Recrystallization mechanisms of fergusonite from metamict mineral precursors

The metamict state and recrystallization of fergusonite in metamict natural samples were studied by thermal methods (TGA-DTA), X-ray powder diffraction (XRD), Raman spectroscopy (RS), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and electron microprobe (EPMA). Two metamict mineral samples of fergusonite were investigated in order to identify the original premetamict crystal structure and to identify recrystallization mechanisms. The TEM data and RS provided evidence on the partial preservation of the original structure in the investigated minerals, which are X-ray amorphous. It was shown that fergusonite could recrystallize from a metamict mineral with original fergusonite structure or from metamictized pyrochlore, which was altered before or after metamictization. Two recrystallization mechanisms were recognized: (a) epitaxial growth occurring at the boundary between preserved premetamict structure fragments and completely metamictized areas, and (b) nucleation-crystal growth mechanism occurring in completely amorphous areas of the minerals, and resulting in recrystallization of the original mineral as well as in the crystallization of a new mineral with a modified chemical composition as compared to the initial matrix.     

Apatite fission track and (U-Th)/He thermochronology of the Rochovce granite (Slovakia) – implications for the thermal evolution of the Western Carpathian-Pannonian region

The thermal evolution of the only known Alpine (Cretaceous) granite in the Western Carpathians (Rochovce granite) is studied by low-temperature thermochronological methods. Our apatite fission track and apatite (U-Th)/He ages range from 17.5 ± 1.1 to 12.9 ± 0.9 Ma, and 12.9 ± 1.8 to 11.3 ± 0.8 Ma, respectively. The data thus show that the Rochovce granite records a thermal event in the Middle to early Late Miocene, which was likely related to mantle upwelling, volcanic activity, and increased heat flow. During the thermal maximum between ~17 and 8 Ma, the granite was heated to temperatures ? 60 °C. Increase of cooling rates at ~12 Ma recorded by the apatic fission track and (U-Th)/He data is primarily related to the cessation of the heating event and relaxation of the isotherms associated with the termination of the Neogene volcanic activity. This contradicts the accepted concept, which stipulates that the internal parts of the Western Carpathians were not thermally affected during the Cenozoic period. The Miocene thermal event was not restricted to the investigated part of the Western Carpathians, but had regional character and affected several basement areas in the Western Carpathians, the Pannonian basin and the margin of the Eastern Alps.     

Constraints on incipient charnockite formation from zircon geochronology and rare earth element characteristics

We present high spatial resolution ion-microprobe U–Th–Pb geochronology and rare earth element (REE) data combined with cathodoluminescence (CL) and back-scattered electron (BSE) imaging for complex zircons in incipient charnockites from Söndrum, SW Sweden. Examination of closely paired samples across the dehydration zone demonstrates that incipient charnockite formation at Söndrum is a zircon-forming process. We determined the age of the dehydration event (i.e. charnockitisation) to 1,397 ± 4 Ma (2σ, MSWD = 1.7). This is the first successful attempt to date incipient charnockite formation using U–Pb systematics of zircon. Internal structure, chemical and isotopic characteristics of zircon indicate that the granitic pegmatite in the core of the incipient charnockite is a melting zone. Commonly observed bulk rock HREE depletion in incipient charnockites is not caused by zircon dissolution but by involvement of garnet as a reactant in the dehydration reactions. Moreover, REE patterns of the newly formed zircon are HREE-enriched, indicating non-concurrent growth and suggesting that the degree of charnockite depletion in HREE might be controlled by the volume of newly formed zircon.     

Synthesis and characterization of high-pressure and high-temperature sphene (CaTiSiO5)

Sphene (CaTiSiO₅), a calcium titanosilicate ceramic has been prepared from a powder mixture of CaCO₃, TiO₂ and SiO₂ using vibro-milling for homogenization and activation of precursors. During the high-pressure and high-temperature synthesis (HPS) process at 4 GPa and 1,200 °C, sphene undergoes into phase transition, from room-temperature phase P2₁ /a to high-temperature phase A2/a. Evidence of that structural phase transition is given in this paper using infrared, Raman spectroscopy and X-ray powder diffraction. Rietveld refinement was employed to get the structural information of the synthesized powder. The most important structural change due to phase transition, the disappearance of the characteristic out-of-center distortion of the Ti atom and moving to the center of octahedra, was confirmed. HPS is an effective method for producing full-dense ceramics without any additives. Reduction of particle size occurred during high-pressure compaction. Microstructure and particle size of both phases were analyzed by scanning electron microscopy.     

热带地区碳酸盐岩上覆红色风化壳的成因机理及元素演化

开展热带岩溶地区红色风化壳元素地球化学演化规律研究,有助于丰富碳酸盐岩风化成土理论的认识。在越南北部选取典型的碳酸盐岩风化剖面,分析热带气候条件下碳酸盐岩上覆红色风化壳中主量元素的物质来源和演化特征。结果表明:无论Ti/Zr的元素比值分析,Hf-Zr、Nb-Ta及Sm-Nd的元素对协变分析,还是上地壳元素平均值(UCC)标准化分析,两个剖面的上覆风化壳均显示原地残积的特征,即两个剖面是碳酸盐岩的原位风化产物。碳酸盐岩风化成土过程中,CaO、MgO淋失明显,Al_2O_3和Fe_2O_3发生富集,显示两个剖面均经历较强的风化过程,但是白云岩和灰岩剖面有一定的分异特征。越南北部白云岩风化剖面从基岩到上部土层显示出稳定的Ti-Fe元素共富集特征,而灰岩剖面中Fe的增长速率明显超过Ti。白云岩上覆风化壳经历了强烈的风化作用,其脱硅作用弱于灰岩风化剖面,而富集铝的作用强于灰岩。迁移系数的演化规律说明两个剖面中长石成分(钾长石、钠长石等)或次生矿物(伊利石等)在风化成土过程中逐渐分解,同时Al、Fe、Si等稳定元素的在风化剖面中不断富集。     

Physical properties and the chemical composition of sphalerites from Yugoslavia

Chemical and spectral analyses are given for 16 sphalerites from Yugoslavia. Since they were formed under various conditions the content of Fe and other metals (Mn and Cd especially) varies widely. The relation between the dimensions of elementary cell and the molar percent of FeS in the sphalerites of Yugoslavia shows only slight differences from Vegard's rule. The indices of refraction and reflectivity as well as dispersion for the wavelengths 440, 460, 480, 500, 540, 580, 620, and 660 nm were measured. For the wavelengths mentioned, diagrams are given showing the relation between reflectivity and microhardness of sphalerite and its chemical composition.

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Zusammenfassung Für 16 jugoslawische Zinkblenden wurde die chemische Zusammensetzung und spektralanalytisch der Gehalt an Spurenelementen ermittelt. Da die Zinkblenden unter sehr verschiedenen Bedingungen entstanden, schwankt ihr Gehalt an Fe und anderen Metallen, besonders Mn und Cd stark. Die Verhältnisse zwischen der Größe der Elementarzelle und den Molprozenten von FeS zeigen nur geringe Abweichungen von der Vegard-Regel. Für die Wellenlängen 440, 460, 480, 500, 540, 580, 620 und 660 nm wurden Refraktionsindices, Absorptionskoeffizient und Reflexionsvermögen ermittelt. Die Beziehungen zwischen Reflexionsvermögen, Mikrohärte und chemischer Zusammensetzung werden in Diagrammen dargestellt.

     

The effect of coherency stress on the mechanism of the reaction albite+K+⇌K-feldspar+Na+ and on the mechanical state of the resulting feldspar

Coherency stress and coherency strain energy generated by Na⁺?K⁺ ion exchange in alkali feldspars are calculated using an isotropic model, and deformation of single crystals of alkali feldspars exposed to molten alkali chlorides at \(P_{H_2 O} \) < 1 bar is described. Coherency stress in alkali feldspars can reach 10–20 kb. When it is large, partial relaxation by fracture and/or plastic deformation takes place under anhydrous conditions, but temporary build-up of stress is unavoidable even under hydrothermal conditions. Because of coherency strain energy, a thin layer of an end-member alkali feldspar produced by cation exchange on a grain of the other end-member alkali feldspar would be unstable with respect to dissolution. Therefore, under hydrothermal conditions one end-member alkali feldspar replaces the other by dissolution and precipitation. The mechanism of the reaction $$Na_x K_{1 - x} AlSi_3 O_{8_{(feld.)} } + yK^ + \rightleftharpoons Na_{x - y} K_{1 + y - x} AlSi_3 O_{8_{(feld.)} } + yNa^ + $$ is primarily controlled by \(P_{H_2 O} \) and by ΔK/(Na + K), the difference between the equilibrium value and the initial value of the atomic K/(Na + K) ratio of the feldspar. When ¦ΔK/(Na + K)¦ is small, the reaction proceeds by cation exchange. When ¦ΔK/(Na + K)¦ is large, cation exchange still occurs if \(P_{H_2 O} \) is very low, but under hydrothermal conditions replacement by dissolution and precipitation occurs.     

Crystallochemical effects of heat treatment on Fe-dominant tourmalines from Dolní Bory (Czech Republic) and Vlachovo (Slovakia)

Heat treatment was performed on selected Fe-dominant tourmalines to establish the nature of any change in optical properties. Two tourmaline samples from Dolní Bory, Czech Republic (TDB) and Vlachovo, Slovakia (TVL) were heated at 450, 700 and 900°C at 0.1 mPa and ambient oxidation conditions for 8 h. EMPA study shows that tourmaline from Vlachovo has schorlitic composition and tourmaline from Dolní Bory is alkali-depleted schorl to foitite. Although the black colour remained unchanged after heating at 450°C, it changed to brown at 700°C and reddish brown at 900°C. No significant changes of chemical composition were observed during heating. X-ray diffraction, infrared and Mössbauer study showed negligible oxidation of tourmaline heated at 450°C, but a significant change in iron valency state and deprotonization at 700°C. The oxidation of Fe is the main cause of tourmaline colour change, and the substitution vector for oxidation of Fe is Fe³⁺OFe _?1 ²⁺ (OH)_?1. The predicted deprotonization of OH was confirmed by infrared spectroscopy, which documented a decrease in OH groups in both samples, mainly at the V site. The oxidation of Fe is mostly significant in the Y site as documented on the compression of the Y-site octahedra and subsequent decrease in the a lattice parameter. This feature is consistent with lattice dimensions in the transition from schorl and foitite dimensions to those consistent with fluor-buergerite. The Z-site octahedra did not compressed and were not affected by heating-induced Fe oxidation, which indicates only negligible content of ^Z Fe²⁺ in original samples. After heating at 900°C, the tourmaline structure collapsed likely due to the thermally induced weakening of bonds in Y and Z octahedra, which results in amorphization of tourmaline. Subsequently, breakdown products including Fe-oxides and mullite replaced alkali-depleted amorphized tourmaline.     

Global change revealed by palaeolimnological records from remote lakes: a review

Over recent decades, palaeolimnological records from remote sites have provided convincing evidence for the onset and development of several facets of global environmental change. Remote lakes, defined here as those occurring in high latitude or high altitude regions, have the advantage of not being overprinted by local anthropogenic processes. As such, many of these sites record broad-scale environmental changes, frequently driven by regime shifts in the Earth system. Here, we review a selection of studies from North America and Europe and discuss their broader implications. The history of investigation has evolved synchronously with the scope and awareness of environmental problems. An initial focus on acid deposition switched to metal and other types of pollutants, then climate change and eventually to atmospheric deposition-fertilising effects. However, none of these topics is independent of the other, and all of them affect ecosystem function and biodiversity in profound ways. Currently, remote lake palaeolimnology is developing unique datasets for each region investigated that benchmark current trends with respect to past, purely natural variability in lake systems. Fostering conceptual and methodological bridges with other environmental disciplines will upturn contribution of remote lake palaeolimnology in solving existing and emerging questions in global change science and planetary stewardship.