Synthesis and physical properties of piemontite Ca2Al3-pMn p 3+ (Si2O7/SiO4/O/OH)

Mn³⁺-bearing piemontites and orthozoisites, Ca₂(Al_3-pMn³⁺ _p)-(Si₂O₇/SiO₄/O/OH), have been synthesized on the join Cz (p = 0.0)-Pm (p = 3.0) of the system CaO-Al₂O₃-(MnO·MnO₂)-SiO₂-H₂O atP = 15 kb,T= 800 °C, and \(f_{O_2 } \) of the Mn₂O₃/MnO₂ buffer. Pure Al-Mn³⁺-piemontites were obtained with 0.5≦p≦1.75, whereas atp=0.25 Mn³⁺-bearing orthozoisite (thulite) formed as single phase product. The limit of piemontite solid solubility is found near p=1.9 at the above conditions. Withp>1.9, the maximum piemontite coexisted with a new high pressure phase CMS-X1, a Ca-bearing braunite (Mn _0.2 ²⁺ Ca_0.8)Mn ₆ ³⁺ O₈(SiO₄), and quartz. Al-Mn³⁺-piemontite lattice constants (LC),b ₀,c ₀,V ₀, increase with increasingp:

Mn3+ in garnets III. Absence of Jahn-Teller distorition in synthetic Mn3+-bearing garnet

Physics and Chemistry of Minerals - The crystal structure of a ternary Mn3+-bearing garnet, close to the composition Gross34 Spess26 CaMnGt40 has been refined to a weighted R-value of 0.051 for 440...     

Microscope-photometric methods for non-destructive Fe2+ – Fe3+ determination in chloritoids (Fe2+, Mn2+, Mg)2 (Al,Fe3+)4 Si2O10(OH)4

Six natural chloritoid crystals with Fe²⁺ and Fe³⁺ contents ranging from 4.15 to 12.81 and from 0.411 to 0.849g-atoms/l, respectively, as determined by means of microprobe and Mössbauer techniques, served as reference material to develop non-destructive microscope-spectrophotometric methods for quantitative Fe²⁺ – Fe³⁺ determinations in chloritoids from unpolarized spectra of (001) platelets. Fe²⁺ concentrations in g-atom/l can be obtained from [ [Fe³⁺]=C₁xD₁/t where D₁ = log₁₀(I_0/I at 28,000 cm^-1 and t=crystal thickness in cm; C₁ is a conttant that may be influenced somewhat by experimental conditions and is found to be 0.002289 with the experimental set-up used in this study. Fe²⁺ concentrations in g-atom/l can be obtained from [Fe²⁺]=C₁xD₁/D₁-C₃ with D₂=log₁₀(I₀/I) at 16,300 cm^?1 and constants C₄ = 45.36 and C₅ = 3.540. Due to the uncertainties in absorbance measurements, D₁ and D₂ and the thickness measurements, the accuracies are ±0.05 and ±0.15 g-atom/l for [Fe³⁺] and [Fe²⁺], respectively. The determinations may be carried out on chloritoid grains in normal thin sections with an areal resolution of ～10 μm.     

Electronic absorption spectroscopy of natural (Fe2+, Fe3+)-bearing spinels of spinel s.s.-hercynite and gahnite-hercynite solid solutions at different temperatures and high-pressures

Natural Fe²⁺, Fe³⁺-bearing spinel solid solutions from the spinel s.s.-hercynite and gahnite-hercynite series were analyzed and studied by electronic absorption spectroscopy in the spectral range 30000–3500 cm^–1 in the temperature and pressure ranges 77 T_K 600 and 10^–4 P_GPa 11.0. Two crystals were light-violet in color (type I) and six green or bluish-green (type II). The spectra of both types of spinels are dominated by an UV-absorption edge near 28000 to 24000 cm^–1, depending on the iron contents, and a very intense band system in the NIR centered around 5000 cm^–1, which is caused by spin-allowed dd-transition of tetrahedral Fe²⁺, derived from ⁵ E⁵ T₂. The strong band is in all spinels studied, split into four sub-bands, which can only be observed in very thin platelets. Between the UV-edge and the high-energy wing of the NIR-band there occur a number of very weak bands in type I spinels while the green type II spinels show some of these with significantly enhanced intensity. The intensity of the very weak bands is nearly independent from temperature. Such bands are attributed to spin-forbidden electronic transitions of ^IVFe²⁺. Temperature and pressure dependence of the intensity enhanced bands of spinels type II indicate that they are caused by ^IVFe²⁺ and ^VIFe³⁺. They are attributed to spin-forbidden transitions ⁶A_1g⁴A_1g, ⁴E_g, ⁴T_2g and ⁴T_1g of ^VIFe³⁺, the two latter being strongly intensified by exchange-coupling interaction with adjacent ^IVFe²⁺. The pressure dependence of ^IVFe²⁺ dd-band system in the NIR caused by spin-allowed ⁵ E⁵ T₂ transition noticeably differs from that of octahedral Fe²⁺, an effect which is attributed to a dynamic Jahn-Teller effect of ^IVFe²⁺ in the spinel structure.

Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—Cobalt-containing olivines

Polarized electronic absorption spectra of single crystalline Co₂[SiO₄] and (Co_0.64Mg_0.36)₂[SiO₄] (E|| a (|| Z), E || b (|| X), E || c (|| Y)) have been studied in the temperature range 293 T/K 1273. The three polarized spectra show a total of 15 bands. Five bands are caused by spin-allowed transitions in Co²⁺ ions at M1 sites which appear in all polarization directions. Seven polarization-dependent bands can be ascribed to spin-allowed transitions in Co²⁺ ions at M2 sites and three bands may be assigned to spin-forbidden transitions. The assignment of bands due to Co²⁺ ions at M1 and M2 sites has been made on the basis of transition energies and intensity ratios. Further arguments have been derived from the comparison of spectra of crystals with different cobalt content, from the analysis of the polarization dependence of the spectra, and from the evolution of band intensities with temperature.     

Saisonales Vorkommen von Arten der Saprolegniales und Leptomitales im Auesee und in der Fulda in Kassel (Hessen) unter Berücksichtigung fischpathogener Arten

Seasonal Occurrence of Species of Saprolegniales and Leptomitales in Lake Aue and the River Fulda in Kassel (Hesse) with Special Consideration of Fish Pathogenic Species In this study, we examined the occurrence of species of aquatic Oomycetes of Saprolegniales und Leptomitales in Lake Aue and the river Fulda in Kassel (Hesse, Germany) with special consideration of fish pathogenic species. We monthly collected water samples of both water bodies from July 2003 to June 2004. The baiting method was used to gain an insight into the specific seasonal occurrence of aquatic Oomycetes. Some species show a seasonal periodicity. Nine of 11 species of Saprolegniales isolated from the two water bodies, and Leptomitus lacteus (Roth) C. Agardh, one of the two species of Leptomitales, were already documented on fish according to references. Additionally, 7 of 10 species could according to references already be detected on fish species present in the two water bodies. Simultaneous measurements of limnological‐chemical parameters were done during the sampling of water for the isolation of aquatic Oomycetes. The results of some measurements, concerning the river Fulda, were additionally compared with the predetermined guideline values and limit values of water bodies of fish of the “Cyprinid region”.     

Spatial and seasonal variability of polygonal tundra water balance: Lena River Delta, northern Siberia (Russia)

The summer water balance of a typical Siberian polygonal tundra catchment is investigated in order to identify the spatial and temporal dynamics of its main hydrological processes. The results show that, besides precipitation and evapotranspiration, lateral flow considerably influences the site-specific hydrological conditions. The prominent microtopography of the polygonal tundra strongly controls lateral flow and storage behaviour of the investigated catchment. Intact rims of low-centred polygons build hydrological barriers, which release storage water later in summer than polygons with degraded rims and troughs above degraded ice wedges. The barrier function of rims is strongly controlled by soil thaw, which opens new subsurface flow paths and increases subsurface hydrological connectivity. Therefore, soil thaw dynamics determine the magnitude and timing of subsurface outflow and the redistribution of storage within the catchment. Hydraulic conductivities in the elevated polygonal rims sharply decrease with the transition from organic to mineral layers. This interface causes a rapid shallow subsurface drainage of rainwater towards the depressed polygon centres and troughs. The re-release of storage water from the centres through deeper and less conductive layers helps maintain a high water table in the surface drainage network of troughs throughout the summer.     

Geochemical pattern classification of recent volcanic products from Mt. Etna, Italy, based on Kohonen maps and fuzzy clustering

We present the application of a classification method based on Kohonen maps and fuzzy clustering to geochemical analyses of volcanic products erupted on Mt. Etna from 1995 to 2005. Based on 13 major and trace elements, the classification allows a new way to visualize distinct compositional features of magma both considering long period as well as single eruptive events, such as in 2001 and 2002–03 flank eruptions. Products of the various vents do not necessarily form homogeneous groups, but show clear trends of chemical evolution with time. Using a convenient color code, the graphical visualization of the results in just a single picture allows the rapid identification of the compositional features of each sample and their comparison with all the products analyzed in the 10-year-long time span. This single picture accounts for the mutual interactions of the 13 components avoiding shortcomings of classical low-dimensional plots where components relevant for the discrimination have to be found in a priori study of many diagrams. On the basis of the synoptic information provided by pattern classification, we identify links between the products of different eruptive vents which deliver a reliable picture of a multifaceted plumbing system, in agreement with geochemical and geophysical evidence reported in literature. The analysis of the 13-dimensional data set using the Kohonen maps and fuzzy clustering simultaneously turned out to be straightforward and easy. Accordingly, the results of this application will be useful also as a contextual data set for new data in future ongoing eruptive episodes.     

Palaeolimnology of Lake Zeribar, Iran, and its climatic implications

Lake Zeribar sediments covering the time period of the last 25,000 years were examined for the contents of seeds, fruits, Characeae, diatoms, and molluscs. Reconstructions of the variations in the lake water level, salinity, and trophy suggest a sequence of climatic changes. Three pronounced stages of low and varying lake-water level occurred ca. 17,700–15,400, 12,600–12,000, and 10,000–6000 cal yr BP. Some water-level changes were correlated with variations in salinity. The most pronounced increase of salinity occurred 17,700–15,700 and 12,600–12,000 cal yr BP, and less distinct ones occurred about 6400–5900 and 2500 cal yr BP. Diatom assemblages indicated a strong increase of lake trophy ca. 20,200 cal yr BP. Between 6000 and 5000 cal yr BP diatoms characteristic of eutrophy increased in core 63J, and at about 3200 cal yr BP a distinct increase in mesotrophic forms occurred in core 70B. The changes in the occurrence of various organisms indicate increased temperatures about 21,000 cal yr BP, between 15,400 and 12,600, about 12,000, and about 11,700 cal yr BP. The reduced occurrence or disappearance of some of them suggest temperature decreases about 17,700–15,400 and 12,600–12,000 cal yr BP.