Alternative Validation of a LC-MS/MS-Multi-Method for Pesticides in Drinking Water     

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   

The Bayesian approach to an internally consistent thermodynamic database: theory, database, and generation of phase diagrams     

Niranjan D. Chatterjee  Ralf Krüger  Gerd Haller  Walter Olbricht 《Contributions to Mineralogy and Petrology》1998,133(1-2):149-168

An internally consistent thermodynamic dataset has been derived for 148 endmember phases (145 solids and 3 fluids) comprising the elements Li, Na, K, Be, Mg, Ca, Ti, Cr, Mn, Fe, Zn, Al, Si, C, H, and O. This has been achieved by simultaneous treatment of phase property (like standard enthalpy of formation, standard entropy, molar heat capacity, molar volume, thermal expansivity, bulk modulus etc.) and reaction reversal data by the Bayesian method. The theory underlying the approach, and the computational methods involved, are briefly outlined. (For the benefit of readers unfamiliar with inference statistics, the basic concepts of the Bayes method are also presented in such a way that they can be grasped intuitively.) Although not yet addressed, this method can be extended to refine the thermodynamic mixing properties of crystalline solutions. The sources of the input data, culled from the literature, are summarized in the Appendix. The resulting database is succinctly documented in this paper. It includes the enthalpies of formation and entropies, their uncertainties, and the correlation among them. The database allows calculation of P-T, T-X _CO2, P-X _CO2, and T-f _O2 sections, with error propagation into the computed phase diagrams on a routine basis. A user-friendly computer program has been written to generate such phase diagrams. It is public domain software. The software and the thermodynamic database (which includes a complete documentation of the thermodynamic data above and beyond those listed (Table 2, here) may be downloaded from the web site http://homepage.ruhr-uni-bochum.de/niranjan.chatterjee/Index.htm. Examples of computed phase diagrams are given to illustrate the quality of the data and the capabilities of the software. Received: 11 March 1998 / Accepted: 11 June 1998  相似文献   

Mass models of the Milky Way     

Walter Dehnen  & James Binney 《Monthly notices of the Royal Astronomical Society》1998,294(3):429-438

A parametrized model of the mass distribution within the Milky Way is fitted to the available observational constraints. The most important single parameter is the ratio of the scalelength R _d* of the stellar disc to R ₀. The disc and bulge dominate v _c( R ) at R ≲ R ₀ only for R _d,*/ R ₀≲0.3. Since the only knowledge we have of the halo derives from studies like the present one, we allow it to contribute to the density at all radii. When allowed this freedom, however, the halo causes changes in assumptions relating to R  ≪  R ₀ to affect profoundly the structure of the best-fitting model at R  ≫  R ₀. For example, changing the disc slightly from an exponential surface-density profile significantly changes the form of v _c( R ) at R  ≫  R ₀, where the disc makes a negligible contribution to v _c. Moreover, minor changes in the constraints can cause the halo to develop a deep hole at its centre that is not physically plausible. These problems call into question the proposition that flat rotation curves arise because galaxies have physically distinct haloes rather than outwards-increasing mass-to-light ratios.   The mass distribution of the Galaxy and the relative importance of its various components will remain very uncertain until more observational data can be used to constrain mass models. Data that constrain the Galactic force field at z ≳ R and at R  >  R ₀ are especially important.  相似文献   

Modulation and symmetry changes in stellar dynamos     

E. Knobloch  S. M. Tobias  & N. O. Weiss 《Monthly notices of the Royal Astronomical Society》1998,297(4):1123-1138

Stellar dynamos are governed by non-linear partial differential equations (PDEs) which admit solutions with dipole, quadrupole or mixed symmetry (i.e. with different parities). These PDEs possess periodic solutions that describe magnetic cycles, and numerical studies reveal two different types of modulation. For modulations of Type 1 there are parity changes without significant changes of amplitude, while for Type 2 there are amplitude changes without significant changes in parity. In stars like the Sun, cyclic magnetic activity is interrupted by grand minima that correspond to Type 2 modulation. Although the Sun's magnetic field has maintained dipole symmetry for almost 300 yr, there was a significant parity change at the end of the Maunder Minimum. We infer that the solar field may have flipped from dipole to quadrupole polarity (and back) after deep minima in the past and may do so again in the future. Other stars, with different masses or rotation rates, may exhibit cyclic activity with dipole, quadrupole or mixed parity. The origins of such behaviour can be understood by relating the PDE results to solutions of appropriate low-order systems of ordinary differential equations (ODEs). Type 1 modulation is reproduced in a fourth-order system while Type 2 modulation occurs in a third-order system. Here we construct a new sixth-order system that describes both types of modulation and clarifies the interactions between symmetry-breaking and modulation of activity. Solutions of these non-linear ODEs reproduce the qualitative behaviour found for the PDEs, including flipping of polarity after a prolonged grand minimum. Thus we can be confident that these patterns of behaviour are robust, and will apply to stars that are similar to the Sun.  相似文献   

Local stellar kinematics from Hipparcos data   总被引：1，自引：0，他引：1  

Walter Dehnen  & James J. Binney 《Monthly notices of the Royal Astronomical Society》1998,298(2):387-394

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Wegeners „Kontinentverschiebungen“ zu seiner Zeit und heute     

Prof. Dr. Walter Kertz 《International Journal of Earth Sciences》1981,70(1):15-32

Zusammenfassung Ausgangspunkt der Wegenerschen Theorie war der unmittelbare Eindruck von der Kongruenz der atlantischen Küsten. Das eigentliche Fundament bildeten jedoch die Argumente aus Paläontologie, Geophysik, Geologie, Paläoklimatologie und Astrogeodäsie. Wegener war nicht nur der Schöpfer, sondern auch der Propagandist seiner Theorie. Von bleibendem Wert erwiesen sich seine Forderungen: Jede Theorie der Entstehung der Ozeane und Kontinente muß von allen geowissenschaftlichen Disziplinen getragen werden und sie muß sich durch Messungen bestätigen lassen.

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The starting-point of Wegener's theory was the direct impression of the congruity of the Atlantic coastlines. The fundamental principle, however, is formed by the argumentation of paleontology, geophysics, geology, paleoclimatology and astrogeodesy. Wegener was not only the creator of his theory but he also propagated it. His demands proved to be of lasting value: every theory of the origin of oceans and continents has to be supported by all geosciences and it should be possible to be verified by physical measurements.

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Resume Le point de départ de la théorie de Wegener fut l'impression immédiate de la concordance des côtes atlantiques. Les bases véritables furent les arguments tirés de la Paléontologie, de la Géophysique, de la Géologie, de la Paléoclimatologie et de l'Astrogéodésie. Wegener fut non pas seulement le créateur de sa théorie, mais encore son propagandiste. Sa démarche reste valable d'une théorie de la genèse des continents et des océans qui soit étayée part toutes les sciences de la terre et verifée par des mesures physiques.

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. , , , . , . , , .

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The origin of high-amplitude magnetic anomalies at the intersection of the Juan de Fuca ridge and Blanco fracture zone     

Robert S. Detrick  Walter S. Lynn 《Earth and Planetary Science Letters》1975,26(1):105-113

The intersection of the Juan de Fuca ridge and Blanco fracture zone is characterized by unusually high amplitude magnetic anomalies (over 1500 nT) which appear to be associated with a body roughly 50 km in length and 20 km in width aligned along the fracture zone. Simple three-dimensional magnetic models indicate that this anomaly is probably caused by a highly magnetized block of material situated in the western end of the Blanco fracture zone near its intersection with the Juan de Fuca ridge. Rock magnetization studies of tholeiitic basalts dredged from this area confirm the presence of highly magnetized basalts near the ridge crest/transform fault intersection. These tholeiitic basalts are enriched in iron and titanium relative to “normal” oceanic tholeiites, apparently the result of extensive shallow fractionation involving olivine, plagioclase, and clinopyroxene. Magnetic model studies indicate that an average thickness of no more than 500 m of these iron-rich basalts is necessary to produce the observed anomaly pattern. Comparison of these basalts with samples previously dredged from the Juan de Fuca ridge crest suggests that these Fe-rich, highly magnetized basalts probably “leaked” out of the southernmost portion of the Juan de Fuca ridge.  相似文献   

Zur Stratigraphie,Petrologie und Genese einer Bentonit-Lage aus dem oberen Mittel-Turon (Oberkreide) des südöstlichen Münsterlandes     

Dr. Ekbert Seibertz  Dr. Walter Vortisch 《International Journal of Earth Sciences》1979,68(2):649-679

Zusammenfassung Die Bentonit-Lage kann möglicherweise mit der Lage M₆₈ aus dem Turon von Lüneburg (Norddeutschland) korreliert werden. Identifiziert wurden vulkanische Glasfragmente, Quarz, Na-, K-Feldspat, Oligoklas, Biotit, Muskovit, Calcit, Schwerminerale (u. a. Olivin, Hornblende) und Tonminerale (Kaolinit, Illit, mixed-layer Illit/Smektit, FeBeidellit - z. T. in großen Aggregaten). Die vulkanoklastischen Gläser zeigen alle Übergänge von intakt zu völlig devitriert. Mit Hilfe der Elektronenstrahl-Mikrosonde konnten, bei Berücksichtigung der Kathoden-Lumineszenz, die Feldspäte chemisch analysiert und genetisch in solche mit niedrigerer und solche mit höherer (vulkanoklastisch) Bildungstemperatur gegliedert werden. Von den Schwermineralen dürften vor allem Olivin und Hornblende vulkanogener Herkunft sein. Untersuchungen der durch Umwandlung vulkanischen Materials entstandenen kompakten Smektit-Aggregate mittels Mikrosonde, Röntgendiffraktometrie und Mössbauer-Spektroskopie zeigten, daß es sich hier um ein AI-reiches Glied der Mischungsreihe Nontronit-Beidellit (Fe-reicher Beidellit) handelt. Differentialthermoanalytische Untersuchungen ergaben für Fe-reiche, dioktaedrische, smektitische Tonminerale typische Kurven. Das Ausgangsmaterial des Bentonits war intermediär bis basisch. Äolischer oder kombiniert äolischer und mariner Transport von Exhalationspunkten im mitteleuropäischen Raum werden diskutiert.

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The bentonite can probably be correlated with horizon M₆₈ in the Turonian of Lüneburg in northern Germany. Volcanic glass fragments, quartz, Na and K feldspars, oligoclase, biotite, muscovite, calcite, heavy minerals (i. a. olivine, hornblende) and clay minerals (kaolinite, illite, mixed-layer illite/smectite and Fe-beidellite) were identified. The glass shows a spectrum of all states from unaltered to completely devitrified. Analysis of feldspars by means of electron microprobe and cathodo-luminescence has allowed to divide them into genetically high (pyroclastic) and low temperature forms. Of the heavy minerals, olivine and hornblende most clearly are of volcanic origin. Examinations of smectite aggregates (alteration products of volcanic material) by electron microprobe, x-ray diffractometry, and Mössbauer spectroscopy demonstrated the presence of a member of the continuous series nontronite-beidellite (Fe-rich beidellite). Differential thermal analysis gave typical curves for dioctahedral Fe-rich smectites. The chemical composition of the original material of the bentonite was intermediate to basic. Eolian or eolian and marine current transport from sources in central Europe are considered.

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Résumé La couche de bentonite peut probablement être corrélée avec la couche M₆₈ du Turonien de Lunebourg (au nord de l'Allemagne). Des fragments de verre volcanique, du quartz, du feldspath sodique, du feldspath potassique, de l'oligoclase de la biotite, de la muscovite, de la calcite, des minéraux lourds (p. ex. olivine, hornblende) et des minéraux argileux (kaolinite, illite, mixed-layer illite/smectite, beidellite ferreux — en partie en grands agrégates) ont été identifiés. Les verres pyroclastiques montrent tous les passages du verre intact jusqu'au verre entièrement dévitrifié. A l'aide de la microsonde électronique et en prenant en considération la cathodoluminescence, les feldspaths pouvaient être analysés chimiquement et ordonnés génétiquement selon leur température de formation. Ceux à haute temperature de formation sont pyroclastiques. Parmi les minéraux lourds pouvaient avant tout être d'origine volcanogène, l'olivine et la hornblende. Les études des agrégats de smectites compacts formés par la transformation de matériaux volcaniques montrent grâce à la microsonde, la diffractométrie X et de la spectrométrie de Mössbauer qu'il s'agit dans ce cas là d'un membre riche en Al de la série des mélanges nontronite-beidellite (beidellite ferreux). Des analyses thermiques différentielles donnèrent des courbes typiques pour les minéraux argileux smectitiques, dioctaédriques et riches en Fe. La matière de base de la bentonite était intermédiaire à basique. Transport éolien ou transport combiné, éolien et marin des points d'exhalation dans l'espace européen central seront dicutés.

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Polycyclic aromatic hydrocarbons in Recent lake sediments—I. Compounds having anthropogenic origins     

Stuart G. Wakeham  Christian Schaffner  Walter Giger 《Geochimica et cosmochimica acta》1980,44(3):403-413

Polycyclic aromatic hydrocarbons (PAH) in sediment cores from Lake Lucerne, Lake Zürich, and Greifensee, Switzerland, and Lake Washington, northwest U.S.A., have been isolated, identified and quantified by glass capillary gas chromatography and gas chromatography/mass spectrometry. Surface sediment layers are greatly enriched in PAH—up to 40 times—compared to deeper layers. In addition, concentration increases in upper sediments generally correspond to increasing industrialization and urbanization in the catchment basins of the lakes. Few PAH could be detected in pre-industrial revolution sediments, indicating that background levels for most PAH in aquatic sediments are extremely low.These results are consistent with an anthropogenic source for most of the aromatic hydrocarbons present in the modern sediments. A comparison of PAH distributions in the sediments and in possible source materials shows that urban runoff of street dust may be the most important PAH input to these lacustrine sediments. There is evidence that a significant contribution to the PAH content of street dust comes from material associated with asphalt.  相似文献   

Poly cyclic aromatic hydrocarbons in Recent lake sediments—II. Compounds derived from biogenic precursors during early diagenesis     

Stuart G. Wakeham  Christian Schaffner  Walter Giger 《Geochimica et cosmochimica acta》1980,44(3):415-429

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