Geochemistry of Rare Erath Elements and Trace Metals along the Western Continental Shelf of India

Rare earth elements have occupied an important role in marine geochemical research, particularly as used in the format of REE abundance patterns to describe the geochemical pathways in marine sedimentation and authigenesis. This study concentrates on the distribution pattern of Rare earth elements in the sediments, behavior of Eu and Ce with respect to their occurrence in multiple oxidation states. It also concentrate the depth wise variation of sediment REEs from near shore areas (30m) to deeper depths 200m) in the Arabian Sea. It includes the downcore variation of REEs and other trace elements in the sediment cores and a comparison between the REE distributions of Arabian Sea sediment with the sediments of Andaman Sea. The study gives a general introduction regarding the importance of RRE studies, its occurrence and abundance, electronic configuration, lanthanide contraction, oxidations states and REE supply to the ocean, seawater and sediments.

Influence of the rare-earths oxides doped on the SnO2CoOMnO2Ta2O5 varistor system

The tin dioxide is an n-type semiconductor, which exhibits varistor behavior with high capacity of absorption of energy, whose function is to restrict transitory over-voltages without being destroyed, when it is doped with some oxides. Varistors are used in alternated current fields as well as in continuous current, and it can be applied in great interval of voltages or in great interval of currents. The electric properties of the varistor depend on the defects that happen at the grain boundaries and the adsorption of oxygen. The (98.90-x)%SnO2.0.25%CoO+0.75%MnO2+0.05%Ta2O5+0.05%Tr2O3 systems, in which Tr=La or Nd. Current-voltage measurements were accomplished for determination of the non-linear coefficient were studied. SEM microstructure analysis was made to evaluate the microstructural characteristics of the systems. The results showed that the rare-earth oxides have influenced the electrical behavior presented by the system. (C) 2002 Kluwer Academic Publishers.

Estrutura e algumas propriedades ópticas de difenilfosfinatos de terras-raras

Coordination compounds of trivalent lanthanides cations with diphenylphosphinate are originated from direct reaction between a lanthanide salt and diphenylphosphinic acid. These complexes have peculiar and intriguing features, as (i) quickly obtainment through wet process precipitation, (ii) appreciable thermal stability, similar to inorganic phosphates, (iii) polymeric structure, and consequently, (iv) low solubility in both polar and non-polar solvents. Nowadays, coordination polymers are classified as coordination networks or, in case of porous materials, as metal-organic frameworks (MOFs). By this study, we aim to determine some optical properties of rare-earth diphenylphosphinate (RE = La3+, Eu3+, Gd3+, Lu3+) and conduct an updated classification of these compounds, bringing more details of its structure and the possible proposal of new materials with applications in lighting, detection of ionizing radiation and magnetism. The complexes of trivalent rare-earth cation with diphenylphosphinate were prepared by direct mixture of diphenylphosphinic acid with rare-earth metal chloride, both in ethanolic solution. The solution of diphenylphosphinic acid was kept in a beaker under constant stirring with pH measurements of the solution and gadolinium chloride solution was then dripped slowly with the aid of a burette until its complete addition; the following metal:ligand molar ratios were tested: 1:1, 1:2, 1:3, 2:1 e 3:1. The compounds were characterized by spectroscopic and structural techniques. By Fourier Transform Infrared Spectroscopy (FT-IR), it was possible to check the total ionization of diphenylphosphinic acid in synthesized complexes, confirmed by the absence of the band type A, B, C related to ѵ(O-H) of the acid (2663 cm-1, 2168 cm-1, 1684 cm-1), as well as the disappearance of ѵ(P-OH)=961 cm-1. Furthermore, the occurrence of bands shifts of ѵ(POO-) [symmetrical and asymmetrical] of...

Estrutura e algumas propriedades ópticas de difenilfosfinatos de terras-raras

Coordination compounds of trivalent lanthanides cations with diphenylphosphinate are originated from direct reaction between a lanthanide salt and diphenylphosphinic acid. These complexes have peculiar and intriguing features, as (i) quickly obtainment through wet process precipitation, (ii) appreciable thermal stability, similar to inorganic phosphates, (iii) polymeric structure, and consequently, (iv) low solubility in both polar and non-polar solvents. Nowadays, coordination polymers are classified as coordination networks or, in case of porous materials, as metal-organic frameworks (MOFs). By this study, we aim to determine some optical properties of rare-earth diphenylphosphinate (RE = La3+, Eu3+, Gd3+, Lu3+) and conduct an updated classification of these compounds, bringing more details of its structure and the possible proposal of new materials with applications in lighting, detection of ionizing radiation and magnetism. The complexes of trivalent rare-earth cation with diphenylphosphinate were prepared by direct mixture of diphenylphosphinic acid with rare-earth metal chloride, both in ethanolic solution. The solution of diphenylphosphinic acid was kept in a beaker under constant stirring with pH measurements of the solution and gadolinium chloride solution was then dripped slowly with the aid of a burette until its complete addition; the following metal:ligand molar ratios were tested: 1:1, 1:2, 1:3, 2:1 e 3:1. The compounds were characterized by spectroscopic and structural techniques. By Fourier Transform Infrared Spectroscopy (FT-IR), it was possible to check the total ionization of diphenylphosphinic acid in synthesized complexes, confirmed by the absence of the band type A, B, C related to ѵ(O-H) of the acid (2663 cm-1, 2168 cm-1, 1684 cm-1), as well as the disappearance of ѵ(P-OH)=961 cm-1. Furthermore, the occurrence of bands shifts of ѵ(POO-) [symmetrical and asymmetrical] of...

Grundlegende Untersuchungen zum Verhalten ausgewählter Seltenerdelemente bei Explosionen und zur Anwendbarkeit spezieller Methoden zu deren Analyse

Bisher ist bei forensischen Untersuchungen von Explosionen die Rückverfolgung der verwendeten Sprengstoffe begrenzt, da das Material in aller Regel bei der Explosion zerstört wird. Die Rückverfolgung von Sprengstoffen soll mit Hilfe von Identifikations-Markierungssubstanzen erleichtert werden. Diese stellen einen einzigartigen Code dar, der auch nach einer Sprengung wiedergefunden und identifiziert werden kann. Die dem Code zugeordneten, eindeutigen Informationen können somit ausgelesen werden und liefern der Polizei bei der Aufklärung weitere Ansätze.rnZiel der vorliegenden Arbeit ist es, das Verhalten von ausgewählten Seltenerdelementen (SEE) bei Explosion zu untersuchen. Ein auf Lanthanoidphosphaten basierender Identifikations-Markierungsstoff bietet die Möglichkeit, verschiedene Lanthanoide innerhalb eines einzelnen Partikels zu kombinieren, wodurch eine Vielzahl von Codes generiert werden kann. Somit kann eine Veränderung der Ausgangszusammensetzung des Codes auch nach einer Explosion durch die Analyse eines einzelnen Partikels sehr gut nachvollzogen und somit die Eignung des Markierungsstoffes untersucht werden. Eine weitere Zielsetzung ist die Überprüfung der Anwendbarkeit der Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) und Partikelanalyse mittels Rasterelektronenmikroskopie (REM) für die Analyse der versprengten Identifikations-Markierungssubstanzen. rnDie Ergebnisbetrachtungen der ICP-MS-Analyse und REM-Partikelanalyse deuten zusammenfassend auf eine Fraktionierung der untersuchten Lanthanoide oder deren Umsetzungsprodukte nach Explosion in Abhängigkeit ihrer thermischen Belastbarkeit. Die Befunde zeigen eine Anreicherung der Lanthanoide mit höherer Temperaturbeständigkeit in größeren Partikeln, was eine Anreicherung von Lanthanoiden mit niedrigerer Temperaturbeständigkeit in kleineren Partikeln impliziert. Dies lässt sich in Ansätzen durch einen Fraktionierungsprozess in Abhängigkeit der Temperaturstabilität der Lanthanoide oder deren Umsetzungsprodukten erklären. Die der Fraktionierung zugrunde liegenden Mechanismen und deren gegenseitige Beeinflussung bei einer Explosion konnten im Rahmen dieser Arbeit nicht abschließend geklärt werden.rnDie generelle Anwendbarkeit und unter Umständen notwendige, komplementäre Verwendung der zwei Methoden ICP-MS und REM-Partikelanalyse wird in dieser Arbeit gezeigt. Die ICP-MS stellt mit großer untersuchter Probenfläche und hoher Genauigkeit eine gute Methode zur Charakterisierung der Konzentrationsverhältnisse der untersuchten Lanthanoide dar. Die REM-Partikelanalyse hingegen ermöglicht im Falle von Kontamination der Proben mit anderen Lanthanoid-haltigen Partikeln eine eindeutige Differenzierung der Elementvergesellschaftung pro Partikel. Sie kann somit im Gegensatz zur ICP-MS Aufschluss über die Art und Zusammensetzung der Kontamination geben. rnInnerhalb der vorgenommenen Untersuchungen stellte die bei der ICP-MS angewandte Probennahmetechnik eine ideale Art der Probennahme dar. Bei anderen Oberflächen könnte diese jedoch in Folge der in verschiedenen Partikelgrößen resultierenden Fraktionierung zu systematisch verfälschten Ergebnissen führen. Um die generelle Anwendbarkeit der ICP-MS im Hinblick auf die Analyse versprengter Lanthanoide zu gewährleisten, sollte eine Durchführung weiterer Sprengungen auf unterschiedlichen Probenoberflächen erfolgen und gegebenenfalls weitere Probennahme-, Aufschluss- und Anreicherungsverfahren evaluiert werden.rn

Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Rare element concentrations measured on filtered seawater of water bottle samples during POLARSTRERN cruise ANT-XXIV/3 (GIPY5)

The concentrations of rare earth elements (REEs) in seawater display systematic variations related to weathering inputs, particle scavenging and water mass histories. Here we investigate the REE concentrations of water column profiles in the Atlantic sector of the Southern Ocean, a key region of the global circulation and primary production. The data reveal a pronounced contrast between the vertical profiles in the Antarctic Circumpolar Current (ACC) and those to the south of the ACC in the Weddell Gyre (WG). The ACC profiles exhibit the typical increase of REE concentrations with water depth and a change in the shape of the profiles from near linear for the light REEs to more convex for the heavy REEs. In contrast, the WG profiles exhibit high REE concentrations throughout the water column with only the near surface samples showing slightly reduced concentrations indicative of particle scavenging. Seawater normalised REE patterns reveal the strong remineralisation signal in the ACC with the light REEs preferentially removed in surface waters and the mirror image pattern of their preferential release in deep waters. In the WG the patterns are relatively homogenous reflecting the prevalence of well-mixed Lower Circumpolar Deep Water (LCDW) that follows shoaling isopycnals in the region. In the WG particle scavenging of REEs is comparatively small and limited to the summer months by light limitation and winter sea ice cover. Considering the surface water depletion compared to LCDW and that the surface waters of the WG are replaced every few years, the removal rate is estimated to be on the order of 1 nmol/m3/yr for La and Nd. The negative cerium anomalies observed in deep waters are some of the strongest found globally with only the deepest waters in parts of the Pacific having stronger anomalies. These deep waters have been isolated from fresh continental REE inputs during their long journey through the abyssal Indo-Pacific ocean and suggests that the high REE concentrations found in the ACC and WG reflect contributions from old deep waters.

Lanthanide series rare earths : an annotated list of unclassified references.

AEC Report No. TID-3029.

Hydroxide carbonates and oxide carbonate hydrate of rare earths grown on glass via a hydrothermal route

Carbonates of rare-earths, specifically hydroxide carbonate or oxide carbonate hydrate, could be prepared on common glass by a hydrothermal process involving thiourea. Examples presented in this paper include LaOHCO3, CeOHCO3 and EU2O(CO3)(2) . H2O structures formed on glass from solutions of thiourea and the relevant rare-earth reactants. The crystal structure and habit on the substrates were dependent on the preparative conditions; the influence of the concentrations of reactants and temperature on the crystal morphologies is illustrated. Second harmonic generation was found to occur in the crystals. (C) 2004 Elsevier B.V. All rights reserved.

Examining Perspectives On China's Near-Monopoly Of Rare Earths

China’s behavior as a near-monopolist of rare earths has come under increasing scrutiny in recent years. This thesis first examines the underlying causes behind China’s rise to the status of rare-earths near-monopolist, including government support; lax environmental controls; unregulated production; and relatively low costs compared to the rest of the world. Second, the thesis also examines the preeminent international and domestic factors influencing China’s behavior as a near-monopolist of rare earths. International factors include international demand; international trade pressure; international price-setting authority issues; and geopolitical factors. I next identify domestic factors that exert influence over China’s rare earths-related behavior: environmental protection; rare earth resource protection; rare earths industry regulation; and protecting and aiding China’s domestic rare earths industry. The study concludes with a synthesis of the factors influencing China’s rare-earths-related behavior in the overall context of support and direction by China’s Central Government.

Physico-geochemical and mineral composition of neem tree soils and relation to organic properties

The Neem tree, the oil of which has a long history of pesticide, fertilizer and medicinal use in India, has been studied extensively for its organic compounds. Here we present a physical, mineralogical and geochemical database resulting from the analyses of two Neem soil profiles (epipedons) in India. Neem tree derivatives are used in the manufacture of a variety of products, from anti-bacterial drugs and insecticides to fertilizers and animal feeds. A preliminary geochemical and mineralogical analysis of Neem soils is made to explore the potential for chemical links between Neem tree derivatives and soils. Physical soil characteristics, including colour, texture and clay mineralogy, suggest the two pedons formed under different hydrological regimes, and hence, are products of different leaching environments, one well-drained site, the other poorly drained. Geochemically, the two Neem soils exhibit similarities, with elevated concentrations of Th and rare earth elements. These elements are of interest because of their association with phosphates, especially monazite and apatite, and the potential link to fertilizer derivatives. Higher concentrations of trace elements in the soils may be linked to nutritional derivatives and to cell growth in the Neem tree.

Synteza, modyfikacja powierzchni i charakterystyka fizykochemiczna wielofunkcyjnych nanomateriałów luminescencyjnych zawierających jony pierwiastków ziem rzadkich

Wydział Chemii: Zakład Ziem Rzadkich

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Raman spectroscopic study of the phosphate mineral Churchite-(Y) YPO4.2H2O

Raman spectroscopy has been used to study the rare earth mineral churchite-(Y) of formula (Y,REE)(PO4) •2H2O. The mineral contains yttrium and depending on the locality, a range of rare earth metals. The Raman spectra of two churchite-(Y) mineral samples from Jáchymov and Medvědín in the Czech Republic were compared with the Raman spectra of churchite-(Y) downloaded from the RRUFF data base. The Raman spectra of churchite-(Y) are characterized by an intense sharp band at 975 cm-1 assigned to the ν1 (PO4)3- symmetric stretching mode. A lower intensity band observed at around 1065 cm-1 is attributed to the ν3 (PO43-) antisymmetric stretching mode. The (PO43-) bending modes are observed at 497 cm-1 (ν2) and 563 cm-1(ν4). Some small differences in the band positions between the four churchite-(Y) samples from four different localities were found. These differences are possible to explain as different compositions of the churchite-(Y) minerals.