The Response of a Small Stream in the Lesni Potok Forested Catchment, Central Czech Republic, to a Short-Term In-Stream Acidification

Lesni Potok stream drains a forested headwater catchment in the central Czech Republic. It was artificially acidified with hydrochloric acid (HCl) for four hours to assess the role of stream substrate in acid-neutralisation and recovery. The pH was lowered from 4.7 to 3.2. Desorption of Ca and MP and desorption or solution of Al dominated acid-neutralisation; Al mobilisation was more important later. The stream substrate released 4.542 meq Ca, 1, 184 meq Mg, and 2,329 meq Al over a 45 in long and I in wide stream segment, smaller amounts of Be. Cd, Fe, and Mn were released. Adsorption of SO42- and desorption of F- occurred during the acidification phase of the experiment. The exchange reactions were rapidly reversible for Ca, Mg and SO42- but not symmetric as the substrate resorbed 1083, 790 and 0 meq Ca, Mg, and Al. respectively, in a 4-hour recovery period. Desorption of SO42- occurred during the resorption of Ca and Mg. These exchange and dissolution reactions delay acidification, diminish the pH depression and retard recovery from episodic acidification. The behaviour of the stream substrate-water interaction resembles that for soil-soil water interactions. A mathematical dynamic mass-balance based model, MASS (Modelling Acidification of Stream Sediments), was developed which simulates the adsorption and desorption of base cations during the experiment and was successfully calibrated to the experimental data.

Clay mineralogy and multi-element chemistry of surface sediments on the Aiberian-Arctic Shelf

Clay mineral and bulk chemical (Si, Al, K, Mg, Sr, La, Ce, Nd) analyses of terrigenous surface sediments on the Siberian-Arctic shelf indicate that there are five regions with distinct, or endmember, sedimentary compositions. The formation of these geochemical endmembers is controlled by sediment provenance and grain size sorting. (1) The shale endmember (Al, K and REE rich sediment) is eroded from fine-grained marine sedimentary rocks of the Verkhoyansk Mountains and Kolyma-Omolon superterrain, and discharged to the shelf by the Lena, Yana, Indigirka and Kolyma Rivers. (2) The basalt endmember (Mg rich) originates from NE Siberia's Okhotsk-Chukotsk volcanic belt and Bering Strait inflow, and is prevalent in Chukchi Sea Sediments. Concentrations of the volcanically derived clay mineral smectite are elevated in Chukchi fine-fraction sediments, corroborating the conclusion that Chukchi sediments are volcanic in origin. (3) The mature sandstone endmember (Si rich) is found proximal to Wrangel Island and sections of the Chukchi Sea's Siberian coast and is derived from the sedimentary Chukotka terrain that comprises these landmasses. (4) The immature sandstone endmember (Sr rich) is abundant in the New Siberian Island region and reflects inputs from sedimentary rocks that comprise the islands. (5) The immature sandstone endmember is also prevalent in the western Laptev Sea, where it is eroded from sedimentary deposits blanketing the Siberian platform that are compositionally similar to those on the New Siberian Islands. Western Laptev can be distinguished from New Siberian Island region sediments by their comparatively elevated smectite concentrations and the presence of the basalt endmember, which indicate Siberian platform flood basalts are also a source of western Laptev sediments. In certain locations grain size sorting noticeably affects shelf sediment chemistry. (1) Erosion of fines by currents and sediment ice rafting contributes to the formation of the coarse-grained sandstone endmembers. (2) Bathymetrically controlled grain size sorting, in which fines preferentially accumulate offshore in deeper, less energetic water, helps distribute the fine-grained shale and basalt endmembers. An important implication of these results is that the observed sedimentary geochemical endmembers provide new markers of sediment provenance, which can be used to track sediment transport, ice-rafted debris dispersal or the movement of particle-reactive contaminants.

Mineralogy and geochemistry at DSDP Leg 80 Holes

Cenozoic sediments recovered from Sites 548, 549, and 550 were the objects of mineralogical (bulk sample and <2 - µm fraction) and geochemical (HCl extract) studies. Thin sections of rock pebbles embedded in sediments (upper levels at Site 548, particularly) were examined on a polarizing microscope. This study outlines the vertical and lateral variation and evolution of the sedimentation. In the Paleocene and lower Eocene, the clay fraction is abundant and smectite is practically the sole existing clay mineral. High Mn, Al, Fe, Mg, and K contents were measured in HCl extracts. Through the middle Eocene, carbonates become more abundant - highly dominant at Site 548. Metal contents in HCl extracts are very low. The clay fraction, although dominated at all sites by smectites, becomes richer in illite and poorly crystallized chlorite. At the middle/upper Miocene boundary, a significant decrease in the smectite/(illite + chlorite) ratio occurs at all sites, and this decrease continues into the middle Pliocene. This decrease is marked by an abrupt increase of quartz at Site 548. At the two other sites, carbonates remain highly predominant; HCl extracts reflect the relative abundance of the clay and carbonate fractions. After a brief recurrence of smectite in a high-metal-content interval, illite and chlorite become the dominant clay minerals in the upper Pliocene and the Pleistocene, where numerous variations in mineralogical composition occur in the clay fraction (Sites 548 and 549) or in non-clay components (Site 548). Several pebbles of various nature and origin, encountered in different levels of this interval at Site 548, appear to have an ice-rafting origin. This study points out three main breaks in the general evolution of the sedimentation: the first, corresponding to the lower/middle Eocene boundary, is marked by the increase of carbonates and associated elements; the second, corresponding to the middle/upper Miocene boundary, is marked by a major decrease of the smectite/(illite + chlorite) ratio at all sites and by a massive appearance of quartz at Site 548; and the third, which occurred toward the late Pliocene, is marked by the dominance of primary clay minerals and the arrival of ice-rafted pebbles. Our interpretation of results considers paleohydrological and paleoclimatic phenomena. It is suggested that the major middle/late Miocene break was associated with an increase of the deep bottom-water circulation between the Norwegian Sea and the North Atlantic Ocean, and/or a climatic evolution: humidification and cooling of climate. The changes toward the late Pliocene appear to have been the first effects of the glaciations at the end of Cenozoic.

Sediment geochemistry and water trace metal concentration in Potter Cove

Recent rapid climate warming at the western Antarctic Peninsula (WAP) results in elevated glacial melting, enhanced sedimentary run-off, increased turbidity and impact of ice-scouring in shallow coastal areas. Discharge of mineral suspension from volcanic bedrock ablation and chronic physical disturbance is expected to influence sessile filter feeders such as the Antarctic soft shell clam Laternula elliptica ( King and Broderip, 1832). We investigated effects of sedimentary run-off on the accumulation of trace metals, and together with physical disturbance, the cumulative effect on oxidative stress parameters in younger and older L. elliptica from two stations in Potter Cove (King George Island, Antarctica) which are distinctly impacted by turbidity and ice-scouring. Fe, Mn, Sr, V and Zn concentrations were slightly higher in sediments of the station receiving more sediment run-off, but not enriched in bivalves of this station. The only element that increased in bivalves experimentally exposed to sediment suspension for 28 days was Mn. Concentration of the waste accumulation biomarker lipofuscin in nervous tissue was higher in L. elliptica from the "exposed" compared to the "less exposed" site, whereas protein carbonyl levels in bivalve mantle tissue were higher at the less sediment impacted site. Tissue metal content and lipofuscin in nervous tissue were generally higher in older compared to younger individuals from both field stations. We conclude that elevated sediment ablation does not per se result in higher metal accumulation in L. elliptica. Instead of direct absorbance from sediment particles, metal accumulation in gills seems to indicate uptake of compounds dissolved in the water column, whereas metals in digestive gland appear to originate from enriched planktonic or detritic food. Accumulation of cellular waste products and potentially reactive metals over lifetime presumably alters L. elliptica physiological performance with age and may contribute to higher stress susceptibility in older animals.

Data on multidisciplinary research in the Tajura Rift (Gulf of Aden) during Cruise 7 of R/V Akademik Mstislav Keldysh in winter 1983-1984

In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.

Bulk chemical analysis of sediments ODP Hole 110-671B and 110-672A

Chemical analyses for calcium carbonate, organic carbon, and major constituents (Al, Ti, Ca, Mg, K, Fe) of bulk sediments collected in Hole 671B have been carried out. Organic carbon contents in Pleistocene through middle Miocene sediments above the zone of decollement are very low (<0.1%); below the decollement considerably higher concentrations of organic carbon occur (up to 1 %). Changes in Ti/Al and Fe/Al ratios are minor, but K/Al and Mg/Al ratios show clear trends with the age of the sediments. Preliminary comparisons of these ratios with mineralogic information on clays indicate good correspondence with clay abundances. Calculations of the mass flux of magnesium from the overlying ocean into the pore fluids suggest that addition of magnesium to the sediments is difficult to detect, especially in the absence of a background reference concentration.

Crecimiento y caracterización de Nitruro de Indio por epitaxia de haces moleculares para aplicaciones en el infrarrojo cercano

Los nitruros del grupo III (InN, GaN y AlN) se han asentado como semiconductores importantes para la fabricación de dispositivos optoelectrónicos gracias al amplio rango de la banda prohibida ("bandgap") de estos materiales (0.7-6.2 eV) y a que dicho bandgap sea directo. Asimismo, el marcado carácter iónico de los enlaces en estos materiales les confiere una gran estabilidad química y térmica, haciéndoles así buenos candidatos para trabajar en entornos agresivos. La técnica de crecimiento epitaxial más extendida para los nitruros del grupo III es la epitaxia en fase vapor mediante precursores metalorgánicos (MOVPE) y mediante ésta se han obtenido dispositivos optoelectrónicos de alta eficiencia como los comercializados por Nichia, Sony y Toshiba entre otros. Esta técnica necesita de alta temperatura para la pirólisis de los gases reactivos, lo que a su vez incrementa la calidad cristalina de los materiales obtenidos. Sin embargo, tiene como inconvenientes la existencia de niveles altos de carbono, hidrógeno y otros compuestos orgánicos, procedentes de los precursores, que puede provocar efectos negativos de pasivación sobre los dopantes. Otra técnica de crecimiento utilizada para la obtención de nitruros del grupo III es por medio de epitaxia de haces moleculares (MBE) la cual presenta algunas ventajas sobre el MOVPE, por ejemplo: (i) el entorno de ultra alto vacío requerido (presiones base del orden de 10-11 Torr) minimiza la concentración de impurezas incorporadas al material, (ii) la pureza de los materiales empleados en las fuentes de efusión siempre superan el 99,9999%, (iii) la posibilidad de interrumpir el flujo de cualquiera de los elementos (Ga, In, Al, Si, Mg, etc.) de una manera abrupta (mediante el uso de obturadores mecánicos) dando lugar a intercaras planas a nivel atómico, y (iv) la posibilidad de reducir la velocidad de crecimiento (1 nm/min) permitiendo un control preciso del espesor crecido, y por tanto, fabricar estructuras semiconductoras complejas como las basadas en pozos cuánticos. Desde 1986 hasta la actualidad se ha mejorado mucho la calidad cristalina de las capas de InN, obteniéndose actualmente mediante estas técnicas de crecimiento, capas de InN con un valor de bandgap en torno 0.7 eV. Gracias a los numerosos trabajos presentados sobre las propiedades ópticas de este material, el intervalo de operación de los nitruros del grupo III dentro del espectro electromagnético se ha extendido hasta el infrarrojo cercano. Este hecho ha despertado un gran interés en nuevas aplicaciones, como en el campo fotovoltáico con la fabricación de células solares de multi-unión de alta eficiencia cubriendo todo el espectro solar. Se ha detectado también en este material una importante acumulación de carga eléctrica en la superficie, del orden de 1013 e-cm-2. Esta cantidad de electrones parecen acumularse en una capa de unos 4 a 6 nanómetros, incrementando la conductividad de las capas de InN. Si bien esta alta carga superficial podría utilizarse para la fabricación de sensores, ésta no es la única característica que apoya el uso del InN para la fabricación de este tipo de dispositivos. El principal objetivo de esta tesis es el estudio y optimización del crecimiento mediante la técnica de MBE de capas de nitruro de indio para aplicaciones en el rango del infrarrojo cercano. La optimización conlleva el control de la morfología y el estudio de las propiedades ópticas y eléctricas de las capas crecidas. Este objetivo principal se puede concretar en varios puntos relacionados con (i) el crecimiento de capas de nitruro de indio (InN) y sus aleaciones con galio (InGaN) y aluminio (AlInN), (ii) la caracterización de dichas capas, y (iii) el diseño, crecimiento y caracterización de heteroestructuras para aplicaciones en el rango del infrarrojo cercano. El crecimiento de capas de InN utilizando diferentes sustratos se ve afectado fundamentalmente por la temperatura de crecimiento pudiéndose afirmar que es el parámetro más crítico. El otro parámetro importante que gobierna la morfología y la calidad cristalina de las capas es la razón III/V que ha de ser precisamente controlado. Con razones III/V<<1 y a una temperatura lo suficientemente baja, se obtiene un material formado por nanocristales columnares de muy alta calidad, libres de defectos extendidos y completamente relajados, con una emisión muy intensa. Para la misma temperatura que en el caso anterior y razones III/V ligeramente por encima de estequiometría (III/V > 1), las capas obtenidas presentan una morfología compacta. Aunque también es posible obtener capas compactas en condiciones nominalmente ricas en nitrógeno (III/V <1) a temperaturas superiores.

Optical properties of ZnMgO films grown by spray pyrolysis and their application to UV photodetection

This work presents a comprehensive optical characterization of Zn1−xMgxO thin films grown by spray pyrolysis (SP). Absorption measurements show the high potential of this technique to tune the bandgap from 3.30 to 4.11 eV by changing the Mg acetate content in the precursor solution, leading to a change of the Mg-content ranging from 0 up to 35%, as measured by transmission electron microscopy-energy dispersive x-ray spectroscopy. The optical emission of the films obtained by cathodoluminescence and photoluminescence spectroscopy shows a blue shift of the peak position from 3.26 to 3.89 eV with increasing Mg incorporation, with a clear excitonic contribution even at high Mg contents. The linewidth broadening of the absorption and emission spectra as well as the magnitude of the observed Stokes shift are found to significantly increase with the Mg content. This is shown to be related to both potential fluctuations induced by pure statistical alloy disorder and the presence of a tail of band states, the latter dominating for medium Mg contents. Finally, metal–semiconductor–metal photodiodes were fabricated showing a high sensitivity and a blue shift in the cut-off energy from 3.32 to 4.02 eV, i.e., down to 308 nm. The photodiodes present large UV/dark contrast ratios (102 − 107), indicating the viability of SP as a growth technique to fabricate low cost (Zn, Mg)O-based UV photodetectors reaching short wavelengths.

Modes of occurrence and geochemistry at DSDP Holes 69-505A and 69-505B

The compositions of chrome spinels of Costa Rica Rift basalts from Deep Sea Drilling Project Site 505 vary depending on their occurrences as (1) inclusions in olivine crystals, (2) inclusions in Plagioclase crystals, and (3) isolated crystals in variolitic or glassy samples. The variations are a consequence of (1) changes of melt compositions as crystallization proceeds, and (2) contrasting behavior of olivine and Plagioclase in competition with spinels for Al and Mg. Some spinels have skeletal rims compositionally less magnesian than mineral cores; however, the cores do not appear to be xenocrysts, unlike some texturally similar spinels in Mid-Atlantic Ridge basalts.

Ge/Si ratios in marine siliceous microfossils

A procedure is presented to separate diatoms and radiolaria from marine sediments and from each other, to purify them of elements associated with other phases, and to dissolve them to determine their elemental composition. The cleaning procedure eliminates artifacts due to the presence of detrital clays and the high sorption capacity of hydrated silica. The concentration of trace elements (Al, Fe, Mg, and Ba) that we find in alkaline dissolutions of clean diatoms are at least an order of magnitude lower than previously reported. The overall long-term precision in the determination of Ge/Si in a sub-standard of clean diatoms is ±0.024 * 10**-6 (1 sigma). Ge/Si measured in diatoms and radiolaria from core tops indicates that high-latitude Holocene diatoms accurately record the present-day oceanic Ge/Si, while radiolarian ratios are systematically lower and display more scatter. Evaluation of Ge/Si in diatoms and radiolaria from Hole DSDP 265 (Plio-Pleistocene) suggests that post-depositional alteration of the ratio does not occur at this site, but the average ratio carried by diatoms over this time interval was lower than that in the present ocean.

Transmission electron microscopy sample preparation technique for sintered alloys

Powder metallurgy alloys are typically inhomogeneous with a significant amount of porosity. This complicates conventional transmission electron microscopy sample preparation. However, the use of focused ion beam milling allows site specific transmission electron microscopy samples to be prepared in a short amount of time. This paper presents a method that can be used to produce transmission electron microscopy samples from an Al-Cu-Mg PM alloy. (C) 2003 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

Microchemistry and microstructures of hydrothermally altered shock-metamorphosed basement gneiss, Woodleigh impact structure, Southern Carnarvon Basin, Western Australia

Hydrothermally altered shock-metamorphosed gneisses consisting of relic igneous biotite-K-feldspor-Na-rich alkali feldspar - plagioclase - quartz assemblages ( accessory garnet, corundum, titanite, monazite, zircon), and showing extensive replacement by montmorillonite, illite, sericite, and to a lesser extent chlorite, calcite, epidote, zoisite and pyrite, occur in the basement core uplift of the Woodleigh impact structure, Western Australia. The rocks display extensive hydrothermal clay alteration, complicating identification of pre-hydrothermal and pre-impact textures and compositions. Analysis of quartz-hosted planar deformation features (PDFs) indicates a majority of indexed sets parallel to omega{10 (1) over bar3}, a lesser abundance of sets parallel to pi{10 (1) over bar2}, and some sets parallel to the basal plane (0001) and r,z {10 (1) over bar1}, consistent with pressures about or over 20 GPa. Feldspar-hosted FDFs form reticulate vein networks displaying checkerboard-like to irregular and serrated patterns attributable to preferential replacement of shock-damaged PDFs and/or perthitic twin lamella by clay minerals. The gneisses are pervaded by clay-dominated intergranular and intragranular veins of cryptocrystalline material that display marked departures from bulk-rock chemistry and from mineral compositions. XRD analysis identifies the cryptocrystalline components as illite - montmorillonite, illite and chlorite, while laser Raman analysis identifies high-fluorescence sub-micrometre clay assemblage, feldspar, quartz and minor mica. SEM/EDS-probe and laser-ICPMS analysis indicate low-K high-Mg clay mineral compositions consistent with montmorillonite. Quartz PDF-hosted cryptocrystalline laminae display distinct enrichments in Al, Mg, Ca and K. Altered intergranular veins and feldspar-hosted cryptocrystalline components show consistent enrichment in the relatively refractory elements (Al, Cc, Mg, Fe) and depletion in relatively volatile elements (Si, K, Na). The clay alteration retards determination whether clay-dominated vein networks represent altered shock-induced pseudotachylite veins, diaplectic zones and/or shock-damaged twin lamella, and/or result from purely mineralogical and chemical differentiation affected by hydrothermal fluids, Overall enrichment of the shocked gneiss and of the cryptocrystalline components in Mg and trace ferromagnesian elements (Ni, Cc, Cr) may be attributed alternatively to introduction of siderophile element-rich fluid from the projectile, or/and contamination of hydrothermal fluids by MgO from dolomites surrounding the basement uplift. High Ni/Co and Ni/Cr and anomalous DGE (platinum group elements) may support the former model.

Are metal ions accumulated by saxicolous lichens growing in a rural environment?

The levels of Mn, Cu, zn, Mg and Ca were measured in the lichens Xanthoparmelia conspersa (Ach.) Hale and Parmelia glabratula ssp. fuliginosa (Fr. ex Duby): Laund. growing on a steep slate rock surface in south Gwynedd, Wales, UK. The objective was to test the following hypotheses: 1) that foliose lichens growing in a rural environment concentrate metal ions relative to the substratum, 2) that the concentration of metal ions increases significantly with thallus size and 3) that individual ions accumulate preferentially either in the marginal lobes or thallus centre. Mg and Ca were present in rainfall whereas all ions were present in rock surface runoff and in the substratum. Levels of Mn, Mg and Ca were increased in runoff collected from the bottom compared with the top of the rock surface. In P. glabratula ssp. fuliginosa thalli, ions were present as follows, Mg > Ca=Mn=Zn>Cu, and there were no significant differences in thalli collected from the top and bottom of the rock surface. With the exception of Mg and Ca, ion levels in thalli were similar to or less than those in the substratum. The levels of Ca, Cu and Zn were similar in thalli from under 1 to over 4 cm in diameter. However, the level of Mg increased with thallus size in X. conspersa while the level of Mn decreased with thallus size in both species. Ion levels were similar in the marginal lobes and centres of large diameter (over 4 cm) and small diameter (under 2 cm) X. conspersa thalli. With the exception of Mg, there was no evidence for a significant accumulation of ions relative to the substratum or with thallus size. In addition, there was no evidence to suggest preferential accumulation of ions either in the thallus centre or marginal lobes.

The deoxidation of steel with simple and complex deoxidisers

The deoxidation of steel with complex deoxidisers was studied at 1550°C and compared with silicon, aluminium and silicon/aluminium alloys as standards. The deoxidation alloy systems, Ca/Si/Al, Mg/Si/Al and Mn/Si/Al, were chosen for the low liquidus temperatures of many of their oxide mixtures and the potential deoxidising power of their constituent elements. Product separation rates and compositional relationships following deoxidation were examined. Silicon/aluminium alloy deoxidation resulted in the product compositions and residual oxygen contents expected from equilibrium and stoichiometric considerations, but with the Ca/Si/Al and Mg/Si/Al alloys the volatility of calcium and magnesium prevented them participating in the final solute equilibrium, despite their reported solubility in liquid iron. Electron-probe microanalysis of the products showed various concentrations of lime and magnesia, possibly resulting from reaction between the metal vapours and dissolved oxygen.The consequent reduction of silica activity in the products due to the presence of CaO and hgO produced an indirect effect of calcium and magnesium on the residual oxygen content. Product separation rates, indicated by vacuum fusion analyses, were not significantly influenced by calcium and magnesium but the rapid separation of products having a high Al2O3Si02 ratio was confirmed. Manganese participated in deoxidation, when present either as an alloying element in the steel or as a deoxidation alloy constituent. The compositions of initial oxide products were related to deoxidation alloy compositions. Separated products which were not alumina saturated, dissolved crucible material to achieve saturation. The melt equilibrated with this slag and crucible by diffusion to determine the residual oxygen content. MnO and SiO2 activities were calculated, and the approximate values of MnO deduced for the compositions obtained. Separation rates were greater for products of high interfacial tension. The rates calculated from a model based on Stoke's Law, showed qualitative agreement with experimental data when corrected for coalescence effects.

Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis

A series of [Mg(1−x)Alx(OH)2]x+(CO3)x/n2− hydrotalcite materials with compositions over the range x = 0.25–0.55 have been synthesised using an alkali-free coprecipitation route. All materials exhibit XRD patterns characteristic of the hydrotalcite phase with a steady lattice expansion observed with increasing Mg content. XPS measurements reveal a decrease in both the Al and Mg photoelectron binding energies with Mg incorporation which correlates with the increased intra-layer electron density. All materials are effective catalysts for the liquid phase transesterification of glyceryl tributyrate with methanol for biodiesel production. The rate increases steadily with Mg content, with the Mg rich Mg2.93Al catalyst an order of magnitude more active than MgO, with pure Al2O3 being completely inert. The rate of reaction also correlates with intralayer electron density which can be associated with increased basicity.© 2005 Elsevier B.V. All rights reserved.