The crystal structure of bøgvadite (Na2SrBa2Al4F20)

The crystal structure of bøgvadite, Na₂SrBa₂Al₄F₂₀, has been solved and refined to a R₁ factor of 4.4 % from single-crystal data (MoKα X-ray diffraction, CCD area detector) on a sample from the cryolite deposit at Ivittuut, SW Greenland. Bøgvadite is monoclinic, P2₁/n space group, with unit cell parameters a?=?7.134(1), b?=?19.996(3) and c?=?5.3440(8) Å, β?=?90.02(1)^o. A close proximity of the crystal structure to an orthorhombic symmetry and the presence of the two twin components in a nearly 1:1 ratio suggest that the investigated bøgvadite crystal has originally formed as a high-temperature orthorhombic polymorph which on cooling transformed to the stable low temperature monoclinic structure. The bøgvadite crystal structure has groupings of cation-fluoride coordination polyhedra similar to those found in the crystal structures of the genetically closely associated minerals jarlite and jørgensenite. However, its structure type is different from the latter two. The fluoridoaluminate framework of bøgvadite consists of infinite zig-zag chains of cis-connected AlF₆ coordination octahedra. The ¹ _∞[AlF₅] chains are interconnected by infinite chains of Na-F coordination polyhedra which extend in the same direction. Na is coordinated by nine F atoms if its full surrounding is taken in consideration, but makes significant chemical bonds only to closest five. The chains of AlF₆ and NaF₉ coordination polyhedra form double layers. In the centre of layers, relatively large voids in the form of pentagonal antiprisms are occupied by Sr atoms which make chemical bonds with the closest six F atoms. Between the SrF₁₀ coordinations in the centre of layers run empty channels. The double layers are interconnected by Ba atoms which are coordinated by eight F atoms and fill the spaces between the layers. Bøgvadite belongs to the group of fluoridoaluminates with infinite chains of cis-connected AlF₆ coordination octahedra, alike those found in the crystal structures of Ba-fluoridoaluminates.     

Study of groundwaters using the environmental tritium and hydrochemical data in the Belgrade region

A study of tritium content and some physicochemical parameters has been performed in order to investigate interconnection between surface and atmospheric waters and underground waters in Belgrade area. Samples of the precipitation at Zeleno Brdo-Belgrade meteorological station, the Danube and the Sava river water, and underground water (Ranney wells and piezometers) have been analyzed. The³H content, the content of dissolved ions, total hardness, and electrical conductivity have been measured. The tritium data show existence of two water strata in the aquifer. The upper stratum (about 16 m thick) contains older water (mean monthly³H concentration of 17 TU) and has weak interaction with the river and the precipitation. Below this stratum lies the principal water bearing stratum, strongly connected with the river with the³H concentration similar to that of surface water (mean monthly³H concentration of 50 TU) and spreading out through the entire aquifer. The contribution of the Sava river water and the two water layers at the Ranney well are calculated starting with the hydrological aquifer model, which supposes that three water components are mixed in the pumped Ranney well water. According to calculation results using the³H concentration and physicochemical characteristics as parameters, more than 70 percent of the water pumped by the Ranney well (in 1983) comes from the Sava with a time delay of less that 15 days.Properties of tritium distribution in precipitation, river waters, and underground water in the Belgrade region are established from the results of measurements of³H concentrations in the period 1976–1983.     

Inertial Effects on the Vertical Transport of Suspended Particles in a Turbulent Boundary Layer

In many atmospheric flows, a dispersed phase is actively suspended by turbulence, whose competition with gravitational settling ultimately dictates its vertical distribution. Examples of dispersed phases include snow, sea-spray droplets, dust, or sand, where individual elements of much larger density than the surrounding air are carried by turbulent motions after emission from the surface. In cases where the particle is assumed to deviate from local fluid motions only by its gravitational settling (i.e., they are inertialess), traditional flux balances predict a power-law dependence of particle concentration with height. It is unclear, however, how particle inertia influences this relationship, and this question is the focus of this work. Direct numerical simulations are conducted of turbulent open-channel flow, laden with Lagrangian particles of specified inertia; in this way the study focuses on the turbulent transport which occurs in the lowest few meters of the planetary boundary layer, in regions critical for connecting emission fluxes to the fluxes felt by the full-scale boundary layer. Simulations over a wide range of particle Stokes number, while holding the dimensionless settling velocity constant, are performed to understand the role of particle inertia on vertical dispersion. It is found that particles deviate from their inertialess behaviour in ways that are not easily captured by traditional theory; concentrations are reduced with increasing Stokes number. Furthermore, a similarity-based eddy diffusivity for particle concentration fails as particles experience inertial acceleration, precluding a closed-form solution for particle concentration as in the case of inertialess particles. The primary consequence of this result is that typical flux parametrizations connecting surface emission models (e.g., saltation models or sea-spray generation functions) to elevated boundary conditions may overestimate particle concentrations due to the reduced vertical transport caused by inertia in between; likewise particle emission may be underestimated if inferred from concentration measurements aloft.     

Modelling of atmospheric dispersion of heavy metals in the Celje area,Slovenia

The aim of this research was to determine how fast the level of heavy metal concentrations in the air decreases in relation to increasing distance from the source of pollution and what the influence area is of the zinc smelting plant which existed for 100 years in Celje. In that period it produced approximately 580,000 tons of raw Zn from sphalerite ore by the pyrometallurgical process. The production left behind a heavily contaminated area, where the concentrations of Pb and Zn in the soil can be expressed as a percentage. A model has been made on the basis of the data of concentrations of Zn and Cd in the soil and attic dust regarding the distance and direction from the source of the pollution. Because Celje lies in a basin we chose a linear model, which describes the decreasing of the concentrations of Zn and Cd only in one direction. Sampling has been conducted on the four river valleys which stretch from the source of the pollution in all four directions: north, west, south and east, up to 13 km from the source. The power function with a negative exponent was used. With the solution to the calculated functions according to the distance, we can estimate the theoretical distance when the concentrations drop to the natural background level. The range of influence of the zinc smelting plant has been estimated to be between 14 and 52 km for the presence of anthropogenic Zn in attic dust and between 9 and 14 km for the presence of anthropogenic Zn in the soil, depending on the direction from the plant. Correlations between the measured values and the ones from the model are high: from 0.75 up to 0.98.     

The provenance of Australian uranium ore concentrates by elemental and isotopic analysis

Elemental and isotopic ratio analyses of U ore concentrate samples, from the 3 operating U mining facilities in Australia, were carried out to determine if significant variations exist between their products, thereby allowing the U ore concentrate’s origin to be identified. Elemental analyses were conducted using inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF). Lead isotope ratios were measured using ICP-MS and U isotope analyses were conducted using thermal ionisation mass spectrometry (TIMS). Minute quantities of sample, such as that obtained from a swipe, were also examined for elemental concentrations using secondary ion mass spectrometry (SIMS). The results of multivariate statistical analysis show clear patterns in the trace elemental composition of the processed U ores, indicating that it is possible to use this feature as a unique identifier of an Australian U ore concentrate’s source. Secondary ion mass spectrometry analyses also allow individual particles to be differentiated using this ‘fingerprinting’ technique. Isotope ratios determined using TIMS reveal that there is a significant difference in the n(²³⁴U)/n(²³⁸U) isotope ratio between the U ore concentrate from each mine.     

Magnesium isotope fractionation in silicate melts by chemical and thermal diffusion

Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100-200 °C from one end to the other. The chemical diffusion experiments showed fractionations of ²⁶Mg/²⁴Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to D_26Mg/D_24Mg=(24/26)^β with β = 0.05. The thermal diffusion experiments showed that a temperature difference of about 100 °C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1 wt% in the colder end while SiO₂ was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150 °C produced an 8‰ enrichment of ²⁶Mg/²⁴Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6 × 10⁻²‰/°C/amu.     

Talc-chlorite-amphibole felses of the KTB pilot hole,Oberpfalz, Bavaria: Protolith characteristics and phase relationships

Summary The metagabbro-amphibolite sequences in the KTB pilot hole contain intercalations of talc-chlorite-amphibole felses (or hosbachites), which show transitional contacts to the adjacent metagabbros. The hosbachites are characterized by relics of a primary igneous texture and still contain igneous minerals like clinopyroxene, biotite and pseudomorphs after olivine, while brown Ca-amphibole was presumably formed in a late-magmatic stage. The geological, textural, mineralogical and geochemical evidence indicates that the hösbachites were derived from ultramafic cumulates, differentiated from a basaltic magma, either in the inner parts of dolerite sills or in small gabbro intrusions. A pervasive metamorphic overprint under medium-pressure, amphibolite-facies conditions which was accompanied by penetrative deformation led to assemblages with green Ca-amphibole ± anthophyllite ± cummingtonite ± tremolite/actinolite + clinochlore + talc + olivine + ilmenite ± Cr-bearing spinel + sulfides. Phase relationships are consistent with a prograde P-T path leading to the formation of anthophyllite from olivine + talc at peak metamorphic temperatures of 640–700°C, at assumed pressures of 8-10 kbar, similar to those derived from mineral assemblages in the adjacent metabasites and metasediments. High-pressure relics locally present in coronitic metagabbros and retrograded eclogites of the KTB pilot hole were not recognized in the hosbachites. A retrograde overprint under greenschist-facies conditions led to the total replacement of igneous or metamorphic olivine by aggregates of antigorite + magnetite, chloritization of biotite and the formation of late tremolite/ actinolite.

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Zusammenfassung Talk- Chlorit-Amphibol-Felse der KTB-Vorbohrung, Oberpfalz: Eduktcharakteristik und Phasenbeziehungen Die Metagabbro-Amphibolit-Folge in der KTB-Vorbohrung enthält Einschaltungen von Talk-Chlorit-Amphibol-Felsen (Hosbachite), die graduelle Übergänge zu den benachbarten Metagabbros aufweisen. Die Hosbachite sind durch Relikte von primären magmatischen Gefügen gekennzeichnet and führen noch magmatische Mineralrelikte wie Klinopyroxen, Biotit and Pseudomorphosen nach Olivin, während brauner CaAmphibol wahrscheinlich spdtmagmatisch gebildet wurde. Verbandsverhältnisse, Reliktgefüge und Reliktminerale sowie Haupt- und Spurenelement-Geochemie sprechen dafür, daß die Hosbachite auf ultramafische Kumulate zurückgehen, die aus einem basischen Magma differenziert wurden, and zwar entweder im Innern von doleritischen Lagergängen oder in kleinen Gabbro-Intrusionen.Eine durchgreifende metamorphe Überprägung unter Bedingungen der Mitteldruck Amphibolitfazies, die von einer penetrativen Deformation begleitet war, fuhrte zu Mineralparagenesen mit grünern Ca-Amphibol ± Anthophyllit ± Cummingtonit + Tremolit/Aktinolith + Klinochlor + Talk + Olivin + Ilmenit + Cr-haltigem Spinell + Sulfiden.Die Phasenbeziehungen weisen darauf hin, daß sich im Zuge eines prograden P-TPfades Anthophyllit aus der Paragenese Olivin + Talk bildete. Als P-T-Bedingungen beim Hbhepunkt der Metamorphose können Temperaturen von 640–700°C in einem angenommenen Druckbereich von 8-10 kbar abgeschätzt wurden, ähnlich wie sie auch aus den Mineralparagenesen in den angrenzenden Metabasiten and Metasedimenten der KTB-Vorbohrung ableitbar sind. Hochdruckrelikte, die gelegentlich in koronitischen Metagabbros and retrograd überprägten Eklogiten der KTB-Vorbohrung auftreten, wurden in den Hösbachiten nicht gefunden. Eine retrograde Überprägung unter grünschieferfaziellen Bedingungen führte zu einer vollständigen Verdrängung von magmatischem und metamorphem Olivin durch Aggregate von Antigorit + Magnetit, zur Chloritisierung von Biotit und zur Bildung einer späten Generation von Tremolit/ Aktinolith.

     

Thermal stability of extended clusters in dravite: a combined EMP,SREF and FTIR study

A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: ^W(F)–^Y(MgMgMg)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]; ^W(OH)–^Y(MgMgAl)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]; ^W(O^2–)–^Y(AlAlAl)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C).