Analysis of Mn-nodules from Slupsk Furrow

Rare earth element concentrations in ferromanganese concretions sampled from Slupsk Furrow in the Polish Exclusive Economic Zone are similar to those of concretions from the Gulf of Bothnia. The lack of positive Ce anomalies in the concretions from Slupsk Furrow indicates that they are formed under less oxidizing conditions than spheroidal concretions from the Gulf of Bothnia. Mossbauer studies indicate that poorly crystalline lepidocrosite is the principal iron oxyhydroxide mineral present in these concretions.

Annotated record of the detailed examination of Mn deposits from DEEPSONDE Expedition stations near the East Pacific Rise

Basalts from the base of a small seamount on ~1.5-m.y.-old crust west of the East Pacific Rise (EPR) at 9°N are intermediate in chemical and isotopic composition between light-rare-earth-element-depleted tholeiite (normal midocean ridge basalt (MORB)) and alkali basalt. Like oceanic alkali basalt, these rocks contain significantly more Ba, K, P, Sr, Ti, U, and Zr than normal MORB. Since the absolute abundances of these elements are still well below alkali basalt levels, the label transitional is adopted for these basalts. A series of fractionated MORB also occurs in this area, northwest of the Siqueiros Fracture Zone - Transform Fault. The normal tholeiites are either olivine-plagioclase or plagioclase-clinopyroxene phyric, while the transitional basalts are spinel-olivine phyric. Fractional crystallization quantitatively accounts for the chemical variability of the tholeiitic series but not for the transitional basalts. The tholeiitic series probably evolved in a crustal magma chamber ~4 km below the crest of the East Pacific Rise. 143Nd/144Nd and other chemical data suggest that the large-ion-lithophile-enriched transitional basalts may represent a hybrid of normal MORB and Siqueiros area alkali basalt. Incompatible element plots of K, P, and U indicate possible derivation of the transitional basalts by magma mixing. Magma mixing of unfractionated normal MORB and Siqueiros alkali basalt has been quantified. Derivation of the transitional basalts from a 1:1 mixture is supported by all available chemical data, including Cr, Cu, Nd, Ni, Sm, Sr, U, and V. This magma mixing apparently occurred at ?<~30 km depth within a few tens of kilometers from the EPR axis. These Siqueiros area EPR transitional basalts are compared with Mid-Atlantic Ridge (MAR) transitional basalts from the Iceland and Azores areas. The Siqueiros area basalts reflect a profound chemical and isotopic heterogeneity in the upper mantle, similar to that found along the MAR. Unlike the MAR, the EPR shows no evidence of plumelike bulges and associated large-scale outpourings of nonnormal MORB resulting from these mantle heterogeneities. Siqueiros alkali basalt and MORB, as well as transitional basalt and MORB, were recovered from single dredge hauls. Such close spatial and temporal proximity of the inferred mantle sources places severe constraints on geometric and physicochemical upper mantle models.

(Table 1) Sedimentary thicknesses, lithologies, ages, and interpreted paleowater depths for ODP Sites 135-840 and 135-841

The sedimentary succession drilled at Sites 840 and 841 on the Tonga forearc allows the sedimentary evolution of the active margin to be reconstructed since shortly after the initiation of subduction during the mid Eocene. Sedimentation has been dominated by submarine fan deposits, principally volcaniclastic turbidites and mass-flows derived from the volcanic arc. Volcaniclastic sedimentation occurred against a background of pelagic nannofossil sedimentation. A number of upward-fining cycles are recognized and are correlated to regional tectonic events, such as the rifting of the Lau Basin at 5.6 Ma. Episodes of sedimentation dating from 16.0 and 10.0 Ma also correlate well with major falls in eustatic sea level and may be at least partially caused by the resulting enhanced erosion of the arc edifice. The early stages of rifting of the Lau Basin are marked by the formation of a brief hiatus at Site 840 (Horizon A), probably a result of the uplift of the Tonga Platform. Controversy exists as to the degree and timing of the uplift of Site 840 before Lau Basin rifting, with estimates ranging from 2500 to 300 m. Structural information favors a lower value. Breakup of the Tonga Arc during rifting resulted in deposition of dacite-dominated, volcaniclastic mass flows, probably reflecting a maximum in arc volcanism at this time. A pelagic interval at Site 840 suggests that no volcanic arc was present adjacent to the Tonga Platform from 5.0 to 3.0 Ma. This represents the time between separation of the Lau Ridge from the Tonga Platform and the start of activity on the Tofua Arc at 3.0 Ma. The sedimentary successions at both sites provide a record of the arc volcanism despite the reworked nature of the deposits. Probe analyses of volcanic glass grains from Site 840 indicate a consistent low-K tholeiite chemistry from 7.0 Ma to the present, possibly reflecting sediment sourcing from a single volcanic center over long periods of time. Trace and rare-earth-element (REE) analyses of basaltic glass grains indicate that thinning of the arc lithosphere had begun by 7.0 Ma and was the principle cause of a progressive depletion of the high-field-strength (HFSE), REE, and large-ion-lithophile (LILE) elements within the arc magmas before rifting. Magmatic underplating of the Tofua Arc has reversed this trend since that time. Increasing fluid flux from the subducting slab since basin rifting has caused a progressive enrichment in LILEs. Subduction erosion of the underside of the forearc lithosphere has caused continuous subsidence and tilting toward the trench since 37.0 Ma. Enhanced subsidence occurred during rifting of the South Fiji and Lau basins. Collision of the Louisville Ridge with the trench has caused no change in the nature of the sedimentation, but it may have been responsible for up to 300 m of uplift at Site 840.

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.

The igneous charnockite—high-K alkali-calcic I-type granite—incipient charnockite association in Trivandrum Block, southern India

The Pan-African (640 Ma) Chengannoor granite intrudes the NW margin of the Neoproterozoic high-grade metamorphic terrain of the Trivandrum Block (TB), southern India, and is spatially associated with the Cardamom hills igneous charnockite massif (CM). Geochemical features characterize the Chengannoor granite as high-K alkali-calcic I-type granite. Within the constraints imposed by the high temperature, anhydrous, K-rich nature of the magmas, comparison with recent experimental studies on various granitold source compositions, and trace- and rare-earth-element modelling, the distinctive features of the Chengannoor granite reflect a source rock of igneous charnockitic nature. A petrogenetic model is proposed whereby there was a period of basaltic underplating; the partial melting of this basaltic lower crust formed the CM charnockites. The Chengannoor granite was produced by the partial melting of the charnoenderbites from the CM, with subsequent fractionation dominated by feldspars. In a regional context, the Chengannoor I-type granite is considered as a possible heat source for the near-UHT nature of metamorphism in the northern part of the TB. This is different from previous studies, which favoured CM charnockite as the major heat source. The Occurrence of incipient charnockites (both large scale as well as small scale) adjacent to the granite as well as pegmatites (which contain CO2, CO2-H2O, F and other volatiles), suggests that the fluids expelled from the alkaline magma upon solidification generated incipient charnockites through fluid-induced lowering of water activity. Thus the granite and associated alkaline pegmatites acted as conduits for the transfer of heat and volatiles in the Achankovil Shear Zone area, causing pervasive as well as patchy charnockite formation. The transport Of CO2 by felsic melts through the southern Indian middle crust is suggested to be part of a crustal-scale fluid system that linked mantle heat and CO2 input with upward migration of crustally derived felsic melts and incipient charnockite formation, resulting in an igneous charnockite - I-type granite - incipient charnockite association.

Theory of strongly correlated electron systems. I. Intersite coulomb interaction and the approximation of renormalized fermions in total energy calculations

The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.

A new estimate for the composition of weathered young upper continental crust from alluvial sediments, Queensland, Australia

We present new major element, trace element and Nd-isotope data for 30 alluvial sediments collected from 25 rivers in Queensland, E Australia. Samples were chosen to represent drainage from the region's most important lithologies, including Tertiary intraplate volcanic rocks, a Cretaceous igneous province (and sedimentary rocks derived thereof) as well as Proterozoic blocks. In most chemical and isotopic aspects, the alluvial sediments represent binary or ternary mixing relationships, with absolute abundances implied to reflect the proportion of lithologies in the catchments. When averaged, the studied sediments differ from other proxies of upper continental crust (UCC) mainly in their relative middle rare earth element enrichment (including an elevated Sm/Nd ratio), higher relative Eu abundance and higher Nb/Ta ratio. These features are inherited from eroded Tertiary intraplate basalts, which commonly form topographic highs in the studied region. Despite the high degree of weathering strong to excellent coherence between similarly incompatible elements is found for all samples. From this coherence, we suggest revisions of the following upper crustal element ratios: Y/Ho = 26.2, Yb/Tm = 6.37, Th/W = 7.14, Th/Tl = 24 and Zr/Hf = 36.9. Lithium, Rb, Cs and Be contents do not seem depleted relative to UCC, which may reflect paucity of K-feldspar in the eroded catchments. Nickel, Cr, Pb, Cu and Zn concentrations are elevated in polluted rivers surrounding the state capital. River sediments in the Proterozoic Georgetown Inlier are elevated in Pb, Cu and Zn but this could be a natural phenomenon reflecting abundant sulphide mineralisation in the area. Except for relative Sr concentrations, which broadly anticorrelate with mean annual rainfall in catchments, there is no obvious relationship between the extent of weathering and climate types, which range from and to tropical. The most likely explanation for this observation is that the weathering profiles in many catchments are several Myr old, established during the much wetter Miocene period. The studied sediment compositions (excluding those from the Proterozoic catchments) are used to propose a new trace element normalisation termed MUQ (MUd from Queensland), which serves as an alternative to UCC proxies derived from sedimentary rocks. Copyright (C) 2005 Elsevier Ltd

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.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

Geochemistry of Atlantis Massif crust

The Atlantis Massif (Mid-Atlantic Ridge, 30°N) is an oceanic core complex marked by distinct variations in crustal architecture, deformation and metamorphism over distances of at least 5 km. We report Sr and Nd isotope data and Rare Earth Element (REE) concentrations of gabbroic and ultramafic rocks drilled at the central dome (IODP Hole 1309D) and recovered by submersible from the southern ridge of the massif that underlie the peridotite-hosted Lost City Hydrothermal Field. Systematic variations between the two areas document variations in seawater penetration and degree of fluid-rock interaction during uplift and emplacement of the massif and hydrothermal activity associated with the formation of Lost City. Homogeneous Sr and Nd isotope compositions of the gabbroic rocks from the two areas (87Sr/86Sr: 0.70261-0.70429 and epsilon-Nd: +9.1 to +12.1) indicate an origin from a depleted mantle. At the central dome, serpentinized peridotites are rare and show elevated seawater-like Sr isotope compositions related to serpentinization at shallow crustal levels, whereas unaltered mantle isotopic compositions preserved in the gabbroic rocks attest to limited seawater interaction at depth. This portion of the massif remained relatively unaffected by Lost City hydrothermal activity. In contrast, pervasive alteration and seawater-like Sr and Nd isotope compositions of serpentinites at the southern wall (87Sr/86Sr: 0.70885-0.70918; epsilon-Nd: -4.7 to +11.3) indicate very high fluid-rock ratios (~20 and up to 10**6) and enhanced fluid fluxes during hydrothermal circulation. Our studies show that Nd isotopes are most sensitive to high fluid fluxes and are thus an important geochemical tracer for quantification of water-rock ratios in hydrothermal systems. Our results suggest that high fluxes and long-lived serpentinization processes may be critical to the formation of Lost City-type systems and that normal faulting and mass wasting in the south facilitate seawater penetration necessary to sustain hydrothermal activity.

An alkalic volcanic suite of the Labrador Trough, Labrador

The Nimish Subgroup igneous suite is a linear belt of volcanic and plutonic rocks in the Dyke Lake area of the southern Labrador Trough. The volcanics are interbedded with the sediments of the Wishart and Sokoman Formations of the Aphebian aged, Knob Lake Group. The sokoman Formation forms a time stratigraphic horizon that separates the lower Petitsikapau Lake Formation from the upper Astray Lake formation of the Nimish Subgroup. The occurrence of these volcanics within the Knob Lake Group is unique relative to Labrador Trough stratigraphy, as elsewhere the Knob Lake Group is a dominantly sedimentary succession and volcanics are restricted to the younger Doublet Group. Stratigraphic relationships between the Nimish Subgroup and the Sokoman formation indicate contemporaneous volcanic, clastic and chemical sedimentary activity. The internal stratigraphy of the Sokoman Formation exhibits a three-fold subdivision that is broadly correlatable with similar subdivisions in the Schefferville "main ore zone", 30 miles to the northwest. A detailed facies and paleogeographic model relating the volcanic activity to iron formation deposition in the Dyke Lake is presented. The rocks of the Dyke Lake area have been affected by lower greenschist facies metamorphism during the Hudsonian orogenic event, circa 1735 my. Geochemical evidence indicates that the igneous rocks of the Nimish Subgroup have been metasomatized with large degrees of mobility in Na₂O, K₂O, CaO, MgO, SiO₂, FeO and Fe₂O₃ suspected. The "immobile trace elements", Ti, Zr, Nb, Y and Ga imply that the Nimish lavas are a mildly alkaline suite that has an alkali basalt-trachyandesite-comendite differentiation scheme. The rare earth element, REE, geochemistry of the Nimish Subgroup is supportive of the alkaline nature of the volcanics and has been used to model the fractional crystallization petrogenesis involved in the two volcanic cycles. The geological, geochemical and geophysical evidence indicates that the Nimish Subgroup lavas are possibly a rift facies, alkaline suite related to the tensional tectonic regime that preceeded the extrusion of voluminous tholeiitic lavas of the Doublet Group.

SOL-GEL Lanthanum Phosphate, Composite and coating for functional Applications.

Lanthanum phosphate is one among the lanthanide family of “Rare Earths” following the periodic table of elements. Known under the generic name, Monazite, the rare earth phosphates have melting points above 1900 °C, high thermal phase stability, low thermal conductivity and thermal expansion coefficient similar to some of the high temperature oxides like alumina and zirconia.

Princípios fundamentais e modelos de transferência de energia inter e intramolecular

This work outlines the historic development of the concept and main theories of energy transfer, as well as the principal experiments carried out to confirm or refute the proposed theories. Energy transfer in coordination compounds is also discussed with a focus on rare earth systems.

Técnica de bombeio e prova para medidas de absorção de estado excitado e de emissão estimulada, em materiais sólidos dopados com íons terras raras

Rare earth ion doped solid state materials are the most important active media of near-infrared and visible lasers and other photonic devices. In these ions, the occurrence of Excited State Absorptions (ESA), from long lived electronic levels, is commonplace. Since ESA can deeply affect the efficiencies of the rare earth emissions, evaluation of these transitions cross sections is of greatest importance in predicting the potential applications of a given material. In this paper a detailed description of the pump-probe technique for ESA measurements is presented, with a review of several examples of applications in Nd3+, Tm3+ and Er3+ doped materials.