The crystal structure of Ca5(PO4)2SiO4 (Silico-Carnotite)

Summary The crystal structure of Ca₅(PO₄)₂SiO₄ (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR _w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm^–3. The crystal contains about 2.5% V₂O₅ as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO₄ ^3–, SiO₄ ^4– and possibly VO₄ ^3– occurs among the anion sites. The structure has some relationship to that of Ca₅(PO₄)₃OH, the predominant inorganic phase in the human body, but suggests that the Ca₅(PO₄)₃OH type structure may not be stable without some of the OH positions being filled. Ca₅(PO₄)₂SiO₄ is more closely related to K₃Na(SO₄)₂ (glaserite) if it is considered that there are systematic cation vacancies in Ca₅(PO₄)₂SiO₄.This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca₂SiO₄ and Ca₃(PO₄)₂ and between Ca₃(PO₄)₂ and CaNaPO₄.

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Die Kristallstruktur vonCa ₅(PO ₄)₂ SiO ₄ (Silicocarnotit)

Zusammenfassung Die Kristallstruktur von Ca₅(PO₄)₂SiO₄ (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR _w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; D_obs.=3,06 g · cm^–3, D_exp.=3,03 g · cm^–3. Der Kristall enthält etwa 2,5% V₂O₅ als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO₄ ^3–, SiO₄ ^4– und möglicherweise VO₄ ^3– auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca₅(PO₄)₃OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca₅(PO₄)₃OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca₅(PO₄)₂SiO₄ zeigt engere Beziehungen zu K₃Na(SO₄)₂ (Glaserit), wenn man berücksichtigt, daß in Ca₅(PO₄)₃SiO₄ systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit derAuffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca₂SiO₄ und Ca₃(PO₄)₂ und zwischen Ca₃(PO₄)₂ und CaNaPO₄ verantwortlich sind.

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With 9 Figures     

Heavy Metal Load of Sediments of the River Gurk (Carinthia/Austria) — Merits and Limitations of Sequential Leaching Schwermetallbelastung des Sediments der Gurk in Kärnten — Vorzüge und Einschränkungen sequentieller Löseverfahren

By means of the analysis of sediments cored in the small river Gurk (Carinthia/Austria), the input of Ag, Cd, Ce, Cr, Hg, La, Mo, Ni, V, and W from a chemical industrial plant could be detected. To estimate the actual load, and to obtain data for comparison with other sites, both unsieved fine sediments and sediments sieved to 20 μm were investigated from the same cores. Environmental mobilities of toxic heavy metals (Co, Cr, Cu, Ni, Zn) have been shown by sequential leaching following Tessier/Förstner. In the last step, HNO₃ leaches a purely geogenic fraction, which is fairly constant along the investigated river. Whereas the additional Cr from the input of the chemical plant is mainly found in the oxalate-leachable fraction, short-time-load to unpolluted sediments in the laboratory is found mainly in hydroxylamine/acetic acid. Both is due to the high affinity of Cr to Fe- and Mn-oxides. Adsorption/desorption experiments reveal that the low carbonate content of the Gurk sediments increases the importance of Fe/Mn-oxides for the sorption of Cr compared to other samples containing carbonate. The Ni-load was primarily found in weak-acid-leachable and oxalate-leachable fractions. Similarly, the oxalate-leachable fraction is dominant for adsorption of other metals and phosphorus. Other interelement relationships among the amounts leached, which are attributable partly to carbonate-, silicate-, organic or coating phases, have been found by means of factor analyses together with marker fractions for each type.     

Convection driven by centrifugal bouyancy in a rotating annulus

Abstract

Drift rates and amplitudes of convection columns driven by centrifugal bouyancy in a cylindrical fluid annulus rotating about a vertical axis have been measured by thermistor probes. Conical top and bottom boundaries of the annular fluid region are responsible for the prograde Rossby wave like dynamics of the convection columns. A constant positive temperature difference between the outer and the inner cylindrical boundaries is generated by the circulation of thermostatically controled water. Mercury and water have been used as converting fluids. The measurements extend the earlier visual observations of Busse and Carrigan (1974) and provide quantitative data for an eventual comparison with nonlinear theories of thermal Rossby waves. The measured drift frequencies are in general agreement with linear theory. Of particular interest is the decline of the amplitude of convection with increasing Rayleigh number in a region beyond the onset of convection.     

Effects of variable wind shear on the mesoscale circulation forced by slab‐symmetric diabatic heating

Abstract

We examine the response of stably stratified airflow to a slab‐symmetric diabatic forcing associated with condensation in long‐lasting precipitation bands. The steady‐state linearized Boussinesq equations are used to model the diagnostic relationship between the vertical motion field, the heating source and the ambient flow. The basic‐state flow is assumed to be horizontally uniform and non‐rotating, but the static stability and wind vary in the vertical. Linear theory shows that the speed of the along‐band wind component is unimportant for slab‐symmetric heating since it cannot contribute towards the advection of buoyancy or vertical motion.

For typical atmospheric stratification and a moving heating source associated with a cloud band, the Taylor‐Goldstein equation is solved numerically. The numerical results show that the cross‐band wind shear tilts the updraft core and broadens it. While the magnitude of the shear is increased, the circulation becomes stronger. The details of the wind profile are also important in determining the intensity and structure of the circulation. When the wind profile indicates a convex bulge (i.e. the low‐level shear is weaker than the upper‐level shear), the circulation becomes slightly weaker in comparison with the linear wind profile. Conversely, the circulation becomes stronger when the wind profile has a concave shape. Increasing the concave bulge tends to enhance the circulation but not in a monotonic fashion. This non‐monotonic relation between the vertical motion and the parabolic wind profile is interpreted in terms of kinetic energy changes of parcels that interchange their altitudes.     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.     

地层错动引起的上覆饱和黏土层变形特性的离心试验研究

地震断层错动会引起上覆土层变形,从而造成断层附近的建筑结构、管线产生附加的变形和内力引起破坏。通过一个土工离心机试验分析上覆饱和黏土层在4步连续断层错动作用下的静力响应行为。着重分析断层错动引起的地层变形的范围、不均匀沉降区的分布特点、剪切裂缝在土层传播路径及地表开裂的位置等工程上重点关注的问题。得到以下几点认识：(1) 基岩断层错动引起的地层变形范围基本上不受基岩错动量大小的影响。(2) 断层错动引起地层的不均匀沉降区基本呈三角形分布,其地表宽度约为1倍左右的土层厚度。(3) 基岩错动引起的主剪切裂缝基本沿竖直方向向上传播,其传播距离取决于基岩错动量及土体的破坏应变。(4) 基岩断层错动在主剪区的下盘一侧边缘会产生张拉裂缝,且产生张拉裂缝所需基岩错动量远小于产生剪切裂缝所需的错动量。     

Development of sustainability evaluation model for implementing product service systems

A new business model, product service systems, is proposed to promote a shift in focus from selling purely products to selling functions. This is achieved through a mix of products and services that fulfill the same consumer demands, while eliciting less environmental impact. Development of product service systems has become an increasingly important strategy in achieving social, economic, and environmental sustainability because product service systems advocates reducing resource consumption, while delivering better and more widely available goods and services. This paper proposes an evaluation framework of sustainable performance to implement product service systems. A literature review discusses 32 criteria categorized into two aspects: product and organization. The fuzzy Delphi method is then applied to identify the consistency of criteria. The relative weights of the selected criteria are determined using Fuzzy analytic hierarchy process. Results indicate that the top three criteria in product aspect are maintenance system (weight?=?0.172), use time or frequency (weight?=?0.145), and price of the product (weight?=?0.132). For the organization aspect, the top three criteria are integrated service plan (weight?=?0.197), product development and design (weight?=?0.144) and optimized transportation network (weight?=?0.089). The demand for implementing product service systems is completely different from selling traditional goods because product service systems must consider the issue of sustainability. The proposed evaluation framework can help companies identify the potential products suitable in implementing product service systems.     

Geochemical and isotopic composition of organic matter in the Kupferschiefer of the Polish Zechstein basin: relation to maturity and base metal mineralization

max vs the present depth of the Kupferschiefer, soluble organic matter (SOM) yields, and relative proportions of saturated and aromatic hydrocarbons of the SOM provide evidence for an oxidative alteration of organic matter in highly mineralized Kupferschiefer samples near the Rote F?ule zones. This is confirmed by differences in the composition of the saturated and aromatic hydrocarbon fractions of the soluble organic matter: Saturated hydrocarbons from Rote F?ule samples are dominated by short-chain n-alkanes and higher abundances of pristane and phytane relative to heptadecane (n-C17) and octadecane (n-C18), respectively, compared with samples more distant to the Rote F?ule zone. Compositional changes of the aromatic hydrocarbon fractions with decreasing distance to that zone are characterized by the occurrence of polycyclic aromatic hydrocarbons and elevated ratios of phenanthrene to methylphenanthrenes that are attributed to demethylation reactions and resulted in a decrease of the methylphenanthrene index (MPI 1). Kupferschiefer samples from the barren zone of the Polish Basin do not show these alteration patterns. The observed variations in organic matter composition with burial depth are consistent with changes due to increasing thermal maturation. Maturity assessment is achieved from MPI 1 and the methyldibenzothiophene ratio (MDR). From the relationship between the maturity of organic matter in terms of vitrinite reflectance values and depth of the Kupferschiefer strata, a continuous increase in reflectance of vitrinite is obtained within the Polish Basin. The alteration pattern of organic matter related to base metal mineralization of the Kupferschiefer corresponds to changes in the isotopic composition of organic carbon and calcite. Kerogen within, or close to, Rote F?ule zone is enriched in ¹³C caused by the preferential release of isotopically light organic compounds through progressive degradation of organic matter. The opposite tendency towards lower δ ¹³C and δ ¹⁸O values of calcite provides evidence for isotopic exchange between carbonate and the oxidizing, ore-bearing solutions and for organic matter remineralization. In contrast, organic matter and calcite from the Kupferschiefer do not show regular trends in δ ¹³C with increasing thermal maturation. Received: 25 June 1999 / Accepted: 1 December 1999