Thermodynamic Analysis of Rare Earth Chlorination and Bromination Processes

Research funded by the Army Research Laboratory (ARL), the Metallurgical and Materials Engineering Department at Montana Tech investigated various methods of extracting and refining rare earth elements (REEs) from mineral ores and concentrates. Extensive thermodynamic, thermogravimetric and differential thermal analyses were performed to evaluate the relative stabilities of various REE compounds in order to assess potential methods for selective separation and recovery of specific REEs. Conversion of rare earth oxides (REO) to rare earth chlorides or bromides is a possible initial step in pyrometallurgical and hydrometallurgical processing of REEs. REO can be converted to chlorides or bromides by roasting in the presence of a chloridizing or bromidizing reactant. (e.g. NH4Cl and NH4Br).

Determination of rare earth elements in geological samples using the agilent SVDV ICP-OES.

2016

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Troca iônica no estado sólido de európio3+ em zeólita Y: influência do tempo de reação

Rare earth elements supported in zeolites are the most important catalysts in the fluid cracking of petroleum. The solid state ion exchange of Eu3+ in Y zeolite was investigated. First of all, the hydrated EuCl3 was well mixed in a ball mill and was then heated at 300ºC for different times. The quantitative determination of Eu3+ showed that the degree of ion exchange depends on the reaction time at constant temperature, being ~95% in 4 h. The X-ray study showed that the crystallinity of the zeolite is little affected by the exchange procedure. The study of spectroscopic properties of Eu3+, emission spectra and lifetime, give information about the migration and position of the ion in the zeolite cages.

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.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Mineralogy and stable oxygen isotope ratios of the Cretaceous-Tertiary boundary

Results of detailed mineralogical, chemical, and oxygen isotope analyses of the clay minerals and zeolites from two Cretaceous-Tertiary (K/T) boundary regions, Stevns Klint, Denmark, and Deep Sea Drilling Project (DSDP) Hole 465A in the north central Pacific Ocean, are presented. In the central part of the Stevns Klint K/T boundary layer, the only clay mineral detected by x-ray diffraction is a pure smectite with > 95 percent expandable layers. No detrital clay minerals or quartz were observed in the clay size fraction in these beds, whereas the clay minerals above and below the boundary layer are illite and mixed-layer smectite-illite of detrital origin as well as quartz. The mineralogical purity of the clay fraction, the presence of smectite only at the boundary, and the d18O value of the smectite (27.2 ± 0.2 per mil) suggest that it formed in situ by alteration of glass. Formation from impact rather than from volcanic glass is supported by its major element chemistry. The high content of iridium and other siderophile elements is not due to the cessation of calcium carbonate deposition and resulting slow sedimentation rates. At DSDP Hole 465A, the principal clay mineral in the boundary zone (80 to 143 centimeters) is a mixed-layer smectite-illite with >=90 percent expandable layers, accompanied by some detrital quartz and small amounts of a euhedral authigenic zeolite (clinoptilolite). The mixed-layer smectite-illite from the interval 118 to 120 centimeters in the zone of high iridium abundance has a very low rare earth element content; the negative cerium anomaly indicates formation in the marine environment. This conclusion is corroborated by the d18O value of this clay mineral (27.1 ± 0.2 per mil). Thus, this mixed-layer smectite-illite formed possibly from the same glass as the K/T boundary smectite at Stevns Klint, Denmark.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

Mineralogy and geochemistry of alteration products in DSDP Leg 81 Holes

Alteration products of basalts from the four holes drilled during Leg 81 were studied and found to be characterized by the widespread occurrence of trioctahedral clay minerals (Mg smectite to chlorite). In some cases zeolites (analcite, chabazite) are associated with the saponite. A more oxidizing stage is marked by a saponite-celadonite association, presenting the geochemical characteristics of hydrothermal processes. Later stages of alteration are represented by palagonitization and subaerial weathering at two sites. These different alteration processes of basalts from Leg 81 record the paleoenvironment during the first opening stages of the Northeast Atlantic Ocean in the Paleocene-Eocene periods.

Geochemistry of basalts from ODP Hole 113-690C

Basalts from Maud Rise, Weddell Sea, are vesicular and olivine-phyric. Major, trace, and rare earth element concentrations are similar to those of alkali basalts from ocean islands and seamounts. The rocks are low in MgO, Cr, Ni, and Sc, and high in TiO2, K2O, P2O5, Zr, and LREE contents. The abundance of "primary" biotite and apatite in the matrix indicates the melting of a hydrous mantle. Prevalence of olivine and absence of plagioclase in the rocks suggests that the volatile in the melt was an H2O-CO2 mixture, where H2O was <0.5. Mantle derived xenocrysts in the basalt include corroded orthopyroxene, chromite, apatite, and olivine. Olivine (Fo90) is too magnesian to be in equilibrium with the basalts, as they contain only 5-6 wt% MgO. Based on the presence of mantle xenocrysts, the high concentration of incompatible elements, the spatial and chemical affinity with other ocean island basalts from the area, and the relative age of the basalt (overlain by late Campanian sediments), it is suggested that Maud Rise was probably generated by hot-spot activity, possible during a ridge crest jump prior to 84 Ma (anomaly 34 time). Iddingsite, a complex intergrowth of montmorillonite and goethite, is the major alteration product of second generation olivine. It is suggested that iddingsite crystallized at low temperatures (<200°C) from an oxidized fluid during deuteric alteration. Vesicles are commonly filled by zeolites which have been replaced by K-feldspars.

Geochemistry at DSDP Leg 60

Eocene to Pleistocene volcanogenic sediments from the Mariana Trough and the Mariana arc-trench system have been studied by X-ray diffraction, X-ray fluorescence, and atomic absorption, and with a scanning electron microscope with an X-ray-energy-dispersive attachment. The mineralogical composition of the volcaniclastic sediments (tuffs) is the same as that of the other associated sediments (mudstones). Diagenetic alterations are significant and seem to result from two processes. The first (low-temperature alteration) develops with age and depth; it consists of the genesis of pure smectite, coupled with zeolites (phillipsite, clinoptilolite). The second is limited to sediments immediately overlying basalts and to the altered basalts themselves. It consists of the massive development of palygorskite, and seems to be linked with hydrothermal activity in the igneous basement.

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.