear-wave coupling theory is demonstrated. The quasi-isotropic approximation allows for a consideration of the limit from weak anisotropy to isotropy, especially in the case of qS waves, where the usual ray theory for anisotropic media fails. 相似文献
The interference of the qS waves is described by traveltime and polarization corrections of interacting isotropic S waves. For qP waves the approach leads to a correction of the traveltime of the P wave in the isotropic background medium.
Seismograms and particle-motion diagrams obtained from numerical computations are presented for models with different strengths of anisotropy.
The equivalence of the quasi-isotropic approximation and the quasi-shear-wave coupling theory is demonstrated. The quasi-isotropic approximation allows for a consideration of the limit from weak anisotropy to isotropy, especially in the case of qS waves, where the usual ray theory for anisotropic media fails. 相似文献
35.
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37.
Alberto G. FAIRÉN James M. DOHM Victor R. BAKER Shane D. THOMPSON William C. MAHANEY Kenneth E. HERKENHOFF J. Alexis P. RODRÍGUEZ Alfonso F. DAVILA Dirk SCHULZE‐MAKUCH M. Ramy EL MAARRY Esther R. UCEDA Ricardo AMILS Hirdy MIYAMOTO Kyeong J. KIM Robert C. ANDERSON Christopher P. McKAY 《Meteoritics & planetary science》2011,46(12):1832-1841
Abstract– Six large iron meteorites have been discovered in the Meridiani Planum region of Mars by the Mars Exploration Rover Opportunity in a nearly 25 km‐long traverse. Herein, we review and synthesize the available data to propose that the discovery and characteristics of the six meteorites could be explained as the result of their impact into a soft and wet surface, sometime during the Noachian or the Hesperian, subsequently to be exposed at the Martian surface through differential erosion. As recorded by its sediments and chemical deposits, Meridiani has been interpreted to have undergone a watery past, including a shallow sea, a playa, an environment of fluctuating ground water, and/or an icy landscape. Meteorites could have been encased upon impact and/or subsequently buried, and kept underground for a long time, shielded from the atmosphere. The meteorites apparently underwent significant chemical weathering due to aqueous alteration, as indicated by cavernous features that suggest differential acidic corrosion removing less resistant material and softer inclusions. During the Amazonian, the almost complete disappearance of surface water and desiccation of the landscape, followed by induration of the sediments and subsequent differential erosion and degradation of Meridiani sediments, including at least 10–80 m of deflation in the last 3–3.5 Gy, would have exposed the buried meteorites. We conclude that the iron meteorites support the hypothesis that Mars once had a denser atmosphere and considerable amounts of water and/or water ice at and/or near the surface. 相似文献
38.
Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea) 总被引:2,自引:0,他引:2
Anna Lichtschlag Janine Felden Florence Schubotz Antje Boetius Dirk de Beer 《Geochimica et cosmochimica acta》2010,74(17):5002-5018
The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m−2 d−1. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m−2 d−1) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 107 mol yr−1. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m−2 d−1. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea. 相似文献
39.
Drosos Kourounis Louis J. Durlofsky Jan Dirk Jansen Khalid Aziz 《Computational Geosciences》2014,18(2):117-137
An adjoint formulation for the gradient-based optimization of oil–gas compositional reservoir simulation problems is presented. The method is implemented within an automatic differentiation-based compositional flow simulator (Stanford’s Automatic Differentiation-based General Purpose Research Simulator, AD-GPRS). The development of adjoint procedures for general compositional problems is much more challenging than for oil–water problems due to the increased complexity of the code and the underlying physics. The treatment of nonlinear constraints, an example of which is a maximum gas rate specification in injection or production wells, when the control variables are well bottom-hole pressures, poses a particular challenge. Two approaches for handling these constraints are presented—a formal treatment within the optimizer and a simpler heuristic treatment in the forward model. The relationship between discrete and continuous adjoint formulations is also elucidated. Results for four example cases of increasing complexity are presented. Improvements in the objective function (cumulative oil produced) relative to reference solutions range from 4.2 to 11.6 %. The heuristic treatment of nonlinear constraints is shown to offer a cost-effective means for obtaining feasible solutions, which are, in some cases, better than those obtained using the formal constraint handling procedure. 相似文献
40.
Numerical simulation of a tunnel surrounded by sand under earthquake using a hypoplastic model 总被引:2,自引:1,他引:1
A numerical model of a centrifuge experiment on tunnel located in sand is being presented. The experiment was carried out under seismic loading using a dynamic actuator. The responses of the tunnel and of the sand were measured. The numerical model is based on a hypoplastic constitutive model with intergranular strains implemented in the FE-code TOCHNOG. The calculated accelerations in the sand match the measured results, while the surface settlement and the bending moments in the tunnel lining are only qualitatively reproduced by the numerical model. 相似文献