EPR evidence for maghemitization of magnetite in a tropical soil

Electron paramagnetic spectroscopy (EPR) was used in combination with standard rock magnetic methods to study magnetic minerals in a tropical soil. The susceptibility and hysteresis measurements showed magnetite grains with a Curie temperature near 850 K as the dominant magnetic remanence carriers in the soil. A minor Ti content in the magnetite was found by energy dispersive X-ray analysis. In order to get insight into the weathering status of the magnetite, different chemical treatments, including oxalate and citrate–bicarbonate–dithionite (CBD) extraction, were applied to the soil samples. The hysteretic properties exhibited no significant differences between the untreated and the CBD or oxalate treated samples. By contrast, the comparison of the EPR spectra revealed a significant broadening of the linewidth (δB) and a shift of the g -values ( g _eff) to lower fields after the CBD treatment. Furthermore, the spectral parameters g _eff and δB exhibited an angular dependence. At low temperature, the CBD treated samples showed a jump in δB between 120 and 100 K, the temperature range characteristic for the Verwey transition in magnetite. The changes in the spectral properties after the CBD treatment, which dissolves ferric oxides, were attributed to the removal of maghemite formed by the oxidation of magnetite, that is, during the maghemitization of the magnetite grains.     

RECENT DEVELOPMENTS IN MULTIVARIATE CALIBRATION

With the goal of understanding global chemical processes,environmental chemists have some of the mostcomplex sample analysis problems.Multivariate calibration is a tool that can be applied successfully inmany situations where traditional univariate analyses cannot.The purpose of this paper is to reviewmultivariate calibration,with an emphasis being placed on the developments in recent years.The inverseand classical models are discussed briefly,with the main emphasis on the biased calibration methods.Principal component regression(PCR)and partial least squares(PLS)are discussed,along with methodsfor quantitative and qualitative validation of the calibration models.Non-linear PCR,non-linear PLSand locally weighted regression are presented as calibration methods for non-linear data.Finally,calibration techniques using a matrix of data per sample(second-order calibration)are discussed briefly.     

Beiträge zur Messung der Evapotranspiration nach dem Austauschverfahren

Zusammenfassung Die Wasserabgabe einer vegetationsbestandenen Bodenfläche, die Evapotranspiration, setzt sich zusammen aus der Verdunstung von Wasser an der Bodenoberfläche (Evaporation) und der wenigstens in der Hauptvegetationszeit viel stärkeren Verdunstung von Wasser durch die Pflanzen (Transpiration). Zur Messung der Transpiration hat sich seit langem die kurzfristige Wägemethode bewährt, zur Messung der Evapotranspiration steht u. a. das der Klimatologie entlehnte Austauschverfahren zur Verfügung. An einem Beispiel (Luzerne) wird die Bestandestranspiration mit der kurzfristigen Wägemethode und die Evapotranspiration nach dem Austauschverfahren gleichzeitig bestimmt und die Ergebnisse werden miteinander verglichen.Vor Anwendung der Austauschmethode werden zunächst einige Schwierigkeiten erörtert, die sich ergeben: 1. bei der Festlegung der Höhen der Meßpunkte über dem Bestand; 2. aus dem Einfluß der Temperaturschichtung auf das Profil der Windgeschwindigkeit; 3. bei der Auswahl der Meßgeräte und der Bildung von Mittelwerten.Die wiedergegebenen Beispiele der Messungen (Abb. 2 bis 6) zeigen nicht nur große Differenzen zwischen den meteorologischen Daten, welche die zu den Messungen verwendeten Gerätepaare angeben, sondern auch starke Unterschiede zwischen den genannten zwei Meßmethoden. Die aufgezeigten Differenzen werden nicht so sehr auf die Mängel, welche die Geräte aufweisen, als vielmehr auf grundsätzliche Schwierigkeiten zurückgeführt, die sich aus der Turbulenz ergeben.

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Summary The evapotranspiration, i. e. the water loss of a soil with vegetation is composed of the evaporation from the surface of the ground and of the evaporation of water from the plants (transpiration), which is much more intensive at least in the main vegetation period. For measuring the transpiration the short-working weighing-method has held good for a long time past; for measuring the evapotranspiration there exists, among others, the procedure of determination of exchange borrowed from climatology. For an example (lucerne) the transpiration of the whole vegetation has been measured by the weighing-method and the evapotranspiration simultaneously by the exchange method and the results are compared with each other.Some difficulties are discussed which arise when using the exchange procedure: 1. the height above vegetation where to measure; 2. the influence of thermal stratification on the profile of wind velocity; 3. the selection of measuring instruments and the formation of mean values.The examples of measurements quoted in this article (Figs. 2–6) are showing great differences not only between the data of the meteorological instruments, but also between the two methods of measurement mentioned above. It must be supposed that these differences are to be attributed not so much to the deficiency of the instruments than to systematic difficulties resulting from the turbulence.

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Résumé La perte en eau d'un sol recouvert de végétation, c'est à dire son évapotranspiration, se compose de l'évaporation à la surface du sol même et de la transpiration végétale, beaucoup plus importante, au moins pendant la période de végétation. La mesure de la transpiration se fait par la méthode de pesée, pour de courts intervalles de temps, éprouvée depuis longtemps; celle de l'évapotranspiration s'appuie entre autres sur le procédé d'échange emprunté à la climatologie. Dans un cas particulier (luzerne) on a appliqué simultanément ces deux méthodes et on a comparé les résultats.La méthode d'échange présente toutefois quelques difficultés résultant: 1. du choix des hauteurs auxquelles se font les mesures au-dessus de la plantation; 2. de l'influence de la stratification thermique sur le profil de vitesse du vent; 3. du choix des appareils et du calcul des moyennes.Les exemples mentionnés (fig. 2 à 6) mettent en évidence, non seulement de grandes différences entre les valeurs des éléments météorologiques fournies par les appareils, mais encore entre les deux méthodes employées. Ces divergences découlent moins des défauts instrumentaux que des difficultés fondamentales résultant de la turbulence.

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Mit 6 Textabbildungen.     

The isotopic composition of strontium and sulfur in seawater of Late Permian (Zechstein) age

The Paleozoic minima of ⁸⁷Sr/⁸⁶Sr ratios and δ³⁴S values in seawater are observed in anhydrite layers of the Stassfurt (A-2) and Aller (A-4) cycles of evaporation of Late Permian age in Germany. These minima were probably caused by extremely low rates of continental runoff and bacterial sulfate reduction. Thereafter conditions changed suddenly, with a steeply increasing supply of radiogenic Sr and of nutrients into seawater. The latter induced a large growth in the production of organic material, in bacterial activity in sediments, and in the flow of isotopically heavy sulfur back into the oceans. This large change in the cycles of S and Sr (as well as of C and O) within the relatively short Zechstein period (2–5 Ma) reflects a considerable modification of the plate tectonic and environmental conditions shortly before the beginning of the Mesozoic era. The Ochoan deposition in the USA is probably of the same age as the Stassfurt-Leine evaporation in W Europe.     

Early Variscan magmatism in the Western Carpathians: U–Pb zircon data from granitoids and orthogneisses of the Tatra Mountains (Slovakia)

This study presents the first U–Pb zircon data on granitoid basement rocks of the Tatra Mountains, part of the Western Carpathians (Slovakia). The Western Carpathians belong to the Alpine Carpathian belt and constitute the eastern continuation of the Variscides. The new age data thus provide important time constraints for the regional geology of the Carpathians as well as for their linkage to the Variscides. U–Pb single zircon analyses with vapour digestion and cathodoluminescence controlled dating (CLC-method) were obtained from two distinct granitoid suites of the Western Tatra Mountains. The resulting data indicate a Proterozoic crustal source for both rock suites. The igneous precursors of the orthogneisses (older granites) intruded in Lower Devonian (405 Ma) and were generated by partial melting of reworked crustal material during subduction realated processes. In the Upper Devonian (365 Ma), at the beginning of continent–continent collision, the older granites were affected by high-grade metamorphism including partial melting, which caused recrystallisation and new zircon growth. A continental collision was also responsible for the generation of the younger granites (350–360 Ma). The presented data suggest multi-stage granitoid magmatism in the Western Carpathians, related to a complex subduction and collision scenario during the Devonian and Carboniferous. Received: 19 February 1999 / Accepted: 3 December 1999     

Deep structure of southeastern europe from Rayleigh waves

The analysis of Rayleigh-wave phase velocities up to about 250 s has allowed of deepening structural knowledge, down to several hundred kilometers underneath the triangular array formed by the WWSSN stations Athens-Istanbul-L'Aquila. For the path L'Aquila-Istanbul a lid-to-low velocity channel contrast of variable size is always present, while for the other two paths. Athens-Istanbul and Athens-L'Aquila. two alternative patterns are possible, one indicating the presence of a contrast between lid and low-velocity channel, the other suggesting the absence of significant layering down to depths of about 350 km.     

Die Genese der stratiformen Sulfidlagerstätte Kalwang (Steiermark), der Grünsteinserie und einer assoziierten silikatreichen Eisenformation

Zusammenfassung Die bearbeitete Lagerstätte ist dem Typ submarin exhalativer Bildung zuzuordnen. Grünschiefermetamorphe Nebengesteine (ehemalige vulkanosedimentäre Abfolge) unterlagenin situ einer hydrothermalen Alteration. Metallösungen (hot brines), welche zur Bildung der Sulfidlager führten, eruptierten im Bereich submariner Fumarolen. Sie entstammten Interaktionen meteorischer Wässer mit vulkanogenen In- und Extrusivprodukten. Die Lösungen bildeten schichtgebundene Erzlager, die zoniert als hoch-bis niedrigtemperierte Bildung vorliegen. Eine assoziierte silikatreiche Eisenformation schließt die Vererzung sowie die vulkanische Tätigkeit ab. Die Grüngesteine werden als Metabasite kontinentaler bis ozeanbodentholeiitischer Edukte gedeutet. Hinsichtlich der geotektonischen Situation verweisen alle Merkmale auf das Milieu einer MORB-Typ assoziierten, alterationsbedingten sulfidischen Vererzung als Folgeprodukt zunehmender Ozeanisierung eines kontinentalen Riftbereiches.

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Genesis of the Kalwang stratiform sulphide deposit, Styria, Austria, and of associated metavolcanics and siliceous banded iron formation

Summary The Kaiwang copper deposit (Styria, Austria) occurs within a Lower Paleozoic volcanosedimentary sequence which forms part of the extensive Nördliche Grauwackenzone of the Eastern Alps. Stratiform bodies of pyrite (0.02–0.05% Ni; 0.05–0.08%Co)-chalcopyrite and (Ni,Co-free) pyrrhotite-chalcopyrite ores are associated with mafic metavolcanic rocks; metapelites and marbles are also present in the ore environment. Comprehensive analyses of major and trace elements suggest that the metavolcanites have been derived from tholeiites of intraplate-to ocean floor affinity linked to the development of an intracontinental rift. Regional metamorphism of lower greenschist grade was preceded by spilitization of the volcanic rocks. Mineralization at Kalwang is submarine-exhalative; some copper sulphides have been deposited in supply channels prior to reaching the sea floor. Towards the hanging-wall, the ore-bearing sequence is terminated by a two metres thick manganiferous iron formation; manganese is concentrated almost exclusively in spessartine garnet. The BIF has been derived from a manganiferous, chamositic precursor sediment. Stratabound base metal deposits further west in the Northern Greywacke Zone show similar evolutionary trends; this points towards a coherent metallogenetic pattern for this important tectonic unit.

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Mit 12 Abbildungen     

Geochemical demobilization of metallic pollutants in solid waste—implications for arsenic in waterworks sludges

During stabilization or demobilization of contaminants in solid waste materials, different approaches can be taken, which also can be combined: (1) sufficient long-term buffer capacity can be provided, according to the environmental conditions; (2) permeability for dissolved contaminants can be reduced by secondary mineral precipitations or by soft gels injected into the pore space of the waste body; and (3) new formations of ‘reservoir minerals' can incorporate potential pollutants in their internal structure. Emphasizing the geochemical engineering approach, two examples are presented from the field of water management, both focussing on the demobilization of arsenic species. The first example (after Driehaus, W., 1994. Arsenentfernung mit Mangandioxid und Eisenhydroxid in der Trinkwasseraufbereitung. Vol. 133, Ser. 15, VDI-Reports, Düsseldorf, 117 pp.) relates to the problems during purification of arsenic-rich raw water, suggesting the potential application of iron and manganese oxide minerals as oxidizing agents and mineral lattice structures for the elimination of arsenic. In the second example, contaminated sludges from water treatment plants were investigated for their leaching characteristics and long-term stability. A pH-stat test procedure was used to assess the leaching characteristics of metals at typical pH values. Due to the presence of iron and manganese oxides pentavalent arsenic is protected against conversion into the mobile trivalent form at neutral to low pH. Experimental data suggest that co-disposal with reducing organic matter and alkaline stabilization material or wastes could negatively influence the binding properties and, therefore, should be avoided.     

Gravity anomalies and subsurface geology in the Westerwald volcanic area, Germany

The area of the present study constitutes an alkaline volcanic province in the eastern sector of the Rhenish massif. A series of gravity measurements were carried out on the volcanic fields of the Westerwald. Three-dimensional modelling and wavelength filtering processing techniques were used to analyze the gravity data. The filtered Bouguer anomaly maps show two major regional gravity features: (a) Increasing Bouguer values towards the northeastern part of the study area could be caused by lateral lithological variations within the upper crust. (2) Local negative Bouguer values in the southwest correlate with magmatic materials of intermediate type. The modelling results indicate that the volcanics of the Westerwald are underlain by two different magmatic complexes at a depth in the range 3.3–10 km with density values of 2680 and 2750 kg/m³. The densities assigned to the local igneous intrusions are in the range of 2314–2948 kg/m³ and at depths between 0.4 and 1.3 km. In the NE a diabase bed was modelled to a maximum depth of approximately 1.6 km using the assigned density of 2800 kg/m³.     

四川黄龙钙华的形成

作者通过现场测试、实验及室内分析,从薄膜(扩散边界层)效应及水化学的变化对黄龙钙华进行了研究,得出黄龙钙华的沉积速率为0.43～4.7mm/a,其中速率较大者出现在流速较快(边界层较薄)的部位,如边石坝上;而速率较小者则出现在流速较慢(边界层较厚)的部位,如钙华池内。