Equilibrium interface segregation in the diopside-forsterite system I: Analytical techniques, thermodynamics, and segregation characteristics

After syntheses of partially molten diopside-forsterite polycrystalline aggregates doped with various solutes, we analyzed the equilibrium segregation of Ni, Mn, Sr, Al, Yb, Y, Nd, La, and Ti at interfaces between diopside/diopside, diopside/forsterite and, forsterite/forsterite grains based on STEM/EDX (scanning transmission electron microscopy/energy dispersive X-ray spectrometry) to examine the effects of ionic size, valence state, co-segregation, and interface type on interface chemistry. We derive relationships between two quantities describing interface segregation and X-ray intensities acquired both from areas that include an interface and from areas that do not. These segregation quantities are (i) interface excess density and (ii) interface enrichment factor, which rely on Gibbsian thermodynamics and the Langmuir-McLean segregation model, respectively. Interface excess densities, which vary from −0.5 to 10 atoms/nm², indicate that the level of interface excess density depends on solutes and sample assemblage. Interface enrichment factors, which range from almost 1 to 130, reveal that the ionic size of the solutes affects their segregation via production of misfit lattice strain due to the difference between the size of a solute ion and that of the ideal strain-free lattice site. The ionic sizes of Yb and Y are almost identical to the size of the strain-free site; however, their segregation is significant indicating that a difference in valence state between the host elements (i.e., Ca and Mg) and the solutes also drives segregation. In contrast to other solutes, segregation characteristics of Al differ from these simple segregation rules. Segregation quantities do not change with interface type, indicating that the number of sites available for segregants and the driving force for segregation are similar among type of interfaces. We compare the element partitioning between diopside-melt and diopside-interfaces within the same sample assemblages. These two partition coefficients coincide if we approximate the number of segregation sites at interfaces as equivalent to 2 mono-atomic layers. Examination of the energetics in crystal-melt partitioning reveals that the interface segregation energy is essentially equal to the solute solution energy in a crystal.     

Influence of the natural organic matter in the removal of caffeine from water by fixed-bed column adsorption

The removal of caffeine from tap water by F-400 granular activated carbon in fixed-bed adsorption experiments was carried out. Textural and chemical characterization of the adsorbent through N₂ adsorption–desorption isotherms, Fourier transform infrared spectrometry, isoelectric point determination and scanning electron microscopy studies was developed in studies previously reported. Caffeine breakthrough curves and total organic carbon profiles at different operation conditions (inlet concentration, volumetric flow rate and mass of adsorbent) were obtained. These experimental results showed a displacement of the natural organic matter from the active sites exerted by caffeine molecules due to their higher affinity to the surface carbon. This behavior led to an overshooting, a local outlet natural organic matter concentration higher than the feed quantity. A competitive effect seems to be observed in the removal of the target compound, decreasing the efficiency of the process. Axial dispersion coefficients and dimensionless numbers were estimated for the caffeine removal onto F-400 activated carbon. Therefore, the regeneration of the adsorbent by adsorption–desorption cycles was studied.     

Petrology and Geochemistry of MORB from 25?E to 46?E along the Southwest Indian Ridge: Evidence for Contrasting Styles of Mantle Enrichment

The 1984 PROTEA expedition, leg 5, to the central SouthwestIndian Ridge recovered basaltic lavas from fracture zones andridge segments between 25?E and 48?E. In terms of petrographyand major element variations the samples are unremarkable forocean ridge basalts and range from aphyric to highly plagioclasephyric and from primitive (mg-number = 70) to moderately evolved(mg-number = 40) in composition. Multiply saturated (i.e., olivine,plagioclase, and clinopyroxene) basalts are common within thisregion. There is no systematic difference in compositional characteristicsbetween basalts dredged from fracture zone walls and those dredgedfrom ridge segments, and fractional crystallization has playedan important role in controlling the overall range in lava compositionin both tectonic environments. Incompatible element abundance ratios in the basalts are morenotable and distinguish between geochemically depleted (N-type)MORB with high Zr/Nb (1668) and Y/Nb (4?723) ratios and low(La/Sm)^m, ratios (0-?76–1?00), and geochemically enriched(E-type) MORB with low Zr/Nb (3?4–15?8) and Y/Nb (0?5–8?8)and high (La/Sm). ratios (1?07–3?8). N-type MORB appearsto be absent in the immediate vicinity of Marion Island, butoccurs further along the ridge to the northeast and southwest.Geochemically enriched MORB occurs at scattered localities alongthe ridge but is particularly abundant along the section ofthe ridge closest to the Marion hotspot. In detail, two distinct varieties of E-type MORB can be recognized.The one type has incompatible element and isotopic ratios similarto, although slightly less enriched than, those characteristicof the Marion hotspot (Zr/Nb=5?8–8?6; Y/Nb=0?5–0?8;Ba/Nb=5?1–9?0). The second type can be distinguished byhaving high Ba/Nb ratios (9–22), unlike any lavas directlyassociated with the Marion hotspot, but similar to those characteristicof DUPAL ocean island basalts (OIB). A single sample from thisgroup for which there are isotopic data indicates derivationfrom an isotopically anomalous source region. A model is proposed whereby the sub-oceanic mantle below thisportion of the southwest Indian Ocean has experienced at leasttwo distinct enrichment events. The one is associated with theupwelling of the Marion mantle plume (geochemically characterizedby having low Ba/Nb ratios and normal OIB isotopic ratios).The other is associated with upwelling from a DUPAL source (characterizedby having high Ba/Nb ratio and unusual isotopic ratios) whichhas been proposed to exist beneath this portion of the southwestIndian Ocean (Hart, 1984). On the basis of Ba/Nb and Nb/U ratios,recycled oceanic lithosphere is favoured as a source for theMarion hotspot, while recycled oceanic lithosphere plus ancientpelagic sediment appears to be the most likely source for theDUPAL anomaly and the DUPAL E-type MORB in this region.     

Sequential extraction procedure in columns. Part 1: Development and description of a new method

A sequential extraction procedure was carried out in columns using reagents that are known to be reliable from batch tests. The intention was to distinguish between different chemical forms of iron and heavy metals in samples from reduced porous aquifers, which demands anaerobic conditions for the extraction procedure and the determination of small amounts of reactive mineral phases in a quartz dominated sediment system. By means of the developed method, anaerobic conditions can be guaranteed in the columns, which could not be realized to full satisfaction in batch tests that were carried out in a glove box. In order to distinguish between the fractions that were water soluble, exchangeable, bound to carbonates and bound to hydroxides, different reagents were pumped through the sediments and sampled after passage of the columns. Sediment samples of 10 kg each were investigated in this way. The extraction steps were known to be complete when analyses revealed that no further major and trace elements were leached out of the columns. This approach enabled well-adjusted amounts of reagents to be used. By means of the sequential extraction procedure in columns the composition of even small amounts of reactive mineral phases can be determined successfully, which contributes to a deeper understanding of the hydrogeochemical processes in aquifers. In batch tests this accuracy cannot be reached because of the surplus of the extraction solution in relation to the amount of sediment (higher solution-sediment ratio). Furthermore, larger samples are much more representative of the composition of the aquifers than smaller ones and the heterogeneity of the sediment does not limit the accuracy of the results as much as in batch tests. In addition, the technique of flushing sediment in a column is much more typical for the situation in an aquifer than suspending a few grams of a sample in the extracting reagents in batch extraction tests. In order to demonstrate the methodical improvements and field applications, the newly developed method was used to investigate the changing binding forms and mobility of iron and trace metals in samples from a lignite overburden dump, which are influenced by pyrite oxidation processes (acidification) followed by the addition of crushed limestone (neutralization) (see "Sequential extraction procedure in columns. Part 2: Application of a new method").     

青藏高原东缘晚新生代成都盆地物源分析与水系演化

成都盆地位于青藏高原东缘,夹于龙门山与龙泉山之间,盆地中充填了3.6Ma以来的大邑砾岩、雅安砾石层和晚更新世—全新世砾石层,其物源均来源于盆地西侧的龙门山,具横向水系和单向充填的特征。本次以物源区分析作为切入点,以岷江和青衣江水系为重点,采用砾岩成分分析、砂岩岩屑成分分析、重矿物分析和砾石的地球化学分析等基本方法,开展青藏高原东缘晚新生代以来的古水系重建工作,研究结果表明,成都盆地主要有两个物源区,其中成都盆地北部的都江堰街子场、崇州白塔山、大邑白岩沟、大邑氮肥厂、彭州丁家湾、彭州葛仙山等剖面中的砾石层在碎屑成分、重矿物和花岗岩砾石的地球化学成分等方面相似,应为古岷江的产物,而其与现代岷江在砾岩成分和重矿物特征等方面的差异性则表明古岷江可能存在改道的现象;成都盆地南部的庙坡剖面和熊坡东剖面中的砾石层在碎屑成分、重矿物和花岗岩砾石的地球化学成分等方面相似,应为古青衣江的产物,但其流向却与现代青衣江的流向不同,表明熊坡背斜是在大邑砾岩沉积之后隆起的,它的隆起迫使古青衣江改道。     

Main results of recent investigations into the physical mechanisms of the interaction of tropical cyclones and the ionosphere

Izvestiya, Atmospheric and Oceanic Physics - International investigations into the correlation between tropical cyclones (TCs) and the ionosphere are associated with great difficulties in proving...     

Evidence for Century-Timescale Acceleration in Mean Sea Levels and for Recent Changes in Extreme Sea Levels

Two of the most important topics in Sea Level Science are addressed in this paper. One is concerned with the evidence for the apparent acceleration in the rate of global sea level change between the nineteenth and twentieth centuries and, thereby, with the question of whether the twentieth century sea level rise was a consequence of an accelerated climate change of anthropogenic origin. An acceleration is indeed observed in both tide gauge and saltmarsh data at different locations around the world, yielding quadratic coefficients ??c?? of order 0.005 mm/year², and with the most rapid changes of rate of sea level rise occurring around the end of the nineteenth century. The second topic refers to whether there is evidence that extreme sea levels have increased in recent decades at rates significantly different from those in mean levels. Recent results, which suggest that at most locations rates of change of extreme and mean sea levels are comparable, are presented. In addition, a short review is given of recent work on extreme sea levels by other authors. This body of work, which is focused primarily on Europe and the Mediterranean, also tends to support mean and extreme sea levels changing at similar rates at most locations.     

Extinction in a photo-electric nucleus counter using adiabatic expansion of 1.21 pressure ratio achieved by increasing or decreasing the original pressure

Summary Comparisons were made of the extinctions as measured with a photoelectric condensation nucleus counter, Dublin School of Cosmic Physics Model 1957, when the «over-pressure method» or the «under-pressure method» with equal pressure expansion ratios were used for producing the adiabatic cooling of the sample in, the fogtube of the counter. Due to theSchlarb effect the extinction measured by the second method is smaller than that by the first. Tables and graphs for converting the extinction obtained by one method into that by the other are given. The advantages of the underpressure method are given and discussed.

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Zusammenfassung Es wird über die Vergleichung der Extinktionen, welche mit einem photo-elektrischen Kondensationskernzähler Modell 1957 der Schule für kosmische Physik in Dublin gemessen werden, berichtet, wenn, bei gleichem Druckexpansions-Verhältnis, die Druckerhöhungs- oder die Expansionsmethode in ein partielles Vakuum für die Erzeugung der adiabatischen Abkühlung der im Nebelrohr des Kernzählers eingeschlossenen Aerosolprobe benützt wird. Wie erwartet, ist als Folge desSchlarb-Effektes die mit der zweiten Methode gemessene Extinktion kleiner. Tabellen und Kurven werden mitgeteilt, welche die Umwandlung der mit der einen Methode erhaltenen Extinktion in jene der anderen ermöglichen, und die Vorteile der Vakuum-Expansions-Methode diskutiert.

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The research reported in this article has been supported in part by the Geophysics Research Directorate of the Air Force Cambridge Research Laboratories, through the European Office of the Air Research Division, United States Air Force under Contract AF 61 (052)-26 and by the Instrumentation Engineering Physics & Analysis Laboratory of the General Electric Co. Schenectady, New York under Retainer Agreement.     

Seismicity, seismic input and site effects in the Sahel—Algiers region (North Algeria)

Algiers city is located in a seismogenic zone. To reduce the impact of seismic risk in this Capital city, a realistic modelling of the seismic ground motion (SGM) is conducted by using the hybrid method that combines the finite differences method and the modal summation. For this purpose, a complete database of geological, geophysical and earthquake data is constructed. A critical re-appraisal of the seismicity of the zone [2.25°E–3.50°E, 36.50°N–37.00°N] is performed and an earthquake list, for the period 1359–2002, is compiled. The analysis of existing and newly retrieved macroseismic information allowed the definition of earthquake parameters of macroseismic events for which a degree of reliability is assigned. Geological cross sections have been built up to model the SGM in the city, caused by the 1989 Mont-Chenoua and the 1924 Douéra earthquakes. Synthetic seismograms and response spectral ratio is produced for Algiers, and they show that the soft sediments in Algiers centre are responsible of the noticed amplification of the SGM.