Spindle-like Lanthanide Orthovanadate Nanoparticles: Facile Synthesis by Ultrasonic Irradiation, Characterization, and Luminescent Properties

A general and facile ultrasonic irradiation method has been established for the synthesis of the lanthanide orthovanadate LnVO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) nanoparticles from an aqueous solution of Ln(NO3)(3) and NH4VO3 without any surfactant or template. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and photoluminescence (PL) spectra as well as kinetic decays were employed to characterize the as-prepared products. Ultrasonic irradiation has a strong effect on the morphology of the LnVO(4) nanoparticles. The SEM and TEEM images illustrate that the as-formed LnVO(4) particles have a spindle-like shape with an equatorial diameter of 30-70 nm and a length of 100-200 am, which are the aggregates of even.

Solvothermal synthesis and luminescent properties of monodisperse LaPO4:Ln (Ln = Eu3+, Ce3+, Tb3+) particles

Monodisperse rare-earth ion (Eu3+, Ce3+, Tb3+) doped LaPO4 particles with oval morphology were successfully prepared through a facile solvothermal process without further hear treatment. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra and the kinetic decays were performed to characterize these samples. The XRD results reveal that all the doped samples are well crystalline at 180 degrees C and assigned to the monoclinic monazite-type structure of the LaPO4 phase. It has been shown that all the as-synthesized samples show perfectly oval morphology with narrow size distribution. The possible growth mechanism of the LapO(4):Ln has been investigated as well.

Vapor phase beckmann rearrangement of cyclohexanone oxime over rare earth pyrophosphates

A new application of rare earth pyrophosphates in vapor phase Beckmann rearrangement of cyclohexanone oxime was investigated. The rare earth phosphates were characterized by means of XRD, FT-IR, NH3-TPD and water contact angle measurement. It was found that the weak surface acidity and appropriate surface hydrophobicity should be two key factors in the excellent performance of these catalysts.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Rare earth elements in bottom sediments of major rivers around the Yellow Sea: implications for sediment provenance

Rare earth elements (REEs) of 91 fine-grained bottom sediment samples from five major rivers in Korea (the Han, Keum, and Yeongsan) and China (the Changjiang and Huanghe) were studied to investigate their potential as source indicator for Yellow Sea shelf sediments, this being the first synthetic report on REE trends for bottom sediments of these rivers. The results show distinct differences in REE contents and their upper continental crust (UCC)-normalized patterns: compared to heavy rare earth elements (HREEs), light rare earth elements (LREEs) are highly enriched in Korean river sediments, in contrast to Chinese river sediments that have a characteristic positive Eu anomaly. This phenomenon is observed also in primary source rocks within the river catchments. This suggests that source rock composition is the primary control on the REE signatures of these river sediments, due largely to variations in the levels of chlorite and monazite, which are more abundant in Korean bottom river sediments. Systematic variations in I LREE pound/I HREE pound ratios, and in (La/Yb)-(Gd/Yb)(UCC) but also (La/Lu)-(La/Y)(UCC) and (La/Y)-(Gd/Lu)(UCC) relations have the greatest discriminatory power. These findings are consistent with, but considerably expand on the limited datasets available to date for suspended sediments. Evidently, the REE fingerprints of these river sediments can serve as a useful diagnostic tool for tracing the provenance of sediments in the Yellow Sea, and for reconstructing their dispersal patterns and the circulation system of the modern shelf, as well as the paleoenvironmental record of this and adjoining marginal seas.

内蒙古白云鄂博超大型REE-Nb-Fe矿床脉状矿化时代与成矿流体特征

Bayan Obo REE-Nb-Fe ore deposit is the largest REE deposit in the world. Owing to its unique type and tremendous economic value, this deposit has widely attracted interests from geological researchers and vast amount of scientific data have been accumulated. However, its genesis, especially ore-forming age and REE sources, have been under dispute for a long time. On the basis of previous research works, this paper mainly conducts studies on the Early Paleozoic ore-forming event in the Bayan Obo deposit. The following results and conclusions can be suggested: Sm-Nd isotopic analytical results of bastnaesite, beloeilite, albite and fluorite samples from a coarse-crystalline ore lode present an isochron age of 436±35Ma. Besides, Rb-Sr isotope dating of the coarse-crystalline biotite lode that intruded into banded ores gives an isochron age of 459±39Ma. The two ages verify the exist of Early Paleozoic ore-forming event at Bayan Obo, which characterized by extensive netted mineralization of REE fluorocarbonates, aeschynite and monazite, accompanied by widely fluorite-riebeckite-aegirine-apatite alteration. Sr-Nd isotope composition of vein minerals is located between EMI and ancient lower crust component in the ISr(t)-εNd(t) correlation diagram, indicating that there is a crustal contamination during veined mineralization. A large area late Paleozoic granitoids are distributed in the southeast region of east open pit of the mine. The granitoids intruded directly into the ore-bearing dolomite, and produced intense skarnization. Moreover, at 650-660m of the drill core on 22 line and 1598m level flat in the south of East Open Pit, we firstly found skarnization rocks. Single grain and low background Rb-Sr isochrone dating on phlogopite in skarn gives 309±12Ma. Considering the intruded contacting relationship, the late Paleozoic granitoids, already extended to the under part of REE ore bodies, must be posterior to the latest intense REE mineralization, and is only a destructive tectonic and magmatic activity. Fluid inclusion types of fluorite in the Bayan Obo deposit consist of multiphase daughter mineral-bearing inclusion, two or three phase CO2-bearing inclusion and two phase aqueous inclusion. Petrography, laser Raman analysis and microthermometry study indicate that the fluids involving in REE-Nb-Fe mineralization at Bayan Obo might be mainly of H2O-CO2-NaCl-(F-REE) system. The presence of REE-carbonate as a daughter mineral in fluid inclusions shows that the original ore-forming fluids are rich in REE elements.

Effect of heating vermiculites on extractability of phosphorus and some essential plant micronutrients

The study assessed the effect of heating vermiculites on extractability of phosphorus, iron, zinc and manganese with respect to their potential agricultural use. Of these elements, phosphorus was from apatite and monazite that occur as accessory minerals in vermiculites. Vermiculites were heated at 15-800 degrees C and digested by acetic acid for extracting phosphorus and diethylene triamine pentaacetic acid (DTPA) for extracting zinc, iron and manganese. Phosphorus in the extract was analysed by a flow injection method while zinc, iron and manganese were measured by atomic absorption spectrometry. The results showed that heating vermiculites to 400 C enhanced extractability of phosphorus from apatite and monazite to a level of 335 mg kg(-1). Further heating to 800 degrees C reduced extractable phosphorus to less than 75 mg kg(-1). Maximum extractable zinc, iron and manganese found were 2.7, 19.1 and 22.9 mg kg(-1), respectively, values that are beneficial and tolerable by most plants. Thus, it was concluded that heating vermiculites to

Geoquímica dos granitóides de Aguiar da Beira, norte de Portugal

A área de Aguiar da Beira está integrada nos terrenos autóctones da Zona Centro-ibérica e é constituída essencialmente por rochas granitóides variscas instaladas durante e após a terceira fase de deformação (D3). As relações de campo mostram que estes granitóides intruíram formações metassedimentares de idade proterozóica superior-câmbrica e as sequências do Ordovícico e do Carbónico do sinclinal Porto-Sátão, cujo extremo SE aflora na área de estudo. Com base na cartografia publicada e nos dados de campo colhidos no âmbito deste trabalho, foi possível individualizar oito intrusões distintas: o granodiorito -granito biotítico de Sernancelhe, o granito gnaissoso de duas micas, o granito moscovítico-biotítico de Vila Nova de Paiva, o granodiorito-granito biotítico-moscovítico de Lagares e os granitos de Touro (biotítico-moscovítico), Aguiar da Beira (moscovítico-biotítico), Pera Velha / Vila da Ponte (biotítico-moscovítico) e Rei Mouro (moscovítico-biotítico). A presença de encraves microgranulares em cinco dos granitóides estudados sugere que os processos de mistura de magmas desempenharam um papel importante na sua petrogénese. As datações U-Pb obtidas em zircões e monazites durante o presente estudo permitiram subdividir os granitóides de Aguiar da Beira em três grupos, de acordo com as suas relações com a terceira fase de deformação (D3): granitóides sin-tectónicos (Sernancelhe e granito gnaissoso; 322-317 Ma), tardi-tectónicos (Vila Nova de Paiva, Lagares e Touro; 308-306 Ma), e tardi- a pós-tectónicos (Aguiar da Beira, Pera Velha / Vila da Ponte e Rei Mouro; 303297 Ma). As assinaturas geoquímicas de elementos maiores e traço dos granitóides estudados, em conjunto com os dados isotópicos Sr-Nd e δ18 (rocha total e zircão) apontam para uma contribuição significativa de protólitos crustais na génese destes magmas. Á excepção do granito gnaissoso, todos os granitóides possuem um carácter transicional entre os granitos do tipo I e do tipo S, o que apoiado pelos dados de geoquímica de rocha total e isotópica, e pela presença de encraves microgranulares de composição mais máfica presentes em muitos deles, indicia uma forte intervenção de processos de hibridização de líquidos de proveniência distinta (crustais e mantélicos), em diferentes proporções, na sua origem. Pelo contrário, as características geoquímicas e isotópicas do granito gnaissoso revelam claras afinidades com os granitos do tipo S, e sugerem que tenha derivado da anatexia de fontes exclusivamente supracrustais. No entanto, parte da variabilidade geoquímica e isotópica observada em todos os granitóides estudados só poderá ser explicada pela actuação de processos de cristalização fraccionada, especialmente intensos no caso do granito gnaissoso e dos granitos tardi- a PÓS-D3.

Geochemistry and Minerology of Chaliyar River Sediments with Special Reference to the Occurrence of Placer Gold

The present work deals with the texture, mineralogy and geochemistry of bedload sediments of the main stream of the Chaliyar basin, a typical small drainage system of the tropics enjoying heavy rain fall and moderate climate, located essentially in the Northern Kerala and flowing over the crystalline rocks (and their laterized duricrust) of the South Indian granulite terrain. As the Chaliyar is the major river draining the Wynad Gold Fields and is known for its placer gold occurrences, the thesis gives special emphasize on understanding the nature and distribution of detrital gold in sediments of the basin, while attempting to infer the provenance characteristics and factors involved in the evolution of sediments in general. Minerologically the chaliyar basin sands are quartzose. The quartz and feldspar contents in the coarse sand fraction of the basin range from 64 to 86% and 2 to 16% respectively. The Q/F ration ranges from 4 to 38 with a slight decrease in the lower reaches. Other minerals present include, hornblende, pyroxene and heavy minerals like opaques, garnet, rutile, biotite, spene, silliminite, zircon, apatite and monazite some of which are seen as inclusions in quartz. The major element composition of Chaliyar bedload sediments in the main channel and the headwater tributaries is related to the mineralogical and textual characteristics of sediments.

Metamorphism and Fluid Inclusion Studies of Charnockites and Associated Rocks from the Madurai Granulite Block , Southern India with Special Reference to Graphite Mineralization

The present research is aimed at studying the charnockites and associated rocks of the Madurai Granulite Block (MGB), especially in terms of their field settings, texture, mineralogy, and mineral chemistry analyzing their petrogenesis with the help of thermobarometrical studies and geochronological constraints. The mechanism of charnockitization by the influx of CO2 rich fluids and its relation to the graphite mineralization is actually a matter of discussion and study. The objectives of the present study are, to delineate petrological and structural relationship of charnockites and associated gneissic rocks, to study the field and petrogenetic aspects of graphite mineralization in the MGB, to establish and re-evaluate the P-T conditions of formation of the rocks with the aid of thermbarometric computations and to compare with the earlier studies, characterization of graphite with XRD, Raman spectroscopy and isotope studies together with a search in to its genesis and its relation to the high-grade metamorphism of the terrain, to evaluate the role of CO2 bearing fluids in the processes of charnockitization as well as in the genesis of graphite within the high-grade terrain and to delineate the metamorphic geochronology of selected rocks using ‘monazite dating’ technique with EPMA.

High T/P evolution and metamorphic ages of the migmatitic basement of northern Sierras Pampeanas, Argentina: Characterization of a mid-crustal segment of the Famatinian belt

New petrologic, thermobarometric and U-Pb monazite geochronologic information allowed to resolve the metamorphic evolution of a high temperature mid-crustal segment of an ancient subduction-related orogen. The EI Portezuelo Metamorphic-Igneous Complex, in the northern Sierras Pampeanas, is mainly composed of migmatites that evolved from amphibolite to granulite metamorphic facies, reaching thermal peak conditions of 670-820 degrees C and 4.5-5.3 kbar. The petrographic study combined with conventional and pseudosection thermobarometry led to deducing a short prograde metamorphic evolution within migmatite blocks. The garnet-absent migmatites represent amphibolite-facies rocks, whereas the cordierite-garnet-K-feldspar-sillimanite migmatites represent higher metamorphic grade rocks. U-Pb geochronology on monazite grains within leucosome record the time of migmatization between approximate to 477 and 470 Ma. Thus, the El Portezuelo Metamorphic-Igneous Complex is an example of exhumed Early Ordovician anatectic middle crust of the Famatinian mobile belt. Homogeneous exposure of similar paleo-depths throughout the Famatinian back-arc and isobaric cooling paths suggest slow exhumation and consequent longstanding crustal residence at high temperatures. High thermal gradients uniformly distributed in the Famatinian back-arc can be explained by shallow convection of a low-viscosity asthenosphere promoted by subducting-slab dehydration. (C) 2011 Elsevier Ltd. All rights reserved.

The Sphene-Centered Ocellar Texture: An Effect of Grain-Supported Flow and Melt Migration in a Hyperdense Magma Mush

The sphene-centered ocellar texture consists of leucocratic ocelli with sphene (titanite) crystals at the center, enclosed in a biotite-rich matrix. This texture has been recognized worldwide in hybrid intermediate rocks. On the basis of structural, petrological, and geochronological data from selected outcrops of the Variscan Ribadelago pluton (NW Iberian Massif), we propose that the ocelli were formed by migration and accumulation of a residual melt through a plagioclase- and biotite-dominated crystalline framework. At the late stage of crystallization, the magma acted as a hyperdense suspension and reacted to the pressure gradient caused by the regional stress field, entering the domain of grain-supported flow. Microstructures reveal that aligned crystal domains arose in the crystal framework from the shearing and compaction of the crystal mush and behaved as magmatic microshears. Relative displacement of adjacent crystal clusters along these microshears corresponded to the onset of Reynolds dilatancy that generated an expansion of the crystal mush, involving melt migration and pore aperture. The mineralogy of the ocelli, dominated by andesine and sphene, represents the composition of the migrating melt. The chemistry of this late, Ti-rich melt stems from the incongruent melting of biotite. Magmatic sphene from the ocelli yields a U-Pb age of 317 +/- 1 Ma, which represents the final crystallization of the hybridized magmatic system. Moreover, this texture offers an opportunity to better understand the rheological behavior of highly crystallized magmas.

Petrogenesis of Upper Paleozoic post-collisional peraluminous leucogranites, Sierra de Ancasti, northwest Argentina

The Santa Rosa and Sauce Guacho plutons are two post-collisional peraluminous Late Devonian to Early Carboniferous leucogranites that intruded the banded schists of the Ancasti Formation. The leucogranites are composed of microcline phenocrysts along with quartz, plagioclase, muscovite, biotite, ilmenite, tourmaline, apatite, monazite and zircon. Their geochemical composition is consistent with S-type granites and mineralogically they belong to MPG granites (muscovite-peraluminous granites). It is proposed that granite magma generation was related to shear zones that concentrated fluids in the metasedimentary crust during a collision or transcurrent tectonics. U-Pb analyses on monazite gave an age of 369.8 +/- 5.3 Ma, while Sm/Nd isotopic data yield epsilon(Nd(t)) values of -5.3 for Sauce Guacho and -5.7 for Santa Rosa indicating crustal provenance. Nd model ages between 1,544 and 1,571 Ma are within the range of magmatic rocks from the Lower Ordovician Famatinian Arc in the Central Sierras Pampeanas.

Caracterização do concentrado de ilmenita produzido na Mina do Guaju, Paraíba, visando identificar inclusões de monazita e outros contaminantes

O presente estudo tem como proposta, identificar o modo como o mineral monazita se encontra no concentrado final de ilmenita. Este concentrado é o produto resultante do beneficiamento do minério extraído de depósitos do tipo pláceres, conhecidos como depósitos de areias pretas. Estes depósitos são formados por dunas litorâneas pertencentes à jazida do Guaju, no município de Mataraca-PB. Todo o processo de lavra e beneficiamento deste minério ocorre na Mina do Guaju, a qual é operada pela empresa Millennium Inorganic Chemicals do Brasil S/A, pertencente a Lyondell Chemical Company. A ilmenita é um mineral composto por óxido de ferro e titânio, FeTiO3. Quase toda a ilmenita produzida na mina é transferida para o processo de fabricação de pigmento. A exigência para o uso na fabricação de pigmento é de que o concentrado final de ilmenita tenha um teor mínimo de 53% de TiO2 e um teor máximo de 0,1% de P2O5, entre outras substâncias. A monazita é o principal mineral fonte de óxido de tório, que é radioativo. No processo de fabricação de pigmento, a monazita é um contaminante indesejado. De acordo com a proposta de trabalho, foi feito um estudo de caracterização mineralógica de amostras do concentrado final de ilmenita fornecidas pela empresa. Inicialmente foram feitas análises em lupa, onde muitos grãos de leucoxeno foram identificados. O leucoxeno é uma alteração da ilmenita que permanece com as mesmas características magnéticas e eletrostáticas, tornando impossível, assim, a sua separação no processo de concentração. Também foi verificada a existência de grãos de monazita liberados em pequenas quantidades neste concentrado, indicando uma provável ineficiência no processo de separação. Numa segunda etapa foram realizadas análises dos grãos de ilmenita com o uso de um Microscópio Eletrônico de Varredura (MEV) acoplado a um Espectrômetro de Dispersão de Energia (EDS), para permitir a determinação de elementos químicos na amostra. Esta análise teve como objetivo verificar a existência de inclusões de monazita nos grãos de ilmenita. Porém, o que se observou foi a existência de algumas inclusões de quartzo e de alguns vazios deixados, provavelmente, por inclusões arrancadas durante o processo de preparação das amostras. Alguns destes vazios apresentaram formas semelhantes a de cristais de monazita, indicando a possibilidade da existência de inclusões deste mineral. Entretanto, a quantidade de grãos com possíveis inclusões de monazita é muito pequena, sendo insignificante como contaminante do concentrado final. Embora alguns vazios se assemelhem à forma da monazita, nenhum dos resultados do EDS identificou vestígios de sua presença. Ao final deste estudo ficou evidente que a principal fonte de contaminação do concentrado final de ilmenita corresponde à monazita, a qual se encontra liberada neste concentrado. Desta forma, há a necessidade de se melhorar o processo de separação dos minerais, de modo que a quantidade de monazita no concentrado final seja a menor possível, não prejudicando o rendimento da recuperação de ilmenita.

Estudo dos óxidos A2B2O7 e ABO3 a base de terras raras, para aplicações térmicas e catalíticas a altas temperaturas

Rare earth elements have recently been involved in a range of advanced technologies like microelectronics, membranes for catalytic conversion and applications in gas sensors. In the family of rare earth elements like cerium can play a key role in such industrial applications. However, the high cost of these materials and the control and efficiencies associated processes required for its use in advanced technologies, are a permanent obstacle to its industrial development. In present study was proposed the creation of phases based on rare earth elements that can be used because of its thermal behavior, ionic conduction and catalytic properties. This way were studied two types of structure (ABO3 and A2B2O7), the basis of rare earths, observing their transport properties of ionic and electronic, as well as their catalytic applications in the treatment of methane. For the process of obtaining the first structure, a new synthesis method based on the use of EDTA citrate mixture was used to develop a precursor, which undergone heat treatment at 950 ° C resulted in the development of submicron phase BaCeO3 powders. The catalytic activity of perovskite begins at 450 ° C to achieve complete conversion at 675 ° C, where at this temperature, the catalytic efficiency of the phase is maximum. The evolution of conductivity with temperature for the perovskite phase revealed a series of electrical changes strongly correlated with structural transitions known in the literature. Finally, we can establish a real correlation between the high catalytic activity observed around the temperature of 650 ° C and increasing the oxygen ionic conductivity. For the second structure, showed clearly that it is possible, through chemical processes optimized to separate the rare earth elements and synthesize a pyrochlore phase TR2Ce2O7 particular formula. This "extracted phase" can be obtained directly at low cost, based on complex systems made of natural minerals and tailings, such as monazite. Moreover, this method is applied to matters of "no cost", which is the case of waste, making a preparation method of phases useful for high technology applications