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Sample records for earth element fractionation

  1. Isotopic fractionation of rare earth elements in geochemical samples

    NASA Astrophysics Data System (ADS)

    Ishibashi, T.; Ohno, T.

    2015-12-01

    The isotopic composition of Rare Earth Elements(REEs) can be fractionated through various physical and chemical reactions in nature [1]. The isotopic variations of REEs occurring naturally has a potentially significant influence in geochemical research fields. The REEs has key features that their chemical similarities and gradual changes of ionic radius, which may help us to understand the mechanisms of isotopic variations of REEs in nature. Among the REEs, geochemical and physicochemical features of Ce, which could be presence as the tetravalent state, be anomalous, and oxidation state of Ce can change by reflecting the redox conditions of the environment. Therefore, the study of the difference in the degree of isotopic fractionation between Ce and other REEs may provide information on the redox conditions. In this study, we developed a new separation method to determine the mass-dependent isotopic fractionations of REEs in geochemical samples, and examined the optimum concentration of hydrochloric acid for the separation. The samples were decomposed by a mixture of acids, then REEs were separated as a group from major elements using cation exchange resin columns and RE Spec resin. The separations within the REEs group were carried out using Ln2Spec resin. For the recovery of La, Ce, Pr, and Nd, 0.1 M HCl was used, and for isolation of Sm, Eu, and Gd, 0.25 M HCl was used. Then, 0.6 M HCl was used for separation of Tb, and Dy, 1 M HCl was used for separation of Ho, Y, and Er, finally, Tm, Yb, and Lu were collected using 2 M HCl. The yields of all REEs were enough to examine isotopic fractionation in geochemical samples. [1] Ohno and Hirata,Analytical Sciences, 29, 271, 2013

  2. Rare Earth Element Fractionation During Evaporation of Chondritic Material

    NASA Astrophysics Data System (ADS)

    Wang, J.; Davis, A. M.; Clayton, R. N.

    1993-07-01

    Evaporation experiments suggest that enrichments in the heavy isotopes of oxygen, magnesium, and silicon in some CAIs are caused by kinetic effects during evaporation [1]. Volatility-fractionated REE patterns found in some CAIs have been modeled with some success using equilibrium thermodynamics [2,3], but little is known about kinetic effects on REE patterns. We have begun an investigation of REE fractionation under conditions where large isotope effects are produced by the kinetic isotope effect. We synthesized a starting material containing CI chondritic relative proportions of MgO, Al2O3, SiO2, CaO, TiO2, and FeO, and doped it with 100 ppm each of the REE. Samples of this material were evaporated in a vacuum furnace [4] at 10^-6 torr and 1800 or 2000 degrees C for periods of a few seconds to 5 hr. The mass fraction evaporated ranged from 7.6 to 95.4%. Most residues consist of olivine and glass. Chemical compositions of the residues were determined by electron and ion microprobe. Results for selected elements are shown in Fig. 1. There is no significant evaporation of Ca, Al, and Ti up to 95% mass loss; the evaporation behavior of Mg, Si, and Fe is similar to that found by Hashimoto [5]. There is no significant evaporation of most of the REE up to 95% mass loss. Ce is much more volatile than the other REE under these conditions: a tenfold negative Ce anomaly developed between 60 and 70% mass loss and the anomaly reached 5 X 10^-4 at 95% mass loss. A small Pr anomaly (50% Pr loss) also appeared in the highest-mass-loss residue. Thermodynamic calculations show that Ce has approximately the same volatility as other LREE under solar nebular oxygen fugacity, but is much more volatile than the other REE under oxidizing conditions [6]. We suspect that conditions in the residue in our vacuum evaporation experiments became oxidizing because evaporation reactions involving most major element oxides involve release of oxygen. The four known HAL-type hibonite

  3. Bishop tuff revisited: new rare Earth element data consistent with crystal fractionation.

    PubMed

    Cameron, K L

    1984-06-22

    The Bishop Tuff of eastern California is the type example of a high-silica rhyolite that, according to Hildreth, supposedly evolved by liquid-state differentiation. New analyses establish that the Bishop Tuff "earlyllate" rare earth element trend reported by Hildreth mimics the relations between groundmass glasses and whole rocks for allanite-bearing pumice. Differences in elemental concentrations between whole rock and groundmass are the result of phenocryst precipitation; thus the data of Hildreth are precisely those expected to result from crystal fractionation. PMID:17837193

  4. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

    NASA Astrophysics Data System (ADS)

    Wang, Lingqing; Liang, Tao

    2015-07-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg-1 with an average value of 4.67 × 103 mg·kg-1, which was significantly higher than the average value in China (181 mg·kg-1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind.

  5. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China.

    PubMed

    Wang, Lingqing; Liang, Tao

    2015-01-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China's largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 10(4) mg·kg(-1) with an average value of 4.67 × 10(3) mg·kg(-1), which was significantly higher than the average value in China (181 mg·kg(-1)). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La(N)/Yb(N), La(N)/Sm(N) and Gd(N)/Yb(N)). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

  6. Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

    PubMed Central

    Wang, Lingqing; Liang, Tao

    2015-01-01

    Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg−1 with an average value of 4.67 × 103 mg·kg−1, which was significantly higher than the average value in China (181 mg·kg−1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

  7. Fractionation in the solar nebula - Condensation of yttrium and the rare earth elements

    NASA Technical Reports Server (NTRS)

    Boynton, W. V.

    1975-01-01

    The condensation of Y and the rare earth elements (REE) from the solar nebula may be controlled by thermodynamic equilibrium between gas and condensed solids. Highly fractionated REE patterns may result if condensates are removed from the gas before condensation is complete. It is found that the fractionation is not a smooth function of REE ionic radius but varies in an extremely irregular pattern. Both Yb and Eu are predicted to be extremely depleted in the early condensate without the requirement of condensation in the divalent state. The model is discussed with respect to a highly fractionated pattern observed by Tanaka and Masuda (1973), in a pink Ca-Al-rich inclusion from the Allende meteorite and can account for the abundances of each REE determined. According to the model this inclusion represents a condensate from a previously fractionated gas rather than from a gas of solar composition. Before the condensation of this inclusion, an earlier condensate was formed and was removed from equilibrium with the gas.

  8. Efficient mobilization and fractionation of rare-earth elements by aqueous fluids upon slab dehydration

    NASA Astrophysics Data System (ADS)

    Tsay, A.; Zajacz, Z.; Sanchez-Valle, C.

    2014-07-01

    The characteristic REE fractionation pattern in arc magmas compared to MOR-basalts results from the selective mobilization of light rare-earth elements (LREE) by slab-derived mobile components. However, the nature and composition of the slab flux, and the actual mechanisms responsible for the transfer of rare-earth elements (REE) from the slab to the mantle wedge remain unclear. We present experimental data on the solubility of selected REE in ligand-bearing aqueous fluids and a hydrous haplogranitic melt at 2.6 GPa and 600-800 °C, spanning the conditions relevant to slab dehydration and melting. The solubilities of REE in aqueous fluids increase more than an order of magnitude with temperature increasing from 600 to 800 °C. Addition of ligands such as Cl-, F-, CO32-, SO42- in relatively small concentrations (0.3-1.5 m [mol/kg H2O]) has a pronounced effect further enhancing REE solubilities. Each ligand yields a characteristic REE pattern by preferential dissolution of either the light or the heavy REE. For example, the addition of NaCl to the aqueous fluids yields highly elevated LREE/HREE ratios (La/Yb=17.4±4.3), whereas the addition of fluoride and sulfate ligands significantly increases the solubility of all REE with moderate LREE/HREE fractionation (La/Yb∼4). The addition of Na2CO3 results in preferential increase of HREE solubilities, and yields La/Yb ratio of 1.6±0.5 by flattening the moderately fractionated REE pattern seen in pure aqueous fluids. The solubilities in hydrous haplogranite melt are moderate in comparison to those observed in aqueous fluids and do not lead to pronounced REE fractionation. Therefore, REE can be effectively mobilized and fractionated by aqueous fluids, compared to felsic hydrous melts. Furthermore, the aqueous fluid chemistry has a major role in determining REE mobilities and fractionation upon slab dehydration in addition to the significant control exerted by temperature. Our results show that chloride-bearing slab

  9. Thulium anomalies and rare earth element patterns in meteorites and Earth: Nebular fractionation and the nugget effect

    NASA Astrophysics Data System (ADS)

    Dauphas, Nicolas; Pourmand, Ali

    2015-08-01

    This study reports the bulk rare earth element (REEs, La-Lu) compositions of 41 chondrites, including 32 falls and 9 finds from carbonaceous (CI, CM, CO and CV), enstatite (EH and EL) and ordinary (H, L and LL) groups, as well as 2 enstatite achondrites (aubrite). The measurements were done in dynamic mode using multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS), allowing precise quantification of mono-isotopic REEs (Pr, Tb, Ho and Tm). The CI-chondrite-normalized REE patterns (LaN/LuN; a proxy for fractionation of light vs. heavy REEs) and Eu anomalies in ordinary and enstatite chondrites show more scatter in more metamorphosed (petrologic types 4-6) than in unequilibrated (types 1-3) chondrites. This is due to parent-body redistribution of the REEs in various carrier phases during metamorphism. A model is presented that predicts the dispersion of elemental and isotopic ratios due to the nugget effect when the analyzed sample mass is limited and elements are concentrated in minor grains. The dispersion in REE patterns of equilibrated ordinary chondrites is reproduced well by this model, considering that REEs are concentrated in 200 μm-size phosphates, which have high LaN/LuN ratios and negative Eu anomalies. Terrestrial rocks and samples from ordinary and enstatite chondrites display negative Tm anomalies of ∼-4.5% relative to CI chondrites. In contrast, CM, CO and CV (except Allende) show no significant Tm anomalies. Allende CV chondrite shows large excess Tm (∼+10%). These anomalies are similar to those found in group II refractory inclusions in meteorites but of much smaller magnitude. The presence of Tm anomalies in meteorites and terrestrial rocks suggests that either (i) the material in the inner part of the solar system was formed from a gas reservoir that had been depleted in refractory dust and carried positive Tm anomalies or (ii) CI chondrites are enriched in refractory dust and are not representative of solar composition for

  10. Rare earth element distributions and fractionation in plankton from the northwestern Mediterranean Sea.

    PubMed

    Strady, Emilie; Kim, Intae; Radakovitch, Olivier; Kim, Guebuem

    2015-01-01

    Rare earth element (REE) concentrations were measured for the first time in plankton from the northwestern Mediterranean Sea. The REE concentrations in phytoplankton (60-200 μm) were 5-15 times higher than those in four size fractions of zooplankton: 200-500 μm, 500-1000 μm, 1000-2000 μm and >2000 μm. The concentrations within these zooplankton fractions exhibited the same ranges with some variation attributed to differences in zooplankton taxonomy. The REE concentrations in plankton were poorly related to the reported REE concentrations of seawater, but they correlated well with the calculated REE(3+), concentrations especially with regard to middle REE (MREEs) and heavy REEs (HREEs). Plankton and seawater revealed different PAAS-normalised REE distributions, with the greatest differences observed in the light REEs. Interestingly, a comparison of PAAS-normalized sediment particles from the study of Fowler et al. (1992) showed concentrations of the same order of magnitude and a similar REE distribution without MREE enrichment. Based on this comparison, we propose a conceptual model that emphasizes the importance of biological scavenging of REEs (especially LREEs) in surface waters. PMID:24972173

  11. Ocean particle chemistry: The fractionation of rare earth elements between suspended particles and seawater

    SciTech Connect

    Sholkovitz, E.R. ); Landing, W.M.; Lewis, B.L. )

    1994-03-01

    Sargasso Sea suspended particles were sequentially digested with three chemical treatments (acetic acid, mild HCl/HNO[sub 3], and HF/HNO[sub 3]/HCl in a bomb). The latter two treatments dissolve detrital minerals, while the acetic acid removes surface coatings (organic matter and Mn oxides). The rare earth element (REE) composition of the surface coatings, in marked contrast to the crust-like REE composition of the two detrital phases, is extensively fractionated with respect to both filtered seawater and the crust. Surface coatings are responsible for the removal and fractionation of REEs from seawater and, as such, play a key role in the marine geochemical cycles of trace elements. Relative to seawater, the surface coatings are systematically enriched tenfold across the trivalent REEs from Lu to La and develop large positive Ce-anomalies. The Ce-anomalies of the coatings switch from being negative (seawater-like) in the upper 100 m to being strongly positive at greater depths. The ingrowth of Ce and LREEs on particle surfaces reflects the in situ oxidation of dissolved Ce(III) to particulate Ce(IV), and the preferential removal of LREE(III)s over HREE(III)s. REEs(III) fractionation of this type is consistent with particle/solution models. Both processes appear to be related to the in situ formation of Mn oxide particles from the oxidation of dissolved Mn(II) in the upper 200 m of the water column. Preferential removal of LREEs in the upper waters is countered by their preferential release at depth due to remineralization of surface coatings on particles. A new method is explored for estimating the residence time of suspended particles by combining Ce concentration data of dissolved and surface-bound phases with the Ce(III) oxidation rate measurements of MOFFETT (1990). A Ce-based residence time of thirteen days is similar in magnitude to the value calculated from U-[sup 234]Th disequilibria in the Sargasso Sea.

  12. Rare Earth Element - Humic Acid Interaction: Experimental Evidence for Kinetic and Equilibrium Fractionation in Aqueous Systems.

    NASA Astrophysics Data System (ADS)

    Sonke, J. E.; Salters, V. J.; Benedetti, M. F.

    2003-12-01

    Dissolved organic matter (DOM) is well known for it's strong binding capacity for trace metals. In order to better predict the role of DOM in the speciation and transport of trace metals in the environment we coupled capillary electrophoresis (CE), a molecular separation technique, to a Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). The combination of these two techniques allows for the study of non-labile metal speciation in aquatic samples. By separating Rare Earth Element (REE) complexes with EDTA and Humic Acid's (i.e. ligand competition) we have been able to determine conditional equilibrium binding constants (Kc) and kinetic rate constants for all 14 REE's with Humic (HA) and Fulvic Acids (FA) as a function of pH (6-9) and ionic strength (IS, 0.01-0.1 mol/L). Assuming a 1:1 binding mechanism, logKc values for REE-FA varied from 9.0 (La) to 10.5 (Lu) at pH 6, 0.1 mol/L IS, and 11.7 (La) to 14.6 (Lu) at pH 9, 0.1 mol/L IS. LogKc values for REE-HA were 10.6 (La) to 12.2 (Lu) at pH 6, 0.1 mol/L IS and 13.2 (La) to 16.5 (Lu) at pH 9, 0.1 mol/L IS. Slightly higher values for Kc were obtained at 0.01 mol/L IS. The general observations of stronger REE-HA binding compared to REE-FA, and stronger binding with increasing pH and decreasing IS correlate with our current understanding of metal-DOM interactions (1). Both Kc's as well as kinetic rate constants increase with increasing REE mass number (decreasing ionic radius); a reflection of the well-known lanthanide contraction. This is the first comprehensive metal binding dataset between REE and DOM, and the first experimental evidence for differential equilibrium and kinetic binding behavior between REE's and DOM. The 30-1000 fold increase in binding strength of heavy REE's with DOM provides for a an equilibrium fractionation mechanism that may explain features of the global geochemical REE cycle such as fractionation related to weathering, estuarine mixing, and REE scavenging in the deep ocean

  13. Effect of earthworms (Eisenia fetida) on the fractionation and bioavailability of rare earth elements in nine Chinese soils.

    PubMed

    Wen, Bei; Liu, Ying; Hu, Xiao-yu; Shan, Xiao-quan

    2006-05-01

    The effect of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), fraction distribution pattern and bioavailability of rare earth elements (REEs) Y, La, Ce, Pr and Nd in nine Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community (Standards, Measurements and Testing Programme) was used to fractionate REEs in soils into water soluble, exchangeable and carbonate bound (B1), Fe- and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). Inoculated with earthworms, the soil pH, DOC and water-soluble rare earth elements fraction increased. A significant correlation was obtained between the increased DOC and the increased water-soluble REEs. REEs in fraction B1 increased after earthworm inoculation, while those in fraction B3 decreased. No significant differences were observed for REEs in fraction B2. The biomass and the concentrations of REEs in wheat shoots and roots increased after the treatment with earthworms. The results demonstrated that earthworm activity increased the mobility and bioavailability of REEs in soils. PMID:16289225

  14. Fractionation mechanisms of rare earth elements (REEs) in hydroponic wheat: an application for metal accumulation by plants.

    PubMed

    Ding, Shiming; Liang, Tao; Zhang, Chaosheng; Huang, Zechun; Xie, Yaning; Chen, Tongbin

    2006-04-15

    Fractionations of rare earth elements (REEs) in wheat (Triticum aestivum L.) were observed through application of exogenous mixed REEs under hydroponic conditions. Middle REE (MREE), light REE (LREE), and heavy REE (HREE) enrichments were found in roots, stems, and leaves, respectively, accompanied by the tetrad effect (an effect that can cause a split of REE patterns into four consecutive segments) in these organs. Investigations into REE speciation in roots and in the xylem sap with X-ray absorption spectroscopy (XAS) and nanometer-sized TiO2 adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations in wheat were caused by the combined effects of chemical precipitation, cell wall absorption, and solution complexation by organic ligands in the xylem vessels. REE fractionations in wheat, which were derived from the small differences of chemical properties across REE series, may reflect a sensitive internal chemical environment that influences plant accumulation for REEs and their analogues actinide radionuclides. PMID:16683609

  15. Accumulation and fractionation of rare earth elements in atmospheric particulates around a mine tailing in Baotou, China

    NASA Astrophysics Data System (ADS)

    Wang, Lingqing; Liang, Tao

    2014-05-01

    Rare earth elements (REEs) have been increasingly emitted into the atmosphere with a worldwide increase in use of these metals. However, the research on REEs in atmospheric particulates is fairly limited. In this paper, atmospheric particulates including total suspended particulate (TSP) matter and particles with an equivalent aerodynamic diameter less than 10 μm (PM10) were collected around a rare earth mine tailing in Baotou, the largest rare earth industrial base in China, in August 2012 and March 2013, for the analyses of REE levels and distributions. The total concentrations of REEs for TSP were 172.91 and 297.49 ng/m3, and those for PM10 were 63.23 and 105.52 ng/m3, in August 2012 and March 2013, respectively. Enrichment factors for all 14 analyzed REEs in the TSP and PM10 indicated that the REE enrichment in atmosphere particulates was caused by anthropogenic sources and influenced by the strong wind in spring season. The spatial distribution of REEs in TSP showed a strong gradient in the prevailing wind direction. The chondrite-normalized patterns of REEs in TSP and PM10 were similar with the conspicuous fractionation between light REEs and heavy REEs.

  16. Fractionation of rare-earth elements in allanite and monazite as related to geology of the Mt. Wheeler mine area, Nevada

    USGS Publications Warehouse

    Lee, D.E.; Bastron, H.

    1967-01-01

    Rare-earth contents of 20 allanites and 13 monazites, accessory minerals from a restricted outcrop area of intrusive granitic rocks, are reported. A quantity called sigma (??), which is the sum of the atomic percentages of La, Ce and Pr, is used as an index of composition with respect to the rare-earth elements. Values of sigma vary from 61.3 to 80.9 at.% for these allanites and monazites, representing an appreciable range of composition in terms of the rare-earth elements. Degree of fractionation of rare earths varies directly with CaO content of the granitic rocks, which in turn depends largely on proximity of limestone. Four xenoliths included in the study suggest that spotty mosaic equilibria are superimposed on the regional gradients and that locally the degree of fractionation of rare earths responds to whole rock composition over distances of a few yards or less. The chemistry of the granitic rocks under study appears to be similar in some respects to that of alkalio rocks and carbonatites. Allanites from the most calcium-rich rocks show a pronounced concentration of the most basic rare earths, and whole-rock concentrations of such rare constituents as total cerium earths, Zr, F, Ti, Ba and Sr increase sympathetically with whole-rock calcium. The explanation for the concentration gradients observed in this chemical system must involve assimilation more than magmatic differentiation. ?? 1967.

  17. [Effects of soil pH value on the bioavailability and fractionation of rare earth elements in wheat seedling (Triticum aestivum L.)].

    PubMed

    Cao, Xinde; Ding, Zhuhong; Hu, Xin; Wang, Xiaorong

    2002-01-30

    The effect of soil pH value on the bioavailability and fractionation of rare earth elements (REEs) in wheat seedling (Triticum aestivum L.) were investigated. The results showed that the concentration of REEs in wheat decreased with increasing pH value, and their inter-relationship was best expressed as quadratic equation, with correlation coefficients from 0.6003 to 0.9572. The response of individual elements to pH value change tended to be Ce > La > Nd > Sm > Gd > Yb > Eu, with Ce most sensitive to changing pH conditions and Eu lest. Chemical fractionation indicated that the order of REEs concentration in three fractions could be as follows: B2(NH2OH.HCl extraction) > B3(H2O2-NH4Ac extract) > B1(HAc extract). The increase of pH value resulted in transformation from B1 to B2 and B3. Multiple regression analysis was utilized to obtain the regression equations for prediction plant uptake of REEs. B1 fraction was most available to wheat. Meanwhile, it was found that the fractionation factors of REEs in wheat were negatively correlated with the soil pH value. PMID:11987417

  18. Impact of plant species, substrate types and porosity on the fractionation of rare-earth elements in plants

    NASA Astrophysics Data System (ADS)

    Semhi, K.; Clauer, N.; Chaudhuri, S.

    2009-04-01

    The distribution and content of rare-earth elements (REEs) were determined in two radish species (Raphanus sativus and Raphanus raphanistrum) that were grown under laboratory-controlled conditions, in three substrates consisting in illite for one and in smectite for the two others, the two latter being of the same type but with different porosities. The plants were split into two segments: the leaves and the stems+roots. The results indicate that both species pick up systematically higher amounts of REEs when grown in the illite substrate, considering that the smectite contains about 3 times more REEs. In R. sativus, the REE concentration of the leaves and of the stems+roots, whatever the substrate, ranges from 1.4 to 1.9 g/g. After normalization to the substrate in which they grew, the distribution patterns for the leaves of those from illite substrate are nearly flat, but irregular with a positive Eu anomaly. Those for the stems+roots are similar, but enriched in heavy REEs, also with a positive Eu anomaly. The REE concentrations of the leaves and the stems+roots of R. sativus grown in smectite are analytically similar at 1.6 and 1.4 g/g, respectively. The REE distribution patterns for the two organs, normalized again to those of the substrate, are very similar, flat with a distinct Eu anomaly. The heavy REE of the stems+roots of R. sativus grown on illite are enriched relative to those of the leaves, and a distinct positive Eu anomaly is observed in both the leaves and stems+roots from species grown on both illite and smectite. In the case of R. raphanistrum, the REE concentrations of the leaves and the stems+roots for those grown in the illite substrate were found to be significantly different at 11.0 and 6.6 g/g, respectively. The REE distribution patterns for the two different plant organs normalized to those of the substrates were found to be quite similar, all being quite flat, with a more or less pronounced Ce negative anomaly, and a prominent

  19. Fractionation of Volatile Elements by Heating of Solid Allende: Implications for the Source Material of Earth, Moon, and the Eucrite Parent Body

    NASA Astrophysics Data System (ADS)

    Jochum, K. P.; Palme, H.

    1993-07-01

    CI-chondrites have average solar-system abundances of moderately volatile (Na, K, Rb, Sn, etc.) and highly volatile (Cs, Pb, etc.) elements. In most other types of chondrites and in samples from differentiated planetary bodies, these elements are more or less depleted relative to CI chondrites. Volatile-element fractionation occurred either by evaporation or incomplete condensation [1]. Recent data on the isotopic composition of K indicate that depletion of volatiles did not occur by evaporation from a melt of CI-chondritic composition [2]. Evaporative loss from a solid, however, would not necessarily lead to isotopic fractionation of K in the residue [e.g., 3]. In order to study loss of volatile elements from solids, we performed a series of heating experiments under variable oxygen fugacities at temperatures of 1050 degrees C to 1300 degrees C. Residues were analyzed by INAA [4]. We report here additional analyses (K, Rb, Cs, Sn, Pb) of these residues by isotope dilution-SSMS. Results (including Na data from INAA) are shown in Fig. 1. Results at other oxygen fugacities are similar, i.e., there is no strong dependence on fO2, contrary to the results for Au, As, and Zn [4]. Elements are arranged in the order of decreasing condensation temperatures. Depletions increase with increasing temperature and, at least for the 1050 degrees C experiment, with decreasing condensation temperature. The CI- normalized Allende pattern has no strong depletions of Cs and Pb, unlike the experimental results, indicating that evaporation from a solid cannot produce patterns observed in volatile-element-depleted meteorites. Even heating at temperatures as low as 1050 degrees C, affecting alkali elements only slightly, leads to large losses of lead, which are an order of magnitude greater than required for producing CV chondrite patterns. Depletions of these elements apparently occurred in the solar nebula before accretion by incomplete condensation or removal of gas during condensation

  20. Controls on the distribution and fractionation of yttrium and rare earth elements in core sediments from the Mandovi estuary, western India

    NASA Astrophysics Data System (ADS)

    Prajith, A.; Rao, V. Purnachandra; Kessarkar, Pratima M.

    2015-01-01

    Mineralogy, major elements (Fe, Mn and Al), rare earths and yttrium (REY) of bulk sediments were analyzed in four gravity cores recovered along the main channel of the Mandovi estuary, western India, to determine the sources and controls on REY distribution. The accelerator mass spectrometer (AMS) ages of total organic carbon indicated modern age for the sediments of the upper estuary and, maximum mean ages of 1588 years AD and 539 years AD for the bottom sediments of the cores in the lower estuary and bay, respectively. The sediments of the upper/middle estuary showed abundant hematite, magnetite and goethite and high Fe, Mn, total-REE (ΣREE) and Y, while those in the lower estuary/bay showed abundant silicate minerals and relatively low Fe, Mn, ΣREE and Y. ΣREE showed significant correlation with clay and silt fractions and Y, Al and organic carbon (OC) content of the sediments. The light to heavy REE ratios (LREE/HREE) of sediments were lower than in Post-Archean Australian Shale (PAAS). The PAAS-normalized rare earths and yttrium (REY; Y inserted between Dy and Ho) patterns of sediments showed middle REE (MREE)- and HREE-enrichment with positive Eu anomaly (Eu/Eu*) and variable Ce anomaly (Ce/Ce*). The REY of sediments is primarily controlled by its texture and REE of source sediment, which is ore material-dominated in the upper/middle estuary and silicate material-dominated in the lower estuary/bay. Low LREE/HREE ratios suggest that very fine-grained sediments were carried away from the estuary because of high-energy conditions. Fractionations of REY (Y/Ho, Sm/Nd, Ce/Ce* and Eu/Eu*) are controlled by different mechanisms. High Y/Ho ratios in clayey silts are due to redistribution of Y and Ho by adsorption onto organic-rich, clays. Variations in Sm/Nd ratios are similar to that of Eu/Eu* in cores from the lower estuary/bay and are controlled by mineral constituents of the sediments. Positive Ce and Eu anomalies are inherited from ore material, and ore

  1. Condensation and fractionation of rare earths in the solar nebula

    NASA Technical Reports Server (NTRS)

    Davis, A. M.; Grossman, L.

    1979-01-01

    The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

  2. Binding and transport of rare earth elements by organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

    NASA Astrophysics Data System (ADS)

    Stolpe, Björn; Guo, Laodong; Shiller, Alan M.

    2013-04-01

    Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of nanocolloids (0.5-40 nm) in the dynamics and transport of rare earth elements (REEs) in northern high latitude watersheds influenced by permafrost. Total dissolved (<0.45 μm) concentrations and the 'nanocolloidal size distributions' (0.5-40 nm) of UV-absorbing dissolved organic matter, Fe, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu were determined by on-line coupling of flow field-flow fractionation (FFF) with a UV-absorbance detector and ICP-MS. Total dissolved and nanocolloidal concentrations of the REEs co-varied with dissolved organic carbon (DOC) in all rivers and between spring flood and late summer baseflow. The nanocolloidal size distributions indicated the presence of three major components of nanocolloids: the 0.5-3 nm 'fulvic-rich nanocolloids' occurring throughout the sampling season, the 'organic/iron-rich nanocolloids' residing in the <8 nm size range during the spring flood, and the 4-40 nm iron-rich nanocolloids occurring during summer baseflow. REEs associated with all the three components of nanocolloids, but the proportions associated with the fulvic-rich nanocolloids during summer baseflow increased with increasing REE molar mass, which is consistent with the increase in stability of organic REE-complexes with increasing REE molar mass. Normalization of the measured REE-concentrations with the average REE-concentrations of the upper continental crust revealed a dynamic change in the physicochemical fractionation of REEs. During the spring flood, REE-binding in all the rivers was dominated by the <8 nm organic/iron-rich nanocolloids, likely being eroded from the upper organic-rich soil horizon by the strong surface runoff of snowmelt water. During the summer, the REE-binding in rivers with large groundwater input was dominated by small (<0.5 nm) organic and/or inorganic complexes, while lower proportions of the REEs

  3. Magnetite fractionation of "chalcophile" elements

    NASA Astrophysics Data System (ADS)

    Mavrogenes, J. A.; Jenner, F. E.; Arculus, R. J.

    2008-12-01

    Submarine-quenched glasses provide the clearest record of magmatic evolution available, especially with respect to potentially volatile elements and compounds. A comprehensive suite of arc- and backarc glasses recovered during several research voyages in the SW Pacific are being analysed by a number of research teams in an effort to document genesis and fractionation processes involved in the evolution of subduction- related magma systems. As part of these studies, a suite of basalt to dacite composition glasses recovered from the arc-like Pacmanus Site in the Manus Backarc Basin have been examined in detail. Sun et al. (2004) found trends of increasing enrichments of Re, Cu, and Au with SiO2 in the range from 50 to 60 wt% SiO2. From this stage of magmatic evolution, marked depletions in all these elements are observed in glasses of higher SiO2 contents. The reasons for this trend have been unclear, although a mechanism involving the cessation of olivine and initiation of magnetite saturation was proposed by Sun et al. Our analysis of a larger suite of glasses from the Manus Basin has now confirmed these trends, and found the same behaviour for Zn and Mn. Similarly, analysis of a suite of basalt to dacite glasses recovered from the arc-like Valu Fa Ridge in the Lau Backarc Basin has produced trends for these elements very similar to those of the Pacmanus location. LA-ICP-MS analysis of microphenocrysts in these glasses has shown that magnetite is highly enriched in Re relative to the coexisting melt (Kd up to 7.8 for Re). Magnetite/melt partition coefficients for Re, Mn and Yb can be used to precisely model the liquid line of descent during magnetite (plus clinopyroxene and plagioclase) fractionation using Re vs. Mn/Yb. The variation of Pt abundances with SiO2 for both these suites contrasts with other nominally chalcophile trace elements in showing rapid early depletion from the most Mg-rich basalt through to more SiO2-rich compositions, with no maximum at 60 wt

  4. Alkali metal and rare earth element evolution of rock-forming minerals from the Gatumba area pegmatites (Rwanda): Quantitative assessment of crystal-melt fractionation in the regional zonation of pegmatite groups

    NASA Astrophysics Data System (ADS)

    Hulsbosch, Niels; Hertogen, Jan; Dewaele, Stijn; André, Luc; Muchez, Philippe

    2014-05-01

    This study presents a general model for the evaluation of Rayleigh fractional crystallisation as the principal differentiation mechanism in the formation of regionally zoned common and rare-element pegmatites. The magmatic evolution of these systems from a granitic source is reconstructed by means of alkali element and rare earth element (REE) analyses of rock-forming minerals (feldspars, micas and tourmaline), which represent a whole sequence of regional pegmatite zonation. The Gatumba pegmatite field (Rwanda, Central Africa) is chosen as case study area because of its well-developed regional zonation sequence. The pegmatites are spatially and temporally related to peraluminous G4-granites (986 ± 10 Ma). The regional zonation is developed around a G4-granite and the proximal pegmatites grade outwardly into biotite, two-mica and muscovite pegmatites. Rare-element (Nb-Ta-Sn) pegmatites occur most distal from the granite.

  5. Scarcity of rare earth elements.

    PubMed

    de Boer, M A; Lammertsma, K

    2013-11-01

    Rare earth elements (REEs) are important for green and a large variety of high-tech technologies and are, therefore, in high demand. As a result, supply with REEs is likely to be disrupted (the degree of depends on the REE) in the near future. The 17 REEs are divided into heavy and light REEs. Other critical elements besides REEs, identified by the European Commission, are also becoming less easily available. Although there is no deficiency in the earth's crust of rare earth oxides, the economic accessibility is limited. The increased demand for REEs, the decreasing export from China, and geopolitical concerns on availability contributed to the (re)opening of mines in Australia and the USA and other mines are slow to follow. As a result, short supply of particularly terbium, dysprosium, praseodymium, and neodymium is expected to be problematic for at least the short term, also because they cannot be substituted. Recycling REEs from electronic waste would be a solution, but so far there are hardly any established REE recycling methods. Decreasing the dependency on REEs, for example, by identifying possible replacements or increasing their efficient use, represents another possibility. PMID:24009098

  6. Trace and rare earth elements fractionation in volcanic- and sediment-hosted Mn ores: a study case of Sardinia (western Italy).

    NASA Astrophysics Data System (ADS)

    Sinisi, Rosa

    2015-04-01

    It is widely accepted that, regardless of the geological environment (continental, marine or hydrothermal), the occurrences of clay minerals and/or mineral phases with clay-type crystal structure (as zeolites and Mn-oxides), play a key role in the trace elements and REEs uptake processes. The REE resources are produced mostly from ion-adsorption type REE deposits of southern China that are formed by weathering of granitic rocks and subsequent chemical adsorption of REE on clay minerals. A significant group of minerals with a high metal uptake capacity is represented by Mn oxides. Their "tunnel" structure, in fact, allows both the absorption (inside the minerals) and adsorption (outside the minerals) of cations and anions producing metal accumulations with economic and environmental significance. However, the ores, mainly that forming within sedimentary environment, often have impurities due to presence of minerals unrelated to mineralization. These minerals can significantly alter the compositional features of the ores and suggest misleading conclusions. In Sardinia (Italy, western Mediterranean), Mn-oxide mineralizations occur and recently their origin has been discussed and identified (Sinisi et al. 2012). In this study the mineralogical and chemical compositions of the Sardinian sediment-hosted and volcanic-hosted Mn-ore are exhibit exploring the possibility that they can represent exploitable trace and REE mineralizations. High contents of metals characterize these Mn deposits. Besides some trace elements (Ni, Cr, Zn, Cu, As, Pb, and U) that commonly typify the Mn oxi-hydroxide ores, all rare earth elements showed high concentrations in the Sardinian deposits, comparable to those of the main actually exploited REE sinks. For this reason, a simple statistical data treatment (R-mode Factor Analysis) was performed on fifteen and nineteen samples of sediment-hosted and volcanic-hosted Mn ore respectively, in order to identify both the mineral phases trapping trace

  7. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  8. Alkali element constraints on Earth-Moon relations

    NASA Technical Reports Server (NTRS)

    Norman, M. D.; Drake, M. J.; Jones, J. H.

    1994-01-01

    Given their range of volatilities, alkali elements are potential tracers of temperature-dependent processes during planetary accretion and formation of the Earth-Moon system. Under the giant impact hypothesis, no direct connection between the composition of the Moon and the Earth is required, and proto-lunar material does not necessarily experience high temperatures. Models calling for multiple collisions with smaller planetesimals derive proto-lunar materials mainly from the Earth's mantle and explicitly invoke vaporization, shock melting and volatility-related fractionation. Na/K, K/Rb, and Rb/Cs should all increase in response to thermal volatization, so theories which derive the Moon substantially from Earth's mantle predict these ratios will be higher in the Moon than in the primitive mantle of the Earth. Despite the overall depletion of volatile elements in the Moon, its Na/K and K/Rb are equal to or less than those of Earth. A new model presented here for the composition of Earth's continental crust, a major repository of the alkali elements, suggests the Rb/Cs of the Moon is also less than that of Earth. Fractionation of the alkali elements between Earth and Moon are in the opposite sense to predictions based on the relative volatilities of these elements, if the Moon formed by high-T processing of Earth's mantle. Earth, rather than the Moon, appears to carry a signature of volatility-related fractionation in the alkali elements. This may reflect an early episode of intense heating on Earth with the Moon's alkali budget accreting from cooler material.

  9. Early cosmochemical fractionation by collisional erosion during the Earth's accretion

    NASA Astrophysics Data System (ADS)

    Boujibar, A.; Andrault, D.; Bolfan-Casanova, N.; Bouhifd, M. A.

    2014-12-01

    Early in the Solar System history, planets grew through energetic collisions between planetesimals. Partial destruction of planetary embryos could have produce heterogeneous bodies, because of widespread internal chemical differentiation through core-segregation, partial melting of silicated mantles and fractional crystallization of magma oceans. On larger proto-planets, including the early Earth, meteoritic impacts have potentially induced erosion of part of the surface, which could have affected significantly the final chemical composition of terrestrial planets. Here we report that collisional erosion of 15-18% of the early Earth's surface reconciles the major apparent compositional differences between the known enstatite chondrites (EC) and the bulk Earth. We base our arguments on experimental measurements of the melting properties of an EC body at pressures between 1 bar and 25 GPa. At low degree of partial melting, the silicate melts are found highly enriched in SiO2, Al2O3 and Na2O and strongly depleted in MgO. Loss through collisional erosion of the surface of such differentiated planetesimal should ultimately raise its Mg/Si ratio and decrease its concentration in incompatible elements. We elaborate auto-coherent models of the Earth formation. Vaporization into space of the protocrusts could be a source of the Na-rich SiO gas that interacted with chondrules and explain the enrichments of enstatite chondrites in SiO2 and volatile lithophile elements.

  10. Rare earth elements in the Amazon basin

    NASA Astrophysics Data System (ADS)

    Gerard, M.; Seyler, P.; Benedetti, M. F.; Alves, V. P.; Boaventura, G. R.; Sondag, F.

    2003-05-01

    The rare earth element (REE) concentrations of the dissolved and particulate fractions and bed sediment between Manaus and Santarém in the Amazon River, and in some major tributaries, were evaluated. A very important zone in the Amazon basin, the encontro das aguas area where the Rio Solimões and the Rio Negro meet, was especially sampled. Different size fractions were isolated by ultrafiltration. Water samples were collected at different stages of the mixing. Three groups of waters are distinguished: group I has a low pH (<5·5) and is represented by the Negro basin rivers; group II has alkalinity less than 0·2 meq l-1 and is represented by the Rios Tapajós and Trombetas; group III has high alkalinity (>0·2 meq l-1) and higher pH (>6·5) and is represented by the Madeira basin rivers, the Solimões and the Amazon. The highest dissolved REE concentration is in the Rio Negro and the lowest in the Rio Tapajós (dissolved REEs vary by more than a factor of ten). The solubility of REEs is pH dependent: in river waters with a pH < 6 the Ce concentration is twice that of La, whereas in rivers with a higher pH the concentrations of Ce and La are similar. Dissolved REE concentrations are positively correlated with the dissolved organic carbon. Correlations between Fe, Al, and La suggest that La is associated with Al (Fe)-rich organic matter and/or related to dissolved Fe-rich inorganic material. Dissolved REEs normalized to North American shale composite show an enrichment in intermediate/heavy REEs (from Eu to Er), except for the shields rivers (such as Rio Negro and Rio Trombetas). Both of them are depleted in heavy REEs and show a relative Ce enrichment. In contrast, for the Andeans rivers (such as Rio Solimões), light REEs are slightly depleted and a negative Ce relative anomaly occurs. The pattern of the Amazon River at Óbidos confirms the major influence of the Rios Negro and Solimões with REE fractionation. For the Rio Negro, 60 to 70% of REEs are

  11. Systematic variation of rare-earth elements in cerium-earth minerals

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J., Jr.; Carron, M.K.; Glass, J.J.

    1957-01-01

    In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (???), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ??? for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ??? for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ??? is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ??? greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements-efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ??? in one crystal and a slightly smaller value of ??? in the outer part of the other crystal compared to the inner part. The ??? of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ??? of monazites in the intruded host rock. These results indicate that the fractionation of the

  12. TWO EXTRASOLAR ASTEROIDS WITH LOW VOLATILE-ELEMENT MASS FRACTIONS

    SciTech Connect

    Jura, M.; Xu, S.; Klein, B.; Zuckerman, B.; Koester, D. E-mail: sxu@astro.ucla.edu E-mail: ben@astro.ucla.edu

    2012-05-01

    Using ultraviolet spectra obtained with the Cosmic Origins Spectrograph on the Hubble Space Telescope, we extend our previous ground-based optical determinations of the composition of the extrasolar asteroids accreted onto two white dwarfs, GD 40 and G241-6. Combining optical and ultraviolet spectra of these stars with He-dominated atmospheres, 13 and 12 polluting elements are confidently detected in GD 40 and G241-6, respectively. For the material accreted onto GD 40, the volatile elements C and S are deficient by more than a factor of 10 and N by at least a factor of 5 compared to their mass fractions in primitive CI chondrites and approach what is inferred for bulk Earth. A similar pattern is found for G241-6 except that S is undepleted. We have also newly detected or placed meaningful upper limits for the amount of Cl, Al, P, Ni, and Cu in the accreted matter. Extending results from optical studies, the mass fractions of refractory elements in the accreted parent bodies are similar to what is measured for bulk Earth and chondrites. Thermal processing, perhaps interior to a snow line, appears to be of central importance in determining the elemental compositions of these particular extrasolar asteroids.

  13. Rare earth elements in Hamersley BIF minerals

    NASA Astrophysics Data System (ADS)

    Alibert, Chantal

    2016-07-01

    Minerals from the Hamersley banded iron formation, Western Australia, were analyzed for Y and rare earth elements (YREEs) by laser ablation ICP-MS to investigate diagenetic pathways, from precursor phases to BIF minerals. One group of apatites carries the seawater REE signature, giving evidence that P and REEs, thoroughly scavenged from the water column by Si-ferrihydrite particles, were released upon microbial Fe3+ reductive dissolution of Si-ferrihydrite in pore-water and finally sequestered mainly in authigenic apatite. The absence of fractionation between apatite and seawater suggests that REE were first incorporated into an amorphous calcium phosphate as fully hydrated cations, i.e. as outer-sphere complexes. The iron oxides and carbonates carry only a small fraction of the whole-rock REE budget. Their REE patterns are distinctly enriched in Yb and show some M-type tetrad effect consistent with experimental Kd(REE) between solid and saline solution with low carbonate ion concentrations. It is deduced that hematite formed at an incipient stage of Fe2+-catalyzed dissolution of Si-ferrihydrite, via a dissolution-reprecipitation pathway. The REE pattern of greenalite, found as sub-micron particles in quartz in a chert-siderite sample, is consistent with its authigenic origin by precipitation in pore-water after dissolution of a small amount of Si-ferrihydrite. Magnetite carries very low YREEs (ppb-level), has an homogeneous pattern distinctly enriched in the mid-REEs compared to hematite, and includes a late population depleted in light-REEs, Ba and As. Magnetite forming aggregates and massive laminae is tentatively interpreted as reflecting some fluid-aided hematite-magnetite re-equilibration or transformation at low-grade metamorphic temperatures.

  14. Rare earth element scavenging in seawater

    NASA Astrophysics Data System (ADS)

    Byrne, Robert H.; Kim, Ki-Hyun

    1990-10-01

    Examinations of rare earth element (REE) adsorption in seawater, using a variety of surface-types, indicated that, for most surfaces, light rare earth elements (LREEs) are preferentially adsorbed compared to the heavy rare earths (HREEs). Exceptions to this behavior were observed only for silica phases (glass surfaces, acid-cleaned diatomaceous earth, and synthetic SiO 2). The affinity of the rare earths for surfaces can be strongly affected by thin organic coatings. Glass surfaces which acquired an organic coating through immersion in Tampa Bay exhibited adsorptive behavior typical of organic-rich, rather than glass, surfaces. Models of rare earth distributions between seawater and carboxylate-rich surfaces indicate that scavenging processes which involve such surfaces should exhibit a strong dependence on pH and carbonate complexation. Scavenging models involving carboxylate surfaces produce relative REE abundance patterns in good general agreement with observed shale-normalized REE abundances in seawater. Scavenging by carboxylate-rich surfaces should produce HREE enrichments in seawater relative to the LREEs and may produce enrichments of lanthanum relative to its immediate trivalent neighbors. Due to the origin of distribution coefficients as a difference between REE solution complexation (which increases strongly with atomic number) and surface complexation (which apparently also increases with atomic number) the relative solution abundance patterns of the REEs produced by scavenging reactions can be quite complex.

  15. What about the rare-earth elements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There is insufficient understanding of the nutritional physiology of pecan trees and orchards; thus, affecting nutmeat yield and quality, disease resistance and alternate bearing. An analysis of the rare-earth element composition of pecan and related hickory cousins found that they hyperaccumulate ...

  16. Cosmochemical fractionation by collisional erosion during the Earth's accretion

    NASA Astrophysics Data System (ADS)

    Boujibar, Asmaa; Andrault, Denis; Bolfan-Casanova, Nathalie; Bouhifd, Mohamed Ali; Monteux, Julien

    2015-09-01

    Early in the Solar System's history, energetic collisions of differentiated bodies affected the final composition of the terrestrial planets through partial destruction. Enstatite chondrites (EC) are the best candidates to represent the primordial terrestrial precursors as they present the most similar isotopic compositions to Earth. Here we report that collisional erosion of >15% of the early Earth's mass can reconcile the remaining compositional differences between EC and the Earth. We base our demonstration on experimental melting of an EC composition at pressures between 1 bar and 25 GPa. At low pressures, the first silicate melts are highly enriched in incompatible elements Si, Al and Na, and depleted in Mg. Loss of proto-crusts through impacts raises the Earth's Mg/Si ratio to its present value. To match all major element compositions, our model implies preferential loss of volatile lithophile elements and re-condensation of refractory lithophile elements after the impacts.

  17. Cosmochemical fractionation by collisional erosion during the Earth's accretion

    PubMed Central

    Boujibar, Asmaa; Andrault, Denis; Bolfan-Casanova, Nathalie; Bouhifd, Mohamed Ali; Monteux, Julien

    2015-01-01

    Early in the Solar System's history, energetic collisions of differentiated bodies affected the final composition of the terrestrial planets through partial destruction. Enstatite chondrites (EC) are the best candidates to represent the primordial terrestrial precursors as they present the most similar isotopic compositions to Earth. Here we report that collisional erosion of >15% of the early Earth's mass can reconcile the remaining compositional differences between EC and the Earth. We base our demonstration on experimental melting of an EC composition at pressures between 1 bar and 25 GPa. At low pressures, the first silicate melts are highly enriched in incompatible elements Si, Al and Na, and depleted in Mg. Loss of proto-crusts through impacts raises the Earth's Mg/Si ratio to its present value. To match all major element compositions, our model implies preferential loss of volatile lithophile elements and re-condensation of refractory lithophile elements after the impacts. PMID:26395157

  18. Cosmochemical fractionation by collisional erosion during the Earth's accretion.

    PubMed

    Boujibar, Asmaa; Andrault, Denis; Bolfan-Casanova, Nathalie; Bouhifd, Mohamed Ali; Monteux, Julien

    2015-01-01

    Early in the Solar System's history, energetic collisions of differentiated bodies affected the final composition of the terrestrial planets through partial destruction. Enstatite chondrites (EC) are the best candidates to represent the primordial terrestrial precursors as they present the most similar isotopic compositions to Earth. Here we report that collisional erosion of >15% of the early Earth's mass can reconcile the remaining compositional differences between EC and the Earth. We base our demonstration on experimental melting of an EC composition at pressures between 1 bar and 25 GPa. At low pressures, the first silicate melts are highly enriched in incompatible elements Si, Al and Na, and depleted in Mg. Loss of proto-crusts through impacts raises the Earth's Mg/Si ratio to its present value. To match all major element compositions, our model implies preferential loss of volatile lithophile elements and re-condensation of refractory lithophile elements after the impacts. PMID:26395157

  19. Isotope fractionation in surface ionization ion source of alkaline-earth iodides

    SciTech Connect

    Suzuki, T.; Kanzaki, C.; Nomura, M.; Fujii, Y.

    2012-02-15

    The relationship between the isotope fractionation of alkaline-earth elements in the surface ionization ion source and the evaporation filament current, i.e., filament temperature, was studied. It was confirmed that the isotope fractionation depends on the evaporation filament temperature; the isotope fractionation in the case of higher temperature of filament becomes larger. The ionization and evaporation process in the surface ionization ion source was discussed, and it was concluded that the isotope fractionation is suppressed by setting at the lower temperature of evaporation filament because the dissociations are inhibited on the evaporation filament.

  20. Rare earth element systematics in hydrothermal fluids

    SciTech Connect

    Michard, A. )

    1989-03-01

    Rare earth element concentrations have been measured in hydrothermal solutions from geothermal fields in Italy, Dominica, Valles Caldera, Salton Sea and the Mid-Atlantic Ridge. The measured abundances show that hydrothermal activity is not expected to affect the REE balance of either continental or oceanic rocks. The REE enrichment of the solutions increases when the pH decreases. High-temperature solutions (> 230{degree}C) percolating through different rock types may show similar REE patterns.

  1. Rare earth elements and permanent magnets (invited)

    NASA Astrophysics Data System (ADS)

    Dent, Peter C.

    2012-04-01

    Rare earth (RE) magnets have become virtually indispensible in a wide variety of industries such as aerospace, automotive, electronics, medical, and military. RE elements are essential ingredients in these high performance magnets based on intermetallic compounds RECo5, RE2TM17 (TM: transition metal), and RE2TM14B. Rare earth magnets are known for their superior magnetic properties—high induction, and coercive force. These properties arise due to the extremely high magnetocrystalline anisotropy made possible by unique 3d-4f interactions between transition metals and rare earths. For more than 40 years, these magnets remain the number one choice in applications that require high magnetic fields in extreme operating conditions—high demagnetization forces and high temperature. EEC produces and specializes in RECo5 and RE2TM17 type sintered magnets. Samarium and gadolinium are key RE ingredients in the powder metallurgical magnet production processes which include melting, crushing, jet milling, pressing, sintering, and heat treating. The magnetic properties and applications of these magnets will be discussed. We will also briefly discuss the past, current, and future of the permanent magnet business. Currently, over 95% of all pure rare earth oxides are sourced from China, which currently controls the market. We will provide insights regarding current and potential new magnet technologies and designer choices, which may mitigate rare earth supply chain issues now and into the future.

  2. Rare earth elements in synthetic zircon. 1. synthesis, and rare earth element and phosphorus doping.

    SciTech Connect

    Hanchar, J. M.; Finch, R. J.; Hoskin, W. O.; Watson, E. B.; Cherniak, D. J.; Mariano, A. N.; Chemical Engineering; George Washington Univ.; Univ. of Canterbury; Australian National Univ.; Rensselaer Polytechnic Inst.

    2001-05-01

    Sedimentary mineral assemblages commonly contain detrital zircon crystals as part of the heavy-mineral fraction. Age spectra determined by U-Pb isotopic analysis of single zircon crystals within a sample may directly image the age composition--but not the chemical composition--of the source region. Rare earth element (REE) abundances have been measured for zircons from a range of common crustal igneous rock types from different tectonic environments, as well as kimberlite, carbonatite, and high-grade metamorphic rocks, to assess the potential of using zircon REE characteristics to infer the rock types present in sediment source regions. Except for zircon with probable mantle affinities, zircon REE abundances and normalized patterns show little intersample and intrasample variation. To evaluate the actual variation in detrital zircon REE composition in a true sediment of known mixed provenance, zircons from a sandstone sample from the Statfjord Formation (North Sea) were analyzed. Despite a provenance including high-grade metasediment and granitoids and a range in zircon age of 2.82 b.y., the zircon REEs exhibit a narrow abundance range with no systematic differences in pattern shape. These evidences show zircon REE patterns and abundances are generally not useful as indicators of provenance.

  3. Alkaline Element Fractionations in LL-chondritic Breccias

    NASA Astrophysics Data System (ADS)

    Misawa, K.; Yokoyama, T.; Okano, O.

    2010-12-01

    Introduction: Fractionation of moderately volatile lithophile elements including alkaline elements was an important process in the early solar system. Alkali-rich igneous fragments (K-rich fragments) were found in brecciated LL-chondrites. These fragments in Kraehenberg (LL5), Bhola (LL3-6), and Yamato (Y)-74442 (LL4) show fractionated alkaline element patterns; for example, abundances of alkaline elements in the Kraehenberg fragment are ~0.5 x CI for Na, ~12 x CI for K,~45 x CI for Rb, and ~70 x CI for Cs [1]. In order to understand moderately volatile element fractionations, we have undertaken mineralogical and petrological studies on K-rich fragments in Kraehenberg [1], Bhola [2], and Y-74442 [3, 4]. Results and Discussion: Kraehenberg, Bhola, and Y-74442 consist of mineral fragments, K-rich fragments, impact-melt clasts, chondrules, and matrix. K-rich fragments in these meteorites are composed of 10-100 µm-sized euhedral olivine (~60 vol.%) and groundmass of brown glasses (~40 vol.%, including microcrystalline pyroxene) which are highly enriched in alkaline elements. Dendritic pyroxene and chromite (~1 µm in size) along with troilite (~10 µm in size) are commonly observed in the groundmass. The textures are different from those of impact melt clasts in ordinary chondrites. Chemical compositions of olivine in the K-rich fragments fall within the compositional range of equilibrated LL-chondrites (Fa26-32 [5]). Groundmass glasses in the Kraehenberg, Bhola, and Y-74442 fragments are almost identical in composition when plotted on a Na+K+Al-oxides-Ca+Mg+Fe-oxides-SiO2 ternary diagram [1]. The fractionation trend is also observed in an angular igneous fragment in Siena (LL5) [6]. The lack of K isotopic fractionation effects in the K-rich clast in Kraehenberg [7] implies that the enrichment of (heavier) alkaline elements occurred near-equilibrium conditions. The K-rich fragments in Kraehenberg and Y-74442 could be early solar system materials (~4.56 Ga [8, 9

  4. Note: Portable rare-earth element analyzer using pyroelectric crystal.

    PubMed

    Imashuku, Susumu; Fuyuno, Naoto; Hanasaki, Kohei; Kawai, Jun

    2013-12-01

    We report a portable rare-earth element analyzer with a palm-top size chamber including the electron source of a pyroelectric crystal and the sample stage utilizing cathodoluminescence (CL) phenomenon. The portable rare-earth element analyzer utilizing CL phenomenon is the smallest reported so far. The portable rare-earth element analyzer detected the rare-earth elements Dy, Tb, Er, and Sm of ppm order in zircon, which were not detected by scanning electron microscopy-energy dispersive X-ray spectroscopy analysis. We also performed an elemental mapping of rare-earth elements by capturing a CL image using CCD camera. PMID:24387481

  5. Note: Portable rare-earth element analyzer using pyroelectric crystal

    SciTech Connect

    Imashuku, Susumu Fuyuno, Naoto; Hanasaki, Kohei; Kawai, Jun

    2013-12-15

    We report a portable rare-earth element analyzer with a palm-top size chamber including the electron source of a pyroelectric crystal and the sample stage utilizing cathodoluminescence (CL) phenomenon. The portable rare-earth element analyzer utilizing CL phenomenon is the smallest reported so far. The portable rare-earth element analyzer detected the rare-earth elements Dy, Tb, Er, and Sm of ppm order in zircon, which were not detected by scanning electron microscopy-energy dispersive X-ray spectroscopy analysis. We also performed an elemental mapping of rare-earth elements by capturing a CL image using CCD camera.

  6. Anthropogenic Cycles of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Du, X.; Graedel, T. E.

    2009-12-01

    This research will develop quantitatively resolved anthropogenic cycles and in-use stocks for the rare earth metals specifically cerium, lanthanum and dysprosium in Japan, China, and the U.S. for the year of 2007. Rare earth elements (REE) is a group of 17 scare metals widely used in a growing number of emerging technologies and have been in high demand for emerging technologies as raw materials during past the three decades. New market participants from newly industrializing countries, primarily China, have had strong impacts on the demand of share. Consequently, the importance to sustain a reliable, steady, uninterrupted supply on global market triggered comprehensive research to recognize and understand the life cycles of rare earths. Moreover, because China plays a dominant role in mining production since 1990, it requires the assessment for the countries, which are almost completely dependent on imports from China with respect to rare earth resources. The study aims to analyze the flows and stocks of rare earth elements individually as elemental form in spite of their natural geological co-occurrence and mixed composition in applications. By applying the method of Material Flow Analysis (MFA) work has been done on evaluating current and historical flows of specific technologically significant materials, for example, copper, zinc, nickel, etc., determining the stocks available in different types of reservoirs (e.g., lithosphere, in-use) and the flows among the reservoirs, developing scenarios of possible futures of metal use, and assessing the environmental and policy implications of the results. Therefore, REE as a new target deserves inclusion because of its potential demand-supply conflict and importance to secure the competitive advantage of technical innovation in future. This work will generate a quantitatively resolved anthropogenic life cycle and in-use stocks for REE for the main target countries for a chosen year, 2007, providing flows and stocks from

  7. Rare earth element patterns in biotite, muscovite and tourmaline minerals

    SciTech Connect

    Laul, J.C.; Lepel, E.A.

    1986-04-21

    Rare earth element concentrations in the minerals biotite and muscovite from the mica schist country rocks of the Etta pegmatite and tourmalines from the Bob Ingersoll pegmatite have been measured by INAA and CNAA. The concentrations range from 10/sup -4/ g/g to 10/sup -10g//sub g/. The REE patterns of biotite, muscovite and tourmaline reported herein are highly fractionated from light to heavy REE. The REE concentrations in biotite and muscovite are high and indigenous. The pegmatite tourmalines contain low concentrations of REE. Variations in tourmaline REE patterns reflect the geochemical evolution of pegmatite melt/fluid system during crystallization.

  8. Siderophile elements and the earth's formation

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Capobianco, C. J.; Drake, M. J.; O'Neill, Hugh

    1992-01-01

    Two comments on a work by Murthy (1991) concerning the abundances of siderophile elements in the earth's mantle are presented. In the first comment it is asserted that the basis of Murthy's extrapolation is the assumption that the Gibbs free energy change for the partitioning reaction is independent of temperature, and as this is generally not a valid assumption thermodynamically, and as this is contradicted by most experimental data, the issue of mantle siderophile elements remains unresolved. In the second comment it is asserted that the extrapolation method used by Murthy does not appear to be valid thermodynamically, and that an extrapolation based on generally accepted thermodynamic assumptions yields different results. In a reply, Murthy takes issue with the comments.

  9. Tipping elements in the Earth's climate system

    SciTech Connect

    Lenton, T.M.; Held, H.; Lucht, W.; Rahmstorf, S.; Kriegler, E. |; Hall, J.W.; Schellnhuber, H.J. |

    2008-02-12

    The term 'tipping point' commonly refers to a critical threshold at which a tiny perturbation can qualitatively alter the state or development of a system. Here the authors introduce the term 'tipping element' to describe large-scale components of the Earth system that may pass a tipping point. They critically evaluate potential policy-relevant tipping elements in the climate system under anthropogenic forcing, drawing on the pertinent literature and a recent international workshop to compile a short list, and they assess where their tipping points lie. An expert elicitation is used to help rank their sensitivity to global warming and the uncertainty about the underlying physical mechanisms. Then the authors explain how, in principle, early warning systems could be established to detect the proximity of some tipping points.

  10. Xenon Fractionation, Hydrogen Escape, and the Oxidation of the Earth

    NASA Astrophysics Data System (ADS)

    Zahnle, K. J.; Catling, D. C.

    2014-12-01

    Xenon in Earth's atmosphere is severely mass fractionated and depleted compared to any plausible solar system source material, yet Kr is unfractionated. These observations seem to imply that Xe has escaped from Earth. Vigorous hydrodynamic hydrogen escape can produce mass fractionation in heavy gases. The required hydrogen flux is very high but within the range permitted by solar EUV heating when Earth was 100 Myrs old or younger. However this model cannot explain why Xe escapes but Kr does not. Recently, what appears to be ancient atmospheric xenon has been recovered from several very ancient (3-3.5 Ga) terrestrial hydrothermal barites and cherts (Pujol 2011, 2013). What is eye-catching about this ancient Xe is that it is less fractionated that Xe in modern air. In other words, it appears that a process was active on Earth some 3 to 3.5 billion years ago that caused xenon to fractionate. By this time the Sun was no longer the EUV source that it used to be. If xenon was being fractionated by escape — currently the only viable hypothesis — it had to be in Earth's Archean atmosphere and under rather modest levels of EUV forcing. It should be possible for Xe, but not Kr, to escape from Earth as an ion. In a hydrodynamically escaping hydrogen wind the hydrogen is partially ionized. The key concepts are that ions are much more strongly coupled to the escaping flow than are neutrals (so that a relatively modest flow of H and H+ to space could carry Xe+ along with it, the flux can be small enough to be consistent with diffusion-limited flux), and that Xe alone among the noble gases is more easily ionized than hydrogen. This sort of escape is possible along the polar field lines, although a weak or absent magnetic field would likely work as well. The extended history of hydrogen escape implicit in Xe escape in the Archean is consistent with other suggestions that hydrogen escape in the Archean was considerable. Hydrogen escape plausibly played the key role in creating

  11. Development of a Rare Earth Element Paleoproxy

    NASA Astrophysics Data System (ADS)

    Haley, B. A.; Klinkhammer, G. P.; McManus, J.

    2002-12-01

    The rare earth elements (REEs) have demonstrated considerable potential as paleoproxies for changes in seawater chemistry. However, their utilization in paleoceanographic investigations has been mainly limited to neodymium isotopic analyses in metalliferous deposits and fossil apatite. The goal of being able to use the entire group of elements in foraminiferal shells has proven difficult. The problem with analysis of these elements in this matrix stems mainly from: (1) the ability to clean the shells of diagenetic aberrations and (2) the paucity of REE data in the environment where forams obtain their primary signature. We recently measured pore water profiles of REEs using an interfaced Ion Chromatograph (IC) and Inductively Coupled Plasma Mass Spectrometer (ICP-MS) in a depth transect off the Coast of California, and a profile from off the Peru-Chile margin. The pore water results are surprising and will alter our view of REE marine geochemistry. For example, they call into question the traditional method of calculating a "Ce-anomaly." The profiles also show dramatic changes in REE concentrations and patterns with depth, and demonstrate that the REE signature preserved in epifaunal benthic versus infaunal foram species and diagenetically added phases should be easily identifiable. Preliminary REE results from forams cleaned via a recently developed flow-through technique will be shown and compared to matching pore water data. We will conclude by outlining the potential of foraminiferal REE content for paleoceanography that ranges from water mass tracer to proxies for organic carbon flux and oxygen concentration.

  12. Rare earth elements materials production from apatite ores

    NASA Astrophysics Data System (ADS)

    Anufrieva, A. V.; Andrienko, O. S.; Buynovskiy, A. S.; Makaseev, Y. N.; Mazov, I. N.; Nefedov, R. A.; Sachkov, V. I.; Stepanova, O. B.; Valkov, A. V.

    2016-01-01

    The paper deals with the study of processing apatite ores with nitric acid and extraction of the rare earth elements. The rare earth elements can be successfully separated and recovered by extraction from the nitrate- phosphate solution, being an tributyl phosphate as extraction agent. The developed scheme of the processing apatite concentrate provides obtaining rare earth concentrates with high qualitative characteristics.

  13. Rare earth elements in river waters

    NASA Technical Reports Server (NTRS)

    Goldstein, Steven J.; Jacobsen, Stein B.

    1988-01-01

    To characterize the input to the oceans of rare earth elements (REE) in the dissolved and the suspended loads of rivers, the REE concentrations were measured in samples of Amazon, Indus, Mississippi, Murray-Darling, and Ohio rivers and in samples of smaller rivers that had more distinct drainage basin lithology and water chemistry. It was found that, in the suspended loads of small rivers, the REE pattern was dependent on drainage basin geology, whereas the suspended loads in major rivers had relatively uniform REE patterns and were heavy-REE depleted relative to the North American Shale composite (NASC). The dissolved loads in the five major rivers had marked relative heavy-REE enrichments, relative to the NASC and the suspended material, with the (La/Yb)N ratio of about 0.4 (as compared with the ratio of about 1.9 in suspended loads).

  14. Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

    SciTech Connect

    Selle, J E

    1992-06-26

    Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.

  15. Rare Earth Elements: A Tool for Understanding the Behaviour of Trivalent Actinides in the Geosphere

    SciTech Connect

    Buil, Belen; Gomez, Paloma; Garralon, Antonio; Turrero, M. Jesus

    2007-07-01

    Rare earth element (REE) concentrations have been determined in groundwaters, granite and fracture fillings in a restored uranium mine. The granitoids normalized REE patterns of groundwaters show heavy rare earth elements (HREE)-enrichment and positive Eu anomalies. This suggests that the REE are fractionated during leaching from the source rocks by groundwaters. Preferential leaching of HREE would be consistent with the greater stability of their aqueous complexes compared to those of the light rare earth elements (LREE), together with the dissolution of certain fracture filling minerals, dissolution/alteration of phyllosilicates and colloidal transport. (authors)

  16. Rare earth element analysis indicates micropollutants in an urban estuary

    NASA Astrophysics Data System (ADS)

    Mohajerin, T. J.; Johannesson, K. H.; Kolker, A.; Burdige, D. J.; Chevis, D.

    2011-12-01

    Rare earth element analysis of Bayou Bienvenue waters shows anomalously high gadolinium, Gd, concentrations relative to its nearest neighbors in the REE series, europium and terbium. The anomalously high Gd concentrations indicate anthropogenic input from waste-water treatment plants in the area as anthropogenic Gd input can be traced back to its use as a contrast agent in magnetic resonance imaging in hospitals. Others have shown that anomalously high levels of Gd in natural waters are likely to be associated with other micropollutants that also occur in hospital effluent and that are not removed in the wastewater treatment process, including pharmaceuticals in the form of steroids, antihistamines, and antibiotics. Estuaries serve as many important ecological roles and have been shown to act as a filter for pollutants. To better understand the transport, biogeochemical cycling, and ultimate fate of trace elements in estuaries, I collected surface water samples from Bayou Bienvenue, a wetland triangle that covers an area of 427 acres directly adjacent to New Orleans, Louisiana. Water samples from Bayou Bienvenue were collected along the salinity gradient and subsequently filtered through progressively smaller pore-size filters. The resulting fractions were analyzed for trace element concentions, including the REEs, by magnetic sector ICP-MS. The attached figure shows the Gd anomaly present in the particulate (>0.45μm) fraction. Upper continental crust (UCC)-normalized plots of colloidal REEs (0.02μm - 0.45μm) fraction is lacking this anomaly indicating anthropogenic Gd is found chiefly in the particulate fraction in Bayou Bienvenue. No clear relationship between Gd concentration and salinity was apparent.

  17. Google Earth locations of USA and seafloor hydrothermal vents with associated rare earth element data

    DOE Data Explorer

    Andrew Fowler

    2016-02-10

    Google Earth .kmz files that contain the locations of geothermal wells and thermal springs in the USA, and seafloor hydrothermal vents that have associated rare earth element data. The file does not contain the actual data, the actual data is available through the GDR website in two tier 3 data sets entitled "Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge (MOR) Hydrothermal Vents" and "Rare earth element content of thermal fluids from Surprise Valley, California"

  18. Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

    NASA Astrophysics Data System (ADS)

    Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

    2009-10-01

    Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

  19. W/Hf Fractionation in Chondrites and the Earth: Constraints on Timing of Core Formation

    NASA Astrophysics Data System (ADS)

    Newsom, H. E.

    1996-03-01

    The recent measurements of the Hf and W isotope systematics in terrestrial and meteorite material has led Lee and Halliday to conclude that terrestrial core formation occurred at least 60 Myr after the formation of the iron meteorites. This calculation depends on assumptions regarding the Hf/W ratio for the bulk silicate Earth, and for the ratio in the chondritic material from which the iron meteorites, and the Earth formed. A new study of the abundance and depletion of W in the Earth, relative to refractory lithophile elements, such as Hf, provides constraints on the terrestrial Hf/W ratio. In the chondrites, the ratio of W to refractory lithophile elements is also variable, because W did not fully participate in the metal-silicate fractionation which occurred in the solar nebula. Therefore, the uncertainties in the Hf/W ratios in the chondrites and in the Earth must be considered to determine the constraints on the timing of core formation in the Earth. In the case of the heterogeneous accretion theory, W is accreted to the Earth's primitive mantle in an additive process, which has important implications for the significance of the Hf-W isotope systematics.

  20. Size distribution of rare earth elements in coal ash

    USGS Publications Warehouse

    Scott, Clinton T.; Deonarine, Amrika; Kolker, Allan; Adams, Monique; Holland, James F.

    2015-01-01

    Rare earth elements (REEs) are utilized in various applications that are vital to the automotive, petrochemical, medical, and information technology industries. As world demand for REEs increases, critical shortages are expected. Due to the retention of REEs during coal combustion, coal fly ash is increasingly considered a potential resource. Previous studies have demonstrated that coal fly ash is variably enriched in REEs relative to feed coal (e.g, Seredin and Dai, 2012) and that enrichment increases with decreasing size fractions (Blissett et al., 2014). In order to further explore the REE resource potential of coal ash, and determine the partitioning behavior of REE as a function of grain size, we studied whole coal and fly ash size-fractions collected from three U.S commercial-scale coal-fired generating stations burning Appalachian or Powder River Basin coal. Whole fly ash was separated into , 5 um, to 5 to 10 um and 10 to 100 um particle size fractions by mechanical shaking using trace-metal clean procedures. In these samples REE enrichments in whole fly ash ranges 5.6 to 18.5 times that of feedcoals. Partitioning results for size separates relative to whole coal and whole fly ash will also be reported. 

  1. Germanium and Rare Earth Element accumulation in woody bioenergy crops

    NASA Astrophysics Data System (ADS)

    Hentschel, Werner

    2016-04-01

    Germanium and REEs are strategic elements that are used for high tech devices and engineered systems, however these elements are hardly concentrated into mineable ore deposits. Since these elements occur widely dispersed in the earth crust with concentrations of several mgṡkg‑1 (Ge 1.6 mgṡkg‑1, Nd 25 mgṡkg‑1) a new possibility to gain these elements could be phytomining, a technique that uses plants to extract elements from soils via their roots. Since knowledge about accumulating plant species is quite limited we conducted research on the concentrations of strategic elements in wood and leaves of fast growing tree species (Salix spec., Populus spec., Betula pendula, Alnus glutinosa, Fraxinus excelsior, Acer pseudoplatanus). In total 35 study sites were selected in the mining affected area around Freiberg (Saxony, Germany), differing in their species composition and degree of contamination with toxic trace metals (Pb, As, Cd). On each site plant tissues (wood and leaves, respectively) of different species were sampled. In addition soil samples were taken from a soil depth of 0 - 30 cm and 30 - 60 cm. The aim of our work was to investigate correlations between the concentrations of the target elements in plant tissues and soil characteristics like pH, texture, nutrients and concentrations in six operationally defined soil fractions (mobile, acid soluble, oxidizable, amorphic oxides, crystalline oxides, residual or siliceous). Concentrations of elements in soil extracts and plant tissues were measured with ICP-MS. The element Nd was selected as representative for the group of REEs, since this element showed a high correlation with the concentrations of the other REE We found that the concentration of Nd in the leaves (0.31 mgṡkg‑1Nd) were several times higher than in herbaceous species (0.05 mgṡkg‑1 Nd). The concentration of Ge in leaves were ten times lower than that of Nd whereas in herbaceous species Nd and Ge were in equal magnitude. Within

  2. Earth's moderately volatile element composition may not be chondritic: Evidence from In, Cd and Zn

    NASA Astrophysics Data System (ADS)

    Wang, Zaicong; Laurenz, Vera; Petitgirard, Sylvain; Becker, Harry

    2016-02-01

    Current models assume that siderophile volatile elements (SVE) are depleted in bulk Earth to the same extent as lithophile elements of similar volatility. The observed additional depletion of many SVE relative to lithophile elements in the bulk silicate Earth (BSE) is ascribed to partitioning of SVE into Earth's core. However, the assumption of similar volatility of moderately volatile elements during Earth formation processes as in solar gas is quite uncertain. Here, these assumptions will be tested by assessing abundances and ratios of indium and cadmium in the BSE using new data on mantle rocks, and the application of high- and low-pressure-temperature metal-silicate partitioning data. New bulk rock abundance data of In and Cd obtained on bulk rocks of peridotite tectonites and xenoliths by isotope dilution refine previous results inferred from basalts and in-situ analyses of silicate minerals in peridotite xenoliths. The CI chondrite-normalized abundance of In in the BSE is similar to zinc and is 3-4 times higher than Cd. New and published low- and high-P-T metal-silicate partitioning data indicate that, during core formation at a range of conditions, In is always more siderophile than Zn and Cd. Adding the fraction of these elements in Earth's core to the BSE results in bulk Earth compositions that yield higher CI chondrite normalized abundances of In in the bulk Earth compared to Zn and Cd. Because In is more volatile than Zn and Cd in gas of solar composition, suprachondritic In/Zn and In/Cd in the bulk Earth suggest that during formation of Earth or its building materials, the volatilities of these elements and perhaps other volatile elements likely have changed significantly (i.e. In became less volatile). The results also suggest that known carbonaceous chondrites likely did not deliver the main volatile element-rich fraction of the Earth. Various arguments suggest that the loss of moderately volatile elements during planetary accretion should be limited

  3. Volatile element depletion and K-39/K-41 fractionation in lunar soils

    NASA Technical Reports Server (NTRS)

    Church, S. E.; Tilton, G. R.; Wright, J. E.; Lee-Hu, C.-N.

    1976-01-01

    Evidence for selective loss and isotopic fractionation (in the case of K) of volatile elements during formation of agglutinates by micrometeoritic bombardment of lunar soils is presented. Concentrations and isotopic compositions of volatile elements (K, Rb, Pb) and nonvolatile elements (U, Th, Ba, Sr, rare earths) in separates taken from soils 14163, 14259, 15041, 68501, and 71500 are examined. Rayleigh fractionation calculations applied to K-39/K-41 isotopic data indicate ten-fold recycling of bulk soil, to account for observed isotopic anomalies. The lunar soil fines fraction seems to be a site of deposition for volatile or labile Pb produced during agglutination. Local fines (below 75 microns) are viewed as representative of the parent material for agglutinates formed in situ by micrometeoritic impact. Magnetic separation of agglutinates from soil 68501 revealed a bimodal population, with one class comprising welded blocky magnetic glasses.

  4. Biogeochemistry of the rare-earth elements with particular reference to hickory trees

    USGS Publications Warehouse

    Robinson, W.O.; Bastron, H.; Murata, K.J.

    1958-01-01

    Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H2SO3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water. ?? 1958.

  5. Nebular fractionation of silicon isotopes and implications for silicon in Earth's core

    NASA Astrophysics Data System (ADS)

    Dauphas, N.; Poitrasson, F.; Burkhardt, C.

    2014-12-01

    The silicate Earth has a heavy silicon isotopic composition relative to all chondrite groups, which was taken as evidence for the presence of sufficient amounts of silicon in Earth's core to explain its density deficit. A difficulty remains, however, in that chondrites themselves show variable silicon isotopic composition. For example, enstatite chondrites, the only group of meteorites that matches the Earth's composition for 17O, 48Ca, 50Ti, 54Cr, and 92Mo, have very light silicon isotopic compositions that would require unrealistic amounts of silicon in Earth's core if they were its main constituents. We have measured the silicon isotopic composition of several achondrites that had not been measured before. In particular, we have found that angrites have a heavy silicon isotopic composition, similar to the Earth and the Moon. These meteorites formed under relatively oxidizing conditions (~IW+1) and core formation in their parent-body occurred at relatively low pressure (<0.1 GPa), so core-mantle silicon isotopic fractionation is excluded as a cause for their Earth-like silicon isotopic composition. Angrites are among the most volatile-depleted meteorites and their heavy silicon isotope signature most likely reflects isotopic fractionation by nebular processes. All chondrite groups and the bulk silicate Earth form a trend in silicon isotopic composition vs. Mg/Si ratio, which we will show quantitatively can be explained by a simple nebular process. This can also explain the similarity in silicon isotopic composition between lunar and terrestrial rocks. Therefore, silicon isotopes in terrestrial rocks provide no constraints on the amount of Si in the core and are consistent with the presence of other light elements such as oxygen.

  6. Earth, Air, Fire and Water in Our Elements

    ERIC Educational Resources Information Center

    Lievesley, Tara

    2007-01-01

    The idea that everything is made of the four "elements", earth, air, fire and water, goes back to the ancient Greeks. In this article, the author talks about the origins of ideas about the elements. The author provides an account that attempts to summarise thousands of years of theoretical development of the elements in a thousand words or so.

  7. Rare earth element association with foraminifera

    NASA Astrophysics Data System (ADS)

    Roberts, Natalie L.; Piotrowski, Alexander M.; Elderfield, Henry; Eglinton, Timothy I.; Lomas, Michael W.

    2012-10-01

    Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ˜20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment-water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes

  8. Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

    USGS Publications Warehouse

    Piper, David Z.; Bau, Michael

    2013-01-01

    The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

  9. Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

    NASA Technical Reports Server (NTRS)

    Righter, Kevin; Pando, K.; Danielson, L.; Nickodem, K.

    2014-01-01

    Depletions of volatile siderophile elements (VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd) in mantles of Earth and Moon, constrain the origin of volatile elements in these bodies, and the overall depletion of volatile elements in Moon relative to Earth. A satisfactory explanation has remained elusive [1,2]. We examine the depletions of VSE in Earth and Moon and quantify the amount of depletion due to core formation and volatility of potential building blocks. We calculate the composition of the Earth's PUM during continuous accretion scenarios with constant and variable fO2. Results suggest that the VSE can be explained by a rather simple scenario of continuous accretion leading to a high PT metal-silicate equilibrium scenario that establishes the siderophile element content of Earth's PUM near the end of accretion [3]. Core formation models for the Moon explain most VSE, but calculated contents of In, Sn, and Zn (all with Tc < 750 K) are all still too high after core formation, and must therefore require an additional process to explain the depletions in the lunar mantle. We discuss possible processes including magmatic degassing, evaporation, condensation, and vapor-liquid fractionation in the lunar disk.

  10. Carbon and nitrogen isotope fractionation during possible organic aerosol formation in Titan and the early Earth

    NASA Astrophysics Data System (ADS)

    Imanaka, H.

    2012-12-01

    Abiotic formation of complex organic macromolecule aerosols is important not only for the potential for prebiotic chemical evolution, but also in the global elemental cycle. The direct clues of the habitable environment and biosphere on the early Earth are mostly obtained from geological records, such as isotope signatures and biomarkers in the ancient organic sediments. The recent Cassini-Huygens mission revealed the generation of complex organic aerosols in Titan's upper atmosphere, and similar processes could have lead to the formation of organic aerosols in the early Earth atmosphere. Understanding the formation reaction network and accompanying isotope fractionation processes of the organic aerosols is necessary to constrain the active organic environment on the early Earth from the available geological evidence. We have investigated the abiotic formation of organic aerosols in simulated atmospheres of Titan and the early, with particular focus on carbon and nitrogen isotope fractionation. Laboratory aerosol analogues, termed tholins, are generated with cold plasma irradiation of reduced gas mixtures, such as N2/CH4 and N2/H2/CO. Stable isotopic ratios of 15N/14N and 13C/12C for the generated tholins are measured with an elemental analysis-isotope ratio mass spectrometer (EA-IR-MS). Our preliminary data for tholins generated from an equivalent N2/CH4 (=90/10) gas mixture at various pressures suggests the 15N isotopic fractionation up to δ15N = -20~25 permil during tholin formation, while 13C isotopic fractionation seems almost negligible. This negative δ15N is even lighter than those observed in kerogens in the Archean sediments (Beaumont and Robert, 1999; Pinti et al., 2001), and the organic haze could have contributed to the source of 15N-depleted kerogens. Furthermore, the δ15N vary with deposition pressure. Previous works demonstrated that the resulted two types of tholin are very different in chemical structure and optical properties (Imanaka et al

  11. Investigating Rare Earth Element Systematics in the Marcellus Shale

    NASA Astrophysics Data System (ADS)

    Yang, J.; Torres, M. E.; Kim, J. H.; Verba, C.

    2014-12-01

    The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO3 ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our

  12. Attenuation of rare earth elements in a boreal estuary

    NASA Astrophysics Data System (ADS)

    Åström, Mats E.; Österholm, Peter; Gustafsson, Jon Petter; Nystrand, Miriam; Peltola, Pasi; Nordmyr, Linda; Boman, Anton

    2012-11-01

    This study focuses on attenuation of rare earth elements (REE) when a boreal creek, acidified and loaded with REE and other metals as a result of wetland drainage, empties into a brackish-water estuary (salinity < 6‰). Surface water was collected in a transect from the creek mouth to the outer estuary, and settling (particulate) material in sediment traps moored at selected locations in the estuary. Ultrafiltration, high-resolution ICP-MS and modeling were applied on the waters, and a variety of chemical reagents were used to extract metals from the settling material. Aluminium, Fe and REE transported by the acidic creek were extensively removed in the inner/central estuary where the acidic water was neutralised, whereas Mn was relatively persistent in solution and thus redistributed to particles and deposited further down the estuary. The REE removal was caused by several contemporary mechanisms: co-precipitation with oxyhydroxides (mainly Al but also Fe), complexation with flocculating humic substances and sorption to suspended particles. Down estuary the dissolved REE pool, remaining after removal, was fractionated: the <1 kDa pool became depleted in the middle REE and the colloidal (0.45 μm-1 kDa) pool depleted in the middle and heavy REE. This fractionation was controlled by the removal process, such that those REE with highest affinity for the settling particles became most depleted in the remaining dissolved pool. Modeling, based on Visual MINTEQ version 3.0 and the Stockholm Humic Model after revision and updating, predicted that the dissolved (<0.45 μm) REE pool in the estuary is bound almost entirely to humic substances. Acid sulphate soils, the source of the REE and other metals in the creek water, are widespread on coastal plains worldwide and therefore the REE attenuation patterns and mechanisms identified in the studied estuary are relevant for recognition of similar geochemical processes and conditions in a variety of coastal locations.

  13. Bioleaching of rare earth elements from monazite sand.

    PubMed

    Brisson, Vanessa L; Zhuang, Wei-Qin; Alvarez-Cohen, Lisa

    2016-02-01

    Three fungal strains were found to be capable of bioleaching rare earth elements from monazite, a rare earth phosphate mineral, utilizing the monazite as a phosphate source and releasing rare earth cations into solution. These organisms include one known phosphate solubilizing fungus, Aspergillus niger ATCC 1015, as well as two newly isolated fungi: an Aspergillus terreus strain ML3-1 and a Paecilomyces spp. strain WE3-F. Although monazite also contains the radioactive element Thorium, bioleaching by these fungi preferentially solubilized rare earth elements over Thorium, leaving the Thorium in the solid residual. Adjustments in growth media composition improved bioleaching performance measured as rare earth release. Cell-free spent medium generated during growth of A. terreus strain ML3-1 and Paecilomyces spp. strain WE3-F in the presence of monazite leached rare earths to concentrations 1.7-3.8 times those of HCl solutions of comparable pH, indicating that compounds exogenously released by these organisms contribute substantially to leaching. Organic acids released by the organisms included acetic, citric, gluconic, itaconic, oxalic, and succinic acids. Abiotic leaching with laboratory prepared solutions of these acids was not as effective as bioleaching or leaching with cell-free spent medium at releasing rare earths from monazite, indicating that compounds other than the identified organic acids contribute to leaching performance. PMID:26332985

  14. MaRGEE: Move and Rotate Google Earth Elements

    NASA Astrophysics Data System (ADS)

    Dordevic, Mladen M.; Whitmeyer, Steven J.

    2015-12-01

    Google Earth is recognized as a highly effective visualization tool for geospatial information. However, there remain serious limitations that have hindered its acceptance as a tool for research and education in the geosciences. One significant limitation is the inability to translate or rotate geometrical elements on the Google Earth virtual globe. Here we present a new JavaScript web application to "Move and Rotate Google Earth Elements" (MaRGEE). MaRGEE includes tools to simplify, translate, and rotate elements, add intermediate steps to a transposition, and batch process multiple transpositions. The transposition algorithm uses spherical geometry calculations, such as the haversine formula, to accurately reposition groups of points, paths, and polygons on the Google Earth globe without distortion. Due to the imminent deprecation of the Google Earth API and browser plugin, MaRGEE uses a Google Maps interface to facilitate and illustrate the transpositions. However, the inherent spatial distortions that result from the Google Maps Web Mercator projection are not apparent once the transposed elements are saved as a KML file and opened in Google Earth. Potential applications of the MaRGEE toolkit include tectonic reconstructions, the movements of glaciers or thrust sheets, and time-based animations of other large- and small-scale geologic processes.

  15. Modeling rammed earth wall using discrete element method

    NASA Astrophysics Data System (ADS)

    Bui, T.-T.; Bui, Q.-B.; Limam, A.; Morel, J.-C.

    2016-03-01

    Rammed earth is attracting renewed interest throughout the world thanks to its "green" characteristics in the context of sustainable development. Several research studies have thus recently been carried out to investigate this material. Some of them attempted to simulate the rammed earth's mechanical behavior by using analytical or numerical models. Most of these studies assumed that there was a perfect cohesion at the interface between earthen layers. This hypothesis proved to be acceptable for the case of vertical loading, but it could be questionable for horizontal loading. To address this problem, discrete element modeling seems to be relevant to simulate a rammed earth wall. To our knowledge, no research has been conducted thus far using discrete element modeling to study a rammed earth wall. This paper presents an assessment of the discrete element modeling's robustness for rammed earth walls. Firstly, a brief description of the discrete element modeling is presented. Then the parameters necessary for discrete element modeling of the material law of the earthen layers and their interfaces law following the Mohr-Coulomb model with a tension cut-off and post-peak softening were given. The relevance of the model and the material parameters were assessed by comparing them with experimental results from the literature. The results showed that, in the case of vertical loading, interfaces did not have an important effect. In the case of diagonal loading, model with interfaces produced better results. Interface characteristics can vary from 85 to 100% of the corresponding earthen layer's characteristics.

  16. Alkali elements in the Earth's core: Evidence from enstatite meteorites

    NASA Technical Reports Server (NTRS)

    Lodders, K.

    1995-01-01

    The abundances of alkali elements in the Earth's core are predicted by assuming that accretion of the Earth started from material similar in composition to enstatite chondrites and that enstatite achondrites (aubrites) provide a natural laboratory to study core-mantle differentiation under extremely reducing conditions. If core formation on the aubrite parent body is comparable with core formation on the early Earth, it is found that 2600 (+/- 1000) ppm Na, 550 (+/- 260) ppm K, 3.4 (+/- 2.1) ppm Rb, and 0.31 (+/- 0.24) ppm Cs can reside in the Earth's core. The alkali-element abundances are consistent with those predicted by independent estimates based on nebula condensation calculations and heat flow data.

  17. Rare earth elements and neodymium isotopes in sedimentary organic matter

    NASA Astrophysics Data System (ADS)

    Freslon, Nicolas; Bayon, Germain; Toucanne, Samuel; Bermell, Sylvain; Bollinger, Claire; Chéron, Sandrine; Etoubleau, Joel; Germain, Yoan; Khripounoff, Alexis; Ponzevera, Emmanuel; Rouget, Marie-Laure

    2014-09-01

    We report rare earth element (REE) and neodymium (Nd) isotope data for the organic fraction of sediments collected from various depositional environments, i.e. rivers (n = 25), estuaries (n = 18), open-ocean settings (n = 15), and cold seeps (n = 12). Sedimentary organic matter (SOM) was extracted using a mixed hydrogen peroxide/nitric acid solution (20%-H2O2-0.02 M-HNO3), after removal of carbonate and oxy-hydroxide phases with dilute hydrochloric acid (0.25 M-HCl). A series of experimental tests indicate that extraction of sedimentary organic compounds using H2O2 may be complicated occasionally by partial dissolution of sulphide minerals and residual carbonates. However, this contamination is expected to be minor for REE because measured concentrations in H2O2 leachates are about two-orders of magnitude higher than in the above mentioned phases. The mean REE concentrations determined in the H2O2 leachates for samples from rivers, estuaries, coastal seas and open-ocean settings yield relatively similar levels, with ΣREE = 109 ± 86 ppm (mean ± s; n = 58). The organic fractions leached from cold seep sediments display even higher concentration levels (285 ± 150 ppm; mean ± s; n = 12). The H2O2 leachates for most sediments exhibit remarkably similar shale-normalized REE patterns, all characterized by a mid-REE enrichment compared to the other REE. This suggests that the distribution of REE in leached sedimentary organic phases is controlled primarily by biogeochemical processes, rather than by the composition of the source from which they derive (e.g. pore, river or sea-water). The Nd isotopic compositions for organic phases leached from river sediments are very similar to those for the corresponding detrital fractions. In contrast, the SOM extracted from marine sediments display εNd values that typically range between the εNd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter

  18. Magnetic Nanofluid Rare Earth Element Extraction Process Report, Techno Economic Analysis, and Results for Geothermal Fluids

    DOE Data Explorer

    Pete McGrail

    2016-03-14

    This GDR submission is an interim technical report and raw data files from the first year of testing on functionalized nanoparticles for rare earth element extraction from geothermal fluids. The report contains Rare Earth Element uptake results (percent removal, mg Rare Earth Element/gram of sorbent, distribution coefficient) for the elements of Neodymium, Europium, Yttrium, Dysprosium, and Cesium. A detailed techno economic analysis is also presented in the report for a scaled up geothermal rare earth element extraction process. All rare earth element uptake testing was done on simulated geothermal brines with one rare earth element in each brine. The rare earth element uptake testing was conducted at room temperature.

  19. Determination of thorium and of rare earth elements in cerium earth minerals and ores

    USGS Publications Warehouse

    Carron, M.K.; Skinner, D.L.; Stevens, R.E.

    1955-01-01

    The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

  20. Anthropogenic disturbance of element cycles at the Earth's surface.

    PubMed

    Sen, Indra S; Peucker-Ehrenbrink, Bernhard

    2012-08-21

    The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes. PMID:22803636

  1. Multi-objective optimization of chromatographic rare earth element separation.

    PubMed

    Knutson, Hans-Kristian; Holmqvist, Anders; Nilsson, Bernt

    2015-10-16

    The importance of rare earth elements in modern technological industry grows, and as a result the interest for developing separation processes increases. This work is a part of developing chromatography as a rare earth element processing method. Process optimization is an important step in process development, and there are several competing objectives that need to be considered in a chromatographic separation process. Most studies are limited to evaluating the two competing objectives productivity and yield, and studies of scenarios with tri-objective optimizations are scarce. Tri-objective optimizations are much needed when evaluating the chromatographic separation of rare earth elements due to the importance of product pool concentration along with productivity and yield as process objectives. In this work, a multi-objective optimization strategy considering productivity, yield and pool concentration is proposed. This was carried out in the frame of a model based optimization study on a batch chromatography separation of the rare earth elements samarium, europium and gadolinium. The findings from the multi-objective optimization were used to provide with a general strategy for achieving desirable operation points, resulting in a productivity ranging between 0.61 and 0.75 kgEu/mcolumn(3), h(-1) and a pool concentration between 0.52 and 0.79 kgEu/m(3), while maintaining a purity above 99% and never falling below an 80% yield for the main target component europium. PMID:26375205

  2. Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

    NASA Technical Reports Server (NTRS)

    Schidlowski, M.

    1983-01-01

    Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

  3. Experimental constraints on light elements in the Earth's outer core.

    PubMed

    Zhang, Youjun; Sekine, Toshimori; He, Hongliang; Yu, Yin; Liu, Fusheng; Zhang, Mingjian

    2016-01-01

    Earth's outer core is liquid and dominantly composed of iron and nickel (~5-10 wt%). Its density, however, is ~8% lower than that of liquid iron, and requires the presence of a significant amount of light element(s). A good way to specify the light element(s) is a direct comparison of density and sound velocity measurements between seismological data and those of possible candidate compositions at the core conditions. We report the sound velocity measurements of a model core composition in the Fe-Ni-Si system at the outer core conditions by shock-wave experiments. Combining with the previous studies, we found that the best estimate for the outer core's light elements is ~6 wt% Si, ~2 wt% S, and possible ~1-2.5 wt% O. This composition satisfies the requirements imposed by seismology, geochemistry, and some models of the early core formation. This finding may help us to further constrain the thermal structure of the Earth and the models of Earth's core formation. PMID:26932596

  4. Miocene Coral Skeleton Rare Earth Element Patterns Reflect River Discharge

    NASA Astrophysics Data System (ADS)

    Mertz-Kraus, R.; Brachert, T. C.; Jochum, K. P.

    2010-12-01

    Rare Earth Element (REE) patterns of modern coral skeletons usually reflect the REE composition of ambient seawater which is characterized by heavy REE enriched relative to light REE with NASC (North American Shale Composite) normalized La/Lu ratios of typically <0.4. The REE concentration in coral aragonite is enriched by 3 to 4 orders of magnitude compared to ambient seawater. Here we report trace element data including REE of coral skeletons of Late Miocene age (~9 Ma, Tortonian) from Crete (Eastern Mediterranean). Analyses were done using a 213 nm Nd:YAG laser coupled to an Element2 ICP-MS along the growth axis of the coral skeletons. The profiles show that Ba/Ca ratios have a seasonally induced pattern with high values around the winter months which are identified by δ18O analyses. REE/Ca ratios co-vary with Ba/Ca ratios. Since the Ba/Ca ratio is a proxy used to monitor river discharge, the co-variation suggests the REE/Ca ratio to be a proxy of comparable quality. NASC-normalized REE patterns of the Tortonian corals have negative Ce anomalies like modern corals. However, the Tortonian corals have REE patterns highly enriched in LREE with (La/Lu)N ratios of 4 to 30 which is 1 to 2 orders of magnitude higher compared to modern corals. Al concentrations are low (<10 ppm) and do not correlate with REE concentrations indicating an insignificant fraction of terrigenous material included in the skeleton. Applying distribution coefficients typical for modern corals, the REE composition of the Tortonian ambient water yields (La/Lu)N of about 2 to 16. This range can be explained by binary mixing of modern Eastern Mediterranean sea surface water ((La/Lu)N=0.35, sea surface salinity (SSS) ~38 ‰) with highly LREE-enriched river water ((La/Lu)N >3, salinity ~0.5 ‰) transporting suspended and colloid phases, also highly enriched, especially in LREE, at a ratio of ~9 (seawater):1 (river water). The river water component is considered because paleoenvironmental

  5. THERMAL CONDUCTIVITY AND ELEMENT FRACTIONATION IN EV Lac

    SciTech Connect

    Laming, J. Martin; Hwang, Una

    2009-12-10

    We present a 100 ks Suzaku observation of the dMe flare star EV Lac, in which the star was captured undergoing a moderate 1500 s flare. During the flare, the count rate increased by about a factor of 50 and the spectrum showed overall enhanced element abundances relative to quiescence. While the quiescent element abundances confirm the inverse first ionization potential (FIP) effect previously documented for EV Lac, with relatively higher depletions for low FIP elements, abundances during the flare spectra show a composition closer to that of the stellar photosphere. We discuss these results in the context of models that explain abundance fractionation in the stellar chromosphere as a result of the ponderomotive force due to Alfven waves. Stars with FIP or inverse FIP effects arising from differently directed ponderomotive forces may have quite different abundance signatures in their evaporated chromospheric plasma during flares, if the same ponderomotive force also affects thermal conduction downward from the corona. The regulation of the thermal conductivity by the ponderomotive force requires a level of turbulence that is somewhat higher than is normally assumed, but plausible in filamentary conduction models.

  6. Thermal Conductivity and Element Fractionation in EV Lac

    NASA Astrophysics Data System (ADS)

    Laming, J. Martin; Hwang, Una

    2009-12-01

    We present a 100 ks Suzaku observation of the dMe flare star EV Lac, in which the star was captured undergoing a moderate 1500 s flare. During the flare, the count rate increased by about a factor of 50 and the spectrum showed overall enhanced element abundances relative to quiescence. While the quiescent element abundances confirm the inverse first ionization potential (FIP) effect previously documented for EV Lac, with relatively higher depletions for low FIP elements, abundances during the flare spectra show a composition closer to that of the stellar photosphere. We discuss these results in the context of models that explain abundance fractionation in the stellar chromosphere as a result of the ponderomotive force due to Alfvén waves. Stars with FIP or inverse FIP effects arising from differently directed ponderomotive forces may have quite different abundance signatures in their evaporated chromospheric plasma during flares, if the same ponderomotive force also affects thermal conduction downward from the corona. The regulation of the thermal conductivity by the ponderomotive force requires a level of turbulence that is somewhat higher than is normally assumed, but plausible in filamentary conduction models.

  7. Metallic elements fractionation in municipal solid waste incineration residues

    NASA Astrophysics Data System (ADS)

    Kowalski, Piotr R.; Kasina, Monika; Michalik, Marek

    2016-04-01

    Municipal solid waste incineration (MSWI) residues are represented by three main materials: bottom ash, fly ash and air pollution control (APC) residues. Among them ˜80 wt% is bottom ash. All of that materials are products of high temperature (>1000° C) treatment of waste. Incineration process allows to obtain significant reduction of waste mass (up to 70%) and volume (up to 90%) what is commonly used in waste management to reduce the amount need to be landfilled or managed in other way. Incineration promote accumulation non-combustible fraction of waste, which part are metallic elements. That type of concentration is object of concerns about the incineration residues impact on the environment and also gives the possibility of attempts to recover them. Metallic elements are not equally distributed among the materials. Several factors influence the process: melting points, volatility and place and forms of metallic occurrence in the incinerated waste. To investigate metallic elements distribution in MSWI residues samples from one of the biggest MSW incineration plant in Poland were collected in 2015. Chemical analysis with emphasis on the metallic elements content were performed using inductively coupled plasma optical emission (ICP-OES) and mass spectrometry (ICP-MS). The bottom ash was a SiO2-CaO-Al2O3-Fe2O3-Na2O rich material, whereas fly ash and APC residues were mostly composed of CaO and SiO2. All of the materials were rich in amorphous phase occurring together with various, mostly silicate crystalline phases. In a mass of bottom ash 11 wt% were metallic elements but also in ashes 8.5 wt% (fly ash) and ˜4.5 wt% (APC residues) of them were present. Among the metallic elements equal distribution between bottom and fly ash was observed for Al (˜3.85 wt%), Mn (770 ppm) and Ni (˜65 ppm). In bottom ash Fe (5.5 wt%), Cr (590 ppm) and Cu (1250 ppm) were concentrated. These values in comparison to fly ash were 5-fold higher for Fe, 3-fold for Cu and 1.5-fold for

  8. Coal fly ash as a resource for rare earth elements.

    PubMed

    Franus, Wojciech; Wiatros-Motyka, Małgorzata M; Wdowin, Magdalena

    2015-06-01

    Rare earth elements (REE) have been recognised as critical raw materials, crucial for many clean technologies. As the gap between their global demand and supply increases, the search for their alternative resources becomes more and more important, especially for the countries which depend highly on their import. Coal fly ash (CFA), which when not utilised is considered waste, has been regarded as the possible source of many elements, including REE. Due to the increase in the energy demand, CFA production is expected to grow, making research into the use of this material a necessity. As Poland is the second biggest coal consumer in the European Union, the authors have studied different coal fly ashes from ten Polish power plants for their rare earth element content. All the fly ashes have a broadly similar distribution of rear earth elements, with light REE being dominant. Most of the samples have REE content relatively high and according to Seredin and Dai (Int J Coal Geol 94: 67-93, 2012) classification can be considered promising REE raw materials. PMID:25613802

  9. The anthropogenic atmospheric elements fraction: A new interpretation of elemental deposits on tree barks

    NASA Astrophysics Data System (ADS)

    Catinon, Mickaël; Ayrault, Sophie; Clocchiatti, Roberto; Boudouma, Omar; Asta, Juliette; Tissut, Michel; Ravanel, Patrick

    The superficial deposit on the bark surface of several trees (mainly Fraxinus excelsior L.) was sampled in the experimental station of the university campus in Grenoble (France). Its composition was studied by scanning electron microscopy-energy dispersive X-ray emission (SEM-EDX) and, after digestion, by inductively coupled plasma-mass spectrometry (ICP-MS). The deposit was composed of 81.3% ± 7.4 organic matter, 9.4% ± 4.9 of geogenic minerals issued from the atmosphere (atmospheric geogenic fraction: AGF) and 9.3% ± 2.7 of a mixture of elements which was called anthropogenic atmospheric elements fraction (AAEF). The SEM-EDX analysis showed the presence of particles of geogenic compounds such as different types of silicates, phosphates, carbonates, sulphates, oxides and also particles of metals such as iron or of alloys of Fe-Zn, Fe-Ni, Ni-Cr and Ca sulphates or phosphates. Typical spheres of "fly ashes" composed of pure iron or Al-silicates were detected. Using the SEM-EDX analysis of the deposit and the average local soil composition, an empiric formula for the AGF (without polluting elements) was chosen, which presented a clear analogy with the global formula of the upper continental crust. In the same way, a formula for the pure organic matter fraction was chosen. Withdrawing the elements corresponding to these two fractions allows a tentative estimation of the content of the AAEF which was supposed to better represent the elemental anthropogenic contamination issued from the atmosphere. In the station, most of Sb, Cd, Sn, Pb, Cu, V and Zn were found in the AAEF. This AAEF composition was compared to that of the deposit in a highway tunnel where Pb and Cu were at a very high level. The meaning and the limits of the AAEF concept were critically discussed.

  10. Removal of Phosphorus in Metallurgical Silicon by Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Tang, Kai; Løvvik, Ole Martin; Safarian, Jafar; Ma, Xiang; Tangstad, Merete

    2014-09-01

    Removal of phosphorus in metallurgical silicon is one of the crucial steps for the production of solar grade Si feedstock. The possibility of doping rare earth elements for phosphorus removal has in this work been studied both theoretically and experimentally. Thermochemical properties of Ce, Nd, and Pr monophosphides have first been estimated by ab initio thermodynamic simulations based on density functional theory and the direct phonon method. The reliability of the first principles calculations was assessed by coupling with the phase diagram data of the Pr-P system. Equilibrium calculations confirmed the existence of stable rare earth monophosphides in solid silicon. Experimental investigations were then carried out, employing a high temperature resistance furnace. The Ce-doped silicon samples were examined by electron probe micro analyzer and inductively coupled plasma analysis. The efficiency of phosphorus removal by means of rare earth doping was discussed in detail in the paper.

  11. Biological availability and environmental behaviour of Rare Earth Elements in soils of Hesse, Central Germany

    NASA Astrophysics Data System (ADS)

    Loell, M.; Duering, R.-A.; Felix-Henningsen, P.

    2009-04-01

    Rare earth elements (REEs) comprise a group of 17 transition metals with very similar chemical and physical properties. They include the elements scandium (Sc), yttrium (Y) and lanthanum (La) and the 14 elements (cerium to lutetium) that follow La in the periodic table. Their average abundance in the earth's crust varies from 0,01 to 0,02% so they are as common as Cu and Pb. Beside their widespread use in industry, REEs are applied in Chinese agriculture. Their beneficial effects both on crop yield and on animal production are reported in various investigations. As a result - by using microelement fertilisers and manure - REEs enter the pedosphere while their fate and behaviour in the environment up to now remains unexamined. The first aim of our investigation was to evaluate the concentration of REEs in agricultural used soils in central Germany (Hesse) by ICP-MS. In addition to their total concentration (aqua regia digestion) their bioavailable contents - determined by EDTA (potentially available fraction) and ammonium nitrate extraction (mobile fraction) - were analysed. The occurrence of the three REE fractions in different soils will be discussed and influencing soil properties (e.g. pH-value, content of clay and organic carbon) will be revealed. Additionally the uptake of REEs by grassland plants was determined and resulting transfer factors will be presented.

  12. Contamination in the Rare-Earth Element Orthophosphate Reference Samples

    PubMed Central

    Donovan, John J.; Hanchar, John M.; Picolli, Phillip M.; Schrier, Marc D.; Boatner, Lynn A.; Jarosewich, Eugene

    2002-01-01

    Several of the fourteen rare-earth element (plus Sc and Y) orthophosphate standards grown at Oak Ridge National Laboratory in the 1980s and widely distributed by the Smithsonian Institution’s Department of Mineral Sciences, are significantly contaminated by Pb. The origin of this impurity is the Pb2P2O7 flux that is derived from the thermal decomposition of PbHPO4. The lead pyrophosphate flux is used to dissolve the oxide starting materials at elevated temperatures (≈1360 °C) prior to the crystal synthesis. Because these rare-earth element standards are extremely stable under the electron beam and considered homogenous, they have been of enormous value to electron probe micro-analysis (EPMA). The monoclinic, monazite structure, orthophosphates show a higher degree of Pb incorporation than the tetragonal xenotime structure, orthophosphates. This paper will attempt to describe and rationalize the extent of the Pb contamination in these otherwise excellent materials.

  13. Determination of the Light Element Fraction in MSL APXS Spectra

    NASA Astrophysics Data System (ADS)

    Perrett, G. M.; Pradler, I.; Campbell, J. L.; Gellert, R.; Leshin, L. A.; Schmidt, M. E.; Team, M.

    2013-12-01

    Additional light invisible components (ALICs), measured using the alpha particle X-ray spectrometer (APXS), represent all light elements (e.g. CO3, OH, H2O) present in a sample below Na, excluding bound oxygen. The method for quantifying ALICs was originally developed for the Mars Exploration Rover (MER) APXS (Mallet et al, 2006; Campbell et al, 2008). This method has been applied to data collected by the Mars Science Laboratory (MSL) APXS up to sol 269 using a new terrestrial calibration. ALICs are investigated using the intensity ratio of Pu L-alpha Compton and Rayleigh scatter peaks (C/R). Peak areas of the scattered X-rays are determined by the GUAPX fitting program. This experimental C/R is compared to a Monte Carlo simulated C/R. The ratio of simulated and experimental C/R values is called the K-value. ALIC concentrations are calculated by comparing the K-value to the fraction of all invisibles present; the invisible fraction is produced from the spectrum fit by GUAPX. This method is applied to MSL spectra with long integration duration (greater than 3 hours) and with energy resolution less than 180 eV at 5.9 keV. These overnight spectra encompass a variety of geologic materials examined by the Curiosity Rover, including volcanic and sedimentary lithologies. Transfer of the K-value calibration produced in the lab to the flight APXS has been completed and temperature, geometry and spectrum duration effects have been thoroughly examined. A typical limit of detection of ALICs is around 5 wt% with uncertainties of approximately 5 wt%. Accurate elemental concentrations are required as input to the Monte Carlo program (Mallet et al, 2006; Lee, 2010). Elemental concentrations are obtained from the GUAPX code using the same long duration, good resolution spectra used for determining the experimental C/R ratios (Campbell et al. 2012). Special attention was given to the assessment of Rb, Sr, and Y as these element peaks overlap the scatter peaks. Mineral effects

  14. Uncovering the Global Life Cycles of the Rare Earth Elements

    PubMed Central

    Du, Xiaoyue; Graedel, T. E.

    2011-01-01

    The rare earth elements (REE) are a group of fifteen elements with unique properties that make them indispensable for a wide variety of emerging, critical technologies. Knowledge of the life cycles of REE remains sparse, despite the current heightened interest in their future availability. Mining is heavily concentrated in China, whose monopoly position and potential restriction of exports render primary supplies vulnerable to short and long-term disruption. To provide an improved perspective we derived the first quantitative life cycles (for the year 2007) for ten REE: lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), and yttrium (Y). Of these REE, Ce and Nd in-use stocks are highest; the in-use stocks of most REE show significant accumulation in modern society. Industrial scrap recycling occurs only from magnet manufacture. We believe there is no post-customer recycling of any of these elements. PMID:22355662

  15. Anthropogenic Disturbance of Element Cycles at the Earth's Surface

    NASA Astrophysics Data System (ADS)

    Sen, I. S.; Peucker-Ehrenbrink, B.

    2012-12-01

    The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts [1]. We determine anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compared it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions and - for helium - hydrodynamic escape from the Earth's atmosphere. In addition, we introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporated uncertainties of element mass fluxes through Monte Carlo simulations [2]. Our assessment indicates that anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium are greater than the respective natural fluxes. For these elements mining is the major factor of human dominance, whereas petroleum burning strongly influence the surficial cycle of rhenium. Apart from these 11 elements there are 15 additional elements whose anthropogenic fluxes may surpass their corresponding natural fluxes. Anthropogenic fluxes of the remaining elements are smaller than their corresponding natural fluxes although a significant human influence is observed for all of them. For example, ~20% of the annual fluxes of C, N, and P can be attributed to human activities. Such disturbances, though small compared with natural fluxes, can significantly alter concentrations in near-surface reservoirs and affect ecosystems if they are sustained over time scales similar to or longer than the residence time of elements in the respective reservoir. Examples are the continuing input of CO2 to the atmosphere that

  16. FRACTIONAL DISTILLATION SEPARATION OF PLUTONIUM VALUES FROM LIGHT ELEMENT VALUES

    DOEpatents

    Cunningham, B.B.

    1957-12-17

    A process is described for removing light element impurities from plutonium. It has been found that plutonium contaminated with impurities may be purified by converting the plutonium to a halide and purifying the halide by a fractional distillation whereby impurities may be distilled from the plutonium halide. A particularly effective method includes the step of forming a lower halide such as the trior tetrahalide and distilling the halide under conditions such that no decomposition of the halide occurs. Molecular distillation methods are particularly suitable for this process. The apparatus may comprise an evaporation plate with means for heating it and a condenser surface with means for cooling it. The condenser surface is placed at a distance from the evaporating surface less than the mean free path of molecular travel of the material being distilled at the pressure and temperature used. The entire evaporating system is evacuated until the pressure is about 10/sup -4/ millimeters of mercury. A high temperuture method is presented for sealing porous materials such as carbon or graphite that may be used as a support or a moderator in a nuclear reactor. The carbon body is subjected to two surface heats simultaneously in an inert atmosphere; the surface to be sealed is heated to 1500 degrees centigrade; and another surface is heated to 300 degrees centigrade, whereupon the carbon vaporizes and flows to the cooler surface where it is deposited to seal that surface. This method may be used to seal a nuclear fuel in the carbon structure.

  17. The Earth Based Ground Stations Element of the Lunar Program

    NASA Technical Reports Server (NTRS)

    Gal-Edd, Jonathan; Fatig, Curtis; Schier, James; Lee, Charles

    2007-01-01

    The Lunar Architecture Team (LAT) is responsible for developing a concept for building and supporting a lunar outpost with several exploration capabilities such as rovers, colonization, and observatories. The lunar outpost is planned to be located at the Moon's South Pole. The LAT Communications and Navigation Team (C&N) is responsible for defining the network infrastructure to support the lunar outpost. The following elements are needed to support lunar outpost activities: A Lunar surface network based on industry standard wireless 802.xx protocols, relay satellites positioned 180 degrees apart to provide South Pole coverage for the half of the lunar 28-day orbit that is obscured from Earth view, earth-based ground stations deployed at geographical locations 120 degrees apart. This paper will focus on the Earth ground stations of the lunar architecture. Two types of ground station networks are discussed. One provides Direct to Earth (DTE) support to lunar users using Kaband 23/26Giga-Hertz (GHz) communication frequencies. The second supports the Lunar Relay Satellite (LRS) that will be using Ka-band 40/37GHz (Q-band). This paper will discuss strategies to provide a robust operational network in support of various lunar missions and trades of building new antennas at non-NASA facilities, to improve coverage and provide site diversification for handling rain attenuation.

  18. Assessing rare earth elements in quartz rich geological samples.

    PubMed

    Santoro, A; Thoss, V; Guevara, S Ribeiro; Urgast, D; Raab, A; Mastrolitti, S; Feldmann, J

    2016-01-01

    Sodium peroxide (Na2O2) fusion coupled to Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) measurements was used to rapidly screen quartz-rich geological samples for rare earth element (REE) content. The method accuracy was checked with a geological reference material and Instrumental Neutron Activation Analysis (INAA) measurements. The used mass-mode combinations presented accurate results (only exception being (157)Gd in He gas mode) with recovery of the geological reference material QLO-1 between 80% and 98% (lower values for Lu, Nd and Sm) and in general comparable to INAA measurements. Low limits of detection for all elements were achieved, generally below 10 pg g(-1), as well as measurement repeatability below 15%. Overall, the Na2O2/ICP-MS/MS method proved to be a suitable lab-based method to quickly and accurately screen rock samples originating from quartz-rich geological areas for rare earth element content; particularly useful if checking commercial viability. PMID:26595776

  19. Rare earth element content of cryptocrystalline magnesites of Konya, Turkey

    NASA Astrophysics Data System (ADS)

    Zedef, Veysel; Russell, Michael

    2016-04-01

    We examined the rare earth element content of several cryptocrystalline magnesites as well as hydromagnesite, host rock serpentinites, lake water and hot spring water from Turkey. Southwestern Turkey hosts cryptocrystalline magnesites, sedimentary magnesites with presently forming, biologically mediated hydromagnesites and travertines. Our results show the REE content of the minerals, rocks and waters are well below detection limits. One hydromagnesite sample from Lake Salda has slightly high La (2.38ppb), Ce (3.91 ppb) and Nd (1.68 ppb) when compared to other samples, but these are also still below detection limits of the method we followed.

  20. Compositional and phase relations among rare earth element minerals

    NASA Technical Reports Server (NTRS)

    Burt, D. M.

    1989-01-01

    A review is presented that mainly treats minerals in which the rare-earth elements are essential constituents, e.g., bastnaesite, monazite, xenotime, aeschynite, allanite. The chemical mechanisms and limits of REE substitution in some rock-forming minerals (zircon, apatite, titanite, garnet) are also derived. Vector representation of complex coupled substitutions in selected REE-bearing minerals is examined and some comments on REE-partitioning between minerals as related to acid-based tendencies and mineral stabilities are presented. As the same or analogous coupled substitutions involving the REE occur in a wide variety of mineral structures, they are discussed together.

  1. Standard reference water samples for rare earth element determinations

    USGS Publications Warehouse

    Verplanck, P.L.; Antweiler, R.C.; Nordstrom, D.K.; Taylor, H.E.

    2001-01-01

    Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45-161 ??g/1). Seventeen international laboratories participated in a 'round-robin' chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

  2. Mimicking the magnetic properties of rare earth elements using superatoms

    PubMed Central

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A. W.

    2015-01-01

    Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel “magic boron” counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters. PMID:25848014

  3. Mimicking the magnetic properties of rare earth elements using superatoms.

    PubMed

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Castleman, A W

    2015-04-21

    Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel "magic boron" counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters. PMID:25848014

  4. A sequential extraction procedure to evaluate the mobilization behavior of rare earth elements in soils and tailings materials.

    PubMed

    Mittermüller, Marc; Saatz, Jessica; Daus, Birgit

    2016-03-01

    A novel sequential extraction method for evaluation of the mobilization behavior of rare earth elements in soils and mine tailings materials is presented. The sequence consists of the following four steps: 0.05 mol L(-1) calcium nitrate (easily soluble and ion exchange fraction), 0.1 mol L(-1) citric acid (fraction mobilized by complexation and carbonate bound), 0.05 mol L(-1) hydroxylamine hydrochloride (pH = 2) (reducible fraction), 1.4 mol L(-1) nitric acid (acid soluble fraction). The procedure was optimized with a certified soil material and a mine tailings material and was applied to eight samples of a soil profile. The different results obtained by using either the developed method or the widespread used BCR-Method for comparison are discussed. There were clear advantages using the newly created sequential extraction procedure in getting more detailed information about the bioavailable fraction and a fraction addressing REE phosphates. PMID:26766351

  5. Bacterial Cell Surface Adsorption of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Park, D.; Reed, D.; Fujita, Y.; Yung, M.; Anderko, A.; Eslamimanesh, A.

    2015-12-01

    Rare earth elements (REE) play a critical role in many emerging clean energy technologies, including high-power magnets, wind turbines, solar panels, hybrid/electric vehicle batteries and lamp phosphors. In order to sustain demand for such technologies given current domestic REE shortages, there is a need to develop new approaches for ore processing/refining and recycling of REE-containing materials. To this end, we have developed a microbially-mediated bioadsorption strategy with application towards enrichment of REE from complex mixtures. Specifically, the bacterium Caulobacter crescentus was genetically engineered to display lanthanide binding tags (LBTs), short peptides that possess high affinity and specificity for rare earth elements, on its cell surface S-layer protein. Under optimal conditions, LBT-displayed cells adsorbed greater than 5-fold more REE than control cells lacking LBTs. Competition binding experiments with a selection of REEs demonstrated that our engineered cells could facilitate separation of light- from heavy- REE. Importantly, binding of REE onto our engineered strains was much more favorable compared to non-REE metals. Finally, REE bound to the cell surface could be stripped off using citrate, providing an effective and non-toxic REE recovery method. Together, this data highlights the potential of our approach for selective REE enrichment from REE containing mixtures.

  6. COLORS OF A SECOND EARTH: ESTIMATING THE FRACTIONAL AREAS OF OCEAN, LAND, AND VEGETATION OF EARTH-LIKE EXOPLANETS

    SciTech Connect

    Fujii, Yuka; Kawahara, Hajime; Suto, Yasushi; Taruya, Atsushi; Fukuda, Satoru; Nakajima, Teruyuki; Turner, Edwin L.

    2010-06-01

    Characterizing the surfaces of rocky exoplanets via their scattered light will be an essential challenge in investigating their habitability and the possible existence of life on their surfaces. We present a reconstruction method for fractional areas of different surface types from the colors of an Earth-like exoplanet. We create mock light curves for Earth without clouds using empirical data. These light curves are fitted to an isotropic scattering model consisting of four surface types: ocean, soil, snow, and vegetation. In an idealized situation where the photometric errors are only photon shot noise, we are able to reproduce the fractional areas of those components fairly well. The results offer some hope for detection of vegetation via the distinct spectral feature of photosynthesis on Earth, known as the red edge. In our reconstruction method, Rayleigh scattering due to the atmosphere plays an important role, and for terrestrial exoplanets with an atmosphere similar to our Earth, it is possible to estimate the presence of oceans and an atmosphere simultaneously.

  7. Colors of a Second Earth: Estimating the Fractional Areas of Ocean, Land, and Vegetation of Earth-like Exoplanets

    NASA Astrophysics Data System (ADS)

    Fujii, Yuka; Kawahara, Hajime; Suto, Yasushi; Taruya, Atsushi; Fukuda, Satoru; Nakajima, Teruyuki; Turner, Edwin L.

    2010-06-01

    Characterizing the surfaces of rocky exoplanets via their scattered light will be an essential challenge in investigating their habitability and the possible existence of life on their surfaces. We present a reconstruction method for fractional areas of different surface types from the colors of an Earth-like exoplanet. We create mock light curves for Earth without clouds using empirical data. These light curves are fitted to an isotropic scattering model consisting of four surface types: ocean, soil, snow, and vegetation. In an idealized situation where the photometric errors are only photon shot noise, we are able to reproduce the fractional areas of those components fairly well. The results offer some hope for detection of vegetation via the distinct spectral feature of photosynthesis on Earth, known as the red edge. In our reconstruction method, Rayleigh scattering due to the atmosphere plays an important role, and for terrestrial exoplanets with an atmosphere similar to our Earth, it is possible to estimate the presence of oceans and an atmosphere simultaneously.

  8. Trace elemental imaging of rare earth elements discriminates tissues at microscale in flat fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Dutheil, Didier B; Cohen, Serge X; Thiaudière, Dominique; Charbonnier, Sylvain; Clément, Gaël; Bertrand, Loïc

    2014-01-01

    The interpretation of flattened fossils remains a major challenge due to compression of their complex anatomies during fossilization, making critical anatomical features invisible or hardly discernible. Key features are often hidden under greatly preserved decay prone tissues, or an unpreparable sedimentary matrix. A method offering access to such anatomical features is of paramount interest to resolve taxonomic affinities and to study fossils after a least possible invasive preparation. Unfortunately, the widely-used X-ray micro-computed tomography, for visualizing hidden or internal structures of a broad range of fossils, is generally inapplicable to flattened specimens, due to the very high differential absorbance in distinct directions. Here we show that synchrotron X-ray fluorescence spectral raster-scanning coupled to spectral decomposition or a much faster Kullback-Leibler divergence based statistical analysis provides microscale visualization of tissues. We imaged exceptionally well-preserved fossils from the Late Cretaceous without needing any prior delicate preparation. The contrasting elemental distributions greatly improved the discrimination of skeletal elements material from both the sedimentary matrix and fossilized soft tissues. Aside content in alkaline earth elements and phosphorus, a critical parameter for tissue discrimination is the distinct amounts of rare earth elements. Local quantification of rare earths may open new avenues for fossil description but also in paleoenvironmental and taphonomical studies. PMID:24489809

  9. Trace Elemental Imaging of Rare Earth Elements Discriminates Tissues at Microscale in Flat Fossils

    PubMed Central

    Gueriau, Pierre; Mocuta, Cristian; Dutheil, Didier B.; Cohen, Serge X.; Thiaudière, Dominique; Charbonnier, Sylvain; Clément, Gaël; Bertrand, Loïc

    2014-01-01

    The interpretation of flattened fossils remains a major challenge due to compression of their complex anatomies during fossilization, making critical anatomical features invisible or hardly discernible. Key features are often hidden under greatly preserved decay prone tissues, or an unpreparable sedimentary matrix. A method offering access to such anatomical features is of paramount interest to resolve taxonomic affinities and to study fossils after a least possible invasive preparation. Unfortunately, the widely-used X-ray micro-computed tomography, for visualizing hidden or internal structures of a broad range of fossils, is generally inapplicable to flattened specimens, due to the very high differential absorbance in distinct directions. Here we show that synchrotron X-ray fluorescence spectral raster-scanning coupled to spectral decomposition or a much faster Kullback-Leibler divergence based statistical analysis provides microscale visualization of tissues. We imaged exceptionally well-preserved fossils from the Late Cretaceous without needing any prior delicate preparation. The contrasting elemental distributions greatly improved the discrimination of skeletal elements material from both the sedimentary matrix and fossilized soft tissues. Aside content in alkaline earth elements and phosphorus, a critical parameter for tissue discrimination is the distinct amounts of rare earth elements. Local quantification of rare earths may open new avenues for fossil description but also in paleoenvironmental and taphonomical studies. PMID:24489809

  10. Distribution of rare earth elements and uranium in various components of ordinary chondrites

    NASA Astrophysics Data System (ADS)

    Ebihara, M.; Honda, M.

    1984-06-01

    Rare earth elements (REE) and uranium were studied for their distributions in various component phases of four ordinary chondrites. Kesen (H4), Richardton (H5), Bruderheim (L6), and Saint Severin (LL6). A selective dissolution method was applied for the phase fractionation. The REE were analysed by neutron activation analysis, and U was determined by neutron-induced fission tracks. The present study revealed that both REE and U are highly enriched in the Ca-phosphate minerals with different enrichment factors, implying chemical fractionation between them. The phosphates seem to be responsible for more than 80 percent of the light REE in all chondrites. On the other hand, only 20-40 percent of the total U resides in the Ca-phosphates. This difference in enrichments might have been caused through the levels of metamorphic activity on the meteoritic parent bodies.

  11. Rare earth elements and neodymium isotopes in world river sediments revisited

    NASA Astrophysics Data System (ADS)

    Bayon, G.; Toucanne, S.; Skonieczny, C.; André, L.; Bermell, S.; Cheron, S.; Dennielou, B.; Etoubleau, J.; Freslon, N.; Gauchery, T.; Germain, Y.; Jorry, S. J.; Ménot, G.; Monin, L.; Ponzevera, E.; Rouget, M.-L.; Tachikawa, K.; Barrat, J. A.

    2015-12-01

    Over the past decades, rare earth elements (REE) and their radioactive isotopes have received tremendous attention in sedimentary geochemistry, as tracers for the geological history of the continental crust and provenance studies. In this study, we report on elemental concentrations and neodymium (Nd) isotopic compositions for a large number of sediments collected near the mouth of rivers worldwide, including some of the world's major rivers. Sediments were leached for removal of non-detrital components, and both clay and silt fractions were retained for separate geochemical analyses. Our aim was to re-examine, at the scale of a large systematic survey, whether or not REE and Nd isotopes could be fractionated during Earth surface processes. Our results confirmed earlier assumptions that river sediments do not generally exhibit any significant grain-size dependent Nd isotopic variability. Most sediments from rivers draining old cratonic areas, sedimentary systems and volcanic provinces displayed similar Nd isotopic signatures in both clay and silt fractions, with ΔεNd(clay-silt) < |1|. A subtle decoupling of Nd isotopes between clays and silts was identified however in a few major river systems (e.g. Nile, Mississippi, Fraser), with clays being systematically shifted towards more radiogenic values. This observation suggests that preferential weathering of volcanic and/or sedimentary rocks relative to more resistant lithologies may occur in river basins, possibly leading locally to Nd isotopic decoupling between different size fractions. Except for volcanogenic sediments, silt fractions generally displayed homogeneous REE concentrations, exhibiting relatively flat shale-normalized patterns. However, clay fractions were almost systematically characterized by a progressive enrichment from the heavy to the light REE and a positive europium (Eu) anomaly. In agreement with results from previous soil investigations, the observed REE fractionation between clays and silts

  12. Rare earth elements in the phosphatic-enriched sediment of the Peru shelf

    USGS Publications Warehouse

    Piper, D.Z.; Baedecker, P.A.; Crock, J.G.; Burnett, W.C.; Loebner, B.J.

    1988-01-01

    Apatite-enriched materials from the Peru shelf have been analyzed for their major oxide and rare earth element (REE) concentrations. The samples consist of (1) the fine fraction of sediment, mostly clay material, (2) phosphatic pellets and fish debris, which are dispersed throughout the fine-grained sediment, (3) tabular-shaped phosphatic crusts, which occur within the uppermost few centimeters of sediment, and (4) phosphatic nodules, which occur on the seafloor. The bulk REE concentrations of the concretions suggest that these elements are partitioned between the enclosed detrital material and the apatite fraction. Analysis of the fine-grained sediment with which the samples are associated suggested that this detrital fraction in the concretions should have shale REE values; the analysis of the fish debris suggested that the apatite fraction might have seawater values. The seawater contribution of REE's is negligible in the nodules and crust, in which the apatite occurs as a fine-grained interstitial cement. That is, the concentration of REE's and the REE patterns are predominantly a function of the amount of enclosed fine-grained sediment. By contrast, the REE pattern of the pelletal apatite suggests a seawater source and the absolute REE concentrations are relatively high. The REE P2O5 ratios of the apatite fraction of these samples thus vary from approximately zero (in the case of the crust and nodules) to as much as approximately 1.2 ?? 10-3 (in the case of the pellets). The range of this ratio suggests that rather subtle variations in the depositional environment might cause a significant variation in the REE content of this authigenic fraction of the sediment. Pelletal glauconite was also recovered from one sediment core. Its REE concentrations closely resemble those of the fish debris. ?? 1988.

  13. Partitioning of light lithophile elements during basalt eruptions on Earth and application to Martian shergottites

    NASA Astrophysics Data System (ADS)

    Edmonds, Marie

    2015-02-01

    An enigmatic record of light lithophile element (LLE) zoning in pyroxenes in basaltic shergottite meteorites, whereby LLE concentrations decrease dramatically from the cores to the rims, has been interpreted as being due to partitioning of LLE into a hydrous vapor during magma ascent to the surface on Mars. These trends are used as evidence that Martian basaltic melts are water-rich (McSween et al., 2001). Lithium and boron are light lithophile elements (LLE) that partition into volcanic minerals and into vapor from silicate melts, making them potential tracers of degassing processes during magma ascent to the surface of Earth and of other planets. While LLE degassing behavior is relatively well understood for silica-rich melts, where water and LLE concentrations are relatively high, very little data exists for LLE abundance, heterogeneity and degassing in basaltic melts. The lack of data hampers interpretation of the trends in the shergottite meteorites. Through a geochemical study of LLE, volatile and trace elements in olivine-hosted melt inclusions from Kilauea Volcano, Hawaii, it can be demonstrated that lithium behaves similarly to the light to middle rare Earth elements during melting, magma mixing and fractionation. Considerable heterogeneity in lithium and boron is inherited from mantle-derived primary melts, which is dominant over the fractionation and degassing signal. Lithium and boron are only very weakly volatile in basaltic melt erupted from Kilauea Volcano, with vapor-melt partition coefficients <0.1. Degassing of LLE is further inhibited at high temperatures. Pyroxene and associated melt inclusion LLE concentrations from a range of volcanoes are used to quantify lithium pyroxene-melt partition coefficients, which correlate negatively with melt H2O content, ranging from 0.13 at low water contents to <0.08 at H2O contents >4 wt%. The observed terrestrial LLE partitioning behavior is extrapolated to Martian primitive melts through modeling. The zoning

  14. The elements of the Earth's magnetism and their secular changes between 1550 and 1915

    NASA Technical Reports Server (NTRS)

    Fritsche, H.

    1983-01-01

    The results of an investigation about the magnetic agents outside the Earth's surface as well as the Earth's magnetic elements for the epochs 1550, 1900, 1915 are presented. The secular changes of the Earth's magnetic elements during the time interval 1550 - 1900 are also included.

  15. Total element concentration and chemical fractionation in airborne particulate matter from Santiago, Chile

    NASA Astrophysics Data System (ADS)

    Richter, Pablo; Griño, Paulina; Ahumada, Inés; Giordano, Ady

    Total element determination and chemical fractionation were carried out in airborne particulate matter (PM 10) from the Cerrillos monitoring station in Santiago, Chile, sampled in July (winter), 1997-2003. Element concentration in the period under study (1997-2003) was statistically analyzed through cluster analysis in order to identify groups of elements having similar behavior along time. Elements such as Cd, Cu, Pb, Ni, As and Mg show a clear decrease in concentration with time. On the contrary, chromium increases its concentration almost linearly during the period. In order to estimate whether the presence of a certain element in PM 10 matrix is mainly due to anthropogenic or natural processes, the enrichment factor of each element was determined. According to their behavior in the sequential extraction procedure, the elements were grouped by multivariate analysis in three clusters: (a) those mobile elements (Pb, Cd, Zn, Mn, Cu and As) which are weakly bound to the matrix (fractions 1 and 2) (b) those elements (V, Ti, and Cr) mainly bound to carbonates and oxides (fraction 3) and (c) the most immobile elements (Ni, Mo, Ca, Mg, Ba and Al), mainly bound to silicates and organic matter (fraction 4). A source of great concern is the fact that elements of such high toxicity as Pb, Cd and As are highly concentrated in both mobile fractions, indicating that these elements have a direct impact on the environment and on the health of the exposed population.

  16. Rare earth element systematics of fossil bone revealed by LA-ICPMS analysis

    NASA Astrophysics Data System (ADS)

    Herwartz, Daniel; Tütken, Thomas; Jochum, Klaus Peter; Sander, P. Martin

    2013-02-01

    Intra-bone rare earth element (REE) fractionation trends were studied by LA-ICPMS analysis to put constraints on (1) the mechanisms controlling REE fractionation within fossil bones; (2) the relative timing of REE uptake in various parts of fossil bone and (3) the origin of REE in fossil bones. We have evaluated REE bone profiles across 54 fossil bones from a broad range of well-characterised taphonomic settings ranging in age from Triassic to early Medieval. REE patterns and concentration gradients are highly variable and intra-bone fractionation trends in (La/Yb)N vs. (La/Sm)N space of few specimens cover almost the entire range previously observed for bulk samples. Intra-bone variability of Ce anomalies, as well as variable Y/Ho and (La/La∗)N is also observed. Sometimes, diagenetic fluids with fractionated, HREE enriched compositions have entered the bone from the marrow cavity, producing secondary REE uptake profiles. Theoretical intra-bone fractionation trends, modelled using lattice strain theory, concur with most REE data but some trends cannot be modelled using realistic boundary conditions. This fact, as well as the occurence of positive and negative Ce anomalies within the same fossil sample, hint towards changing REE compositions of diagenetic fluids over the timescales of REE uptake. Because apparent Ce anomalies frequently evolve over bone profiles and Ce anomalies can be inherited from previous fractionation events, Ce anomalies are a highly ambiguous tracer for constraining ambient redox conditions. In general, bioapatite REE signatures may not always reliably reflect ambient taphonomic or redox conditions and diagenetic fluid compositions. Therefore REE patterns and Ce anomalies of fossil bones must be interpreted cautiously as they vary spatially within skeletal remains and are affected by intra-bone fractionation processes as well as changing compositions of the diagenetic fluid.

  17. Insights into early Earth from Barberton komatiites: Evidence from lithophile isotope and trace element systematics

    NASA Astrophysics Data System (ADS)

    Puchtel, I. S.; Blichert-Toft, J.; Touboul, M.; Walker, R. J.; Byerly, G. R.; Nisbet, E. G.; Anhaeusser, C. R.

    2013-05-01

    Major, minor, and lithophile trace element abundances and Nd and Hf isotope systematics are reported for two sets of remarkably fresh, by Archean standards, samples of komatiitic lavas from the 3.48 Ga Komati and the 3.27 Ga Weltevreden Formations of the Barberton Greenstone Belt (BGB) in South Africa. These data are used to place new constraints on the thermal history of the early Archean mantle, on the timing of its differentiation, and on the origin and chemical nature of early mantle reservoirs and their evolution through time. Projected moderate to strong depletions of highly incompatible lithophile trace elements and water in the mantle sources of both komatiite systems, combined with the partitioning behavior of V during lava differentiation, are consistent with anhydrous conditions during generation of the komatiite magmas. Komati and Weltevreden lavas are inferred to have erupted with temperatures of ∼1600 °C, and, thus, represent the hottest known lavas on Earth. The calculated mantle potential temperatures of ∼1800 °C for both komatiite systems are 150-200 °C higher than those of contemporary ambient mantle. Combined, these observations are consistent with the origin of these BGB komatiite magmas in mantle plumes in the lower mantle. New Sm-Nd and Lu-Hf isotopic data allow precise determination of initial ε143Nd = +0.46 ± 0.10 and +0.50 ± 0.11 and initial ε176Hf = +1.9 ± 0.3 and +4.7 ± 0.8 for the Komati and the Weltevreden system komatiites, respectively. These positive initial values reflect prior fractionation of Sm/Nd and Lu/Hf in the mantle early in Earth history. Conversely, μ142Nd values are 0.0 ± 2.4 and +2.2 ± 4.1 for the Komati and the Weltevreden systems, respectively. These values overlap, within uncertainties, those of modern terrestrial rocks, thus, limiting the magnitudes of possible Sm/Nd fractionations generated by early Earth processes in the sources of these rocks. Combined 142,143Nd and Hf isotope and lithophile trace

  18. Core-Mantle Partitioning of Volatile Elements and the Origin of Volatile Elements in Earth and Moon

    NASA Technical Reports Server (NTRS)

    Righter, K.; Pando, K.; Danielson, L.; Nickodem, K.

    2014-01-01

    Depletions of siderophile elements in mantles have placed constraints on the conditions on core segregation and differentiation in bodies such as Earth, Earth's Moon, Mars, and asteroid 4 Vesta. Among the siderophile elements there are a sub-set that are also volatile (volatile siderophile elements or VSE; Ga, Ge, In, As, Sb, Sn, Bi, Zn, Cu, Cd), and thus can help to constrain the origin of volatile elements in these bodies, and in particular the Earth and Moon. One of the fundamental observations of the geochemistry of the Moon is the overall depletion of volatile elements relative to the Earth, but a satisfactory explanation has remained elusive. Hypotheses for Earth include addition during accretion and core formation and mobilized into the metallic core, multiple stage origin, or addition after the core formed. Any explanation for volatile elements in the Earth's mantle must also be linked to an explanation of these elements in the lunar mantle. New metal-silicate partitioning data will be applied to the origin of volatile elements in both the Earth and Moon, and will evaluate theories for exogenous versus endogenous origin of volatile elements.

  19. Elemental processes of transport and energy conversion in Earth's magnetosphere

    NASA Astrophysics Data System (ADS)

    Angelopoulos, Vassilis

    In the last 5 years observations from several missions and ground based observatories have honed in on the most elemental aspects of flux transport and energy conversion. Dipolarization fronts and their counterpart in the distant magnetotail "anti-dipolarization" fronts, which together are refered to herein as "reconnection fronts", usher the recently reconnected flux tubes from the near-Earth X-points and in the process convert magnetic energy to particle energy and wave radiation. On the tailward side they are responsible for plasmoid formation and acceleration. On the earthward side they result in elemental substorm current wedges or wedglets, which were initially postulated from ground observations alone. Recent observations have revealed how the interaction of wedgelets and the inner magnetosphere takes place. Questions remain with regards to the physics of the energy transfer process from global magnetic energy to local heating and waves, and with regards to the initiation of the X-point activations in space. Observations indicate that the latter may be induced by polar cap or dayside activity, suggesting a direct link between dayside reconnection and nightside phenomena. The likely causal sequence of events and open questions in light of these recent observations, and the field's outlook in anticipation of upcoming coordinated observations from the international Heliophysics System Observatory will be discussed.

  20. Reducing the detection limits of rare earth elements in steels

    SciTech Connect

    Raskevich, V.K.; Maiboroda, I.K.; Frishberg, A.A.; Panfilova, S.Ya.

    1986-12-01

    Chemical and chemicospectral analysis methods make it possible to determine rare-earth elements (REE) reliably in steels, but they are time-consuming and laborious. X-ray fluorescence methods are also characterized by the complicated procedure of preparing standard and production specimens for analysis. In this paper, the authors attempt to develop a spectrographic method of determining the REEs in the steel using standard equipment. The authors prepare synthetic standard specimens for determining Ce, Nd, La, Pr, and Y in steels of various grades by adding titrated solutions of the salts of the determined elements to the powder of the steel without REE with subsequent evaporation, drying, and mixing. The steels were ground by the mechanical method. On the basis of the resulting detection limits and analysis accuracy, the proposed method can be recommended for inspection of the technological process in melting steels and for preparation of standard specimens in the plant. The method is 5-7 times faster than the chemicospectral method.

  1. Chemical properties of rare earth elements in typical medical waste incinerator ashes in China.

    PubMed

    Zhao, Lijuan; Zhang, Fu-Shen; Zhang, Jingxin

    2008-10-30

    Medical waste (MW) ashes from different types of MW incinerators were examined to detect the characteristics and environmental impact of rare earth elements (REEs). The results showed that total REE contents in the ash samples ranged from 10.2 to 78.9 mg/kg. REEs in bottom ash were apparently higher than those in fly ash. Average REE contents in the ashes followed the sequence of Ce>La>Nd>Y>Gd>Pr>Sm>Dy>Er>Yb>Ho>Eu>Tb>Lu>Tm. Some of the elements, such as Sm, Dy, Ho, Er, Yb in the ash samples were in normal or nearly normal distribution, but Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Tm, Lu were not normally distributed, indicating some of the ash samples were enriched with these elements. Crust-normalized REE patterns indicated that two types of the MW ashes were obviously enriched with Gd and La. Sequential extraction results showed that REEs in the ash mainly presented as residual fraction, while exchangeable and carbonate fractions were relatively low. DTPA- and EDTA-extraction tests indicated that REEs in the MW ashes were generally in low bioavailability. PMID:18329796

  2. What fraction of boron-8 solar neutrinos arrive at the earth as a nu(2) mass eigenstate?

    SciTech Connect

    Nunokawa, Hiroshi; Parke, Stephen J.; Zukanovich Funchal, Renata; /Sao Paulo U.

    2006-01-01

    We calculate the fraction of B{sup 8} solar neutrinos that arrive at the Earth as a nu{sub 2} mass eigenstate as a function of the neutrino energy. Weighting this fraction with the B{sup 8} neutrino energy spectrum and the energy dependence of the cross section for the charged current interaction on deuteron with a threshold on the kinetic energy of the recoil electrons of 5.5 MeV, we find that the integrated weighted fraction of nu{sub 2}'s to be 91 {+-} 2 % at the 95% CL. This energy weighting procedure corresponds to the charged current response of the Sudbury Neutrino Observatory (SNO). We have used SNO's current best fit values for the solar mass squared difference and the mixing angle, obtained by combining the data from all solar neutrino experiments and the reactor data from KamLAND. The uncertainty on the nu{sub 2} fraction comes primarily from the uncertainty on the solar delta m{sup 2} rather than from the uncertainty on the solar mixing angle or the Standard Solar Model. Similar results for the Super-Kamiokande experiment are also given. We extend this analysis to three neutrinos and discuss how to extract the modulus of the Maki-Nakagawa-Sakata mixing matrix element U{sub e2} as well as place a lower bound on the electron number density in the solar B{sup 8} neutrino production region.

  3. Assessing the utility of trace and rare earth elements as biosignatures in microbial iron oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Heim, Christine; Simon, Klaus; Ionescu, Danny; Reimer, Andreas; De Beer, Dirk; Quéric, Nadia-Valérie; Reitner, Joachim; Thiel, Volker

    2015-02-01

    Microbial iron oxyhydroxides are common deposits in natural waters, recent sediments and mine drainage systems and often contain significant accumulations of trace and rare earth elements (TREE). TREE patterns are widely used to characterize minerals and rocks, and to elucidate their evolution and origin. Whether and which characteristic TREE signatures distinguish between a biological and an abiological origin of iron minerals is still not well understood. Long-term flow reactor studies were performed in the Äspö Hard Rock Laboratory to investigate the development of microbial mats dominated by iron-oxidizing bacteria, namely Mariprofundus sp. and Gallionella sp. The experiments investigated the accumulation and fractionation of TREE under controlled conditions and enabled us to assess potential biosignatures evolving within the microbial iron oxyhydroxides. Concentrations of Be, Y, Zn, Zr, Hf, W, Th, Pb, and U in the microbial mats were 1e3- to 1e5-fold higher than in the feeder fluids whereas the rare earth elements and Y (REE+Y) contents were 1e4 and 1e6 fold enriched. Except for a hydrothermally induced Eu anomaly, the normalized REE+Y patterns of the microbial iron oxyhydroxides were very similar to published REE+Y distributions of Archaean Banded Iron Formations. The microbial iron oxyhydroxides from the flow reactors were compared to iron oxyhydroxides that were artificially precipitated from the same feeder fluid. These abiotic and inorganic iron oxyhydroxides show the same REE+Y distribution patterns. Our results indicate that the REE+Y mirror quite exactly the water chemistry, but they do not allow to distinguish microbially mediated from inorganic iron precipitates. All TREE studied showed an overall similar fractionation behavior in biogenic, abiotic and inorganic iron oxyhydroxides. Exceptions are Ni and Tl, which were only accumulated in the microbial iron oxyhydroxides and may point to a potential usage of these elements as microbial biosignatures.

  4. Rare earth elements exploitation, geopolitical implications and raw materials trading

    NASA Astrophysics Data System (ADS)

    Chemin, Marie-Charlotte

    2015-04-01

    Rare earth elements (REE) correspond to seventeen elements of the periodic table. They are used in high technology, cracking, electric cars' magnet, metal alloy for batteries, and also in phone construction or ceramics for electronic card. REEs are an important resource for high technology. This project targets 16 years old students in the subject "personalized aid" and will last six weeks. The purpose of this project is to develop autonomy and research in groups for a transdisciplinary work. This project gathers knowledge in geology, geography and economics. During the first session students analyze the geology applications of the REE. They begin the analysis with learning the composition in different rocks such as basalt and diorite to make the link with crystallization. Then they compare it with adakite to understand the formation of these rocks. In the second session, they study REE exploitation. We can find them as oxides in many deposits. The principal concentrations of rare earth elements are associated with uncommon varieties of igneous rocks, such as carbonatites. They can use Qgis, to localize this high concentration. In the third session, they study the environmental costs of REE exploitation. Indeed, the exploitation produces thorium and carcinogenic toxins: sulphates, ammonia and hydrochloric acid. Processing one ton of rare earths produces 2,000 tons of toxic waste. This session focuses, first, on Baotou's region, and then on an example they are free to choose. In the fourth session, they study the geopolitical issues of REE with a focus on China. In fact this country is the largest producer of REE, and is providing 95% of the overall production. REE in China are at the center of a geopolitical strategy. In fact, China implements a sort of protectionism. Indeed, the export tax on REE is very high so, as a foreign company, it is financially attractive to establish a manufacturing subsidiary in China in order to use REE. As a matter of fact

  5. Rare Earth Element Partitioning in Lunar Minerals: An Experimental Study

    NASA Technical Reports Server (NTRS)

    McIntosh, E. C.; Rapp, J. F.; Draper, D. S.

    2016-01-01

    The partitioning behavior of rare earth elements (REE) between minerals and melts is widely used to interpret the petrogenesis and geologic context of terrestrial and extra-terrestrial samples. REE are important tools for modelling the evolution of the lunar interior. The ubiquitous negative Eu anomaly in lunar basalts is one of the main lines of evidence to support the lunar magma ocean (LMO) hypothesis, by which the plagioclase-rich lunar highlands were formed as a flotation crust during differentiation of a global-scale magma ocean. The separation of plagioclase from the mafic cumulates is thought to be the source of the Eu depletion, as Eu is very compatible in plagioclase. Lunar basalts and volcanic glasses are commonly depleted in light REEs (LREE), and more enriched in heavy REEs (HREE). However, there is very little experimental data available on REE partitioning between lunar minerals and melts. In order to interpret the source of these distinctive REE patterns, and to model lunar petrogenetic processes, REE partition coefficients (D) between lunar minerals and melts are needed at conditions relevant to lunar processes. New data on D(sub REE) for plagioclase, and pyroxenes are now available, but there is limited available data for olivine/melt D(sub REE), particularly at pressures higher than 1 bar, and in Fe-rich and reduced compositions - all conditions relevant to the lunar mantle. Based on terrestrial data, REE are highly incompatible in olivine (i.e. D much less than 1), however olivine is the predominant mineral in the lunar interior, so it is important to understand whether it is capable of storing even small amounts of REE, and how the REEs might be fractionatied, in order to understand the trace element budget of the lunar interior. This abstract presents results from high-pressure and temperature experiments investigating REE partitioning between olivine and melt in a composition relevant to lunar magmatism.

  6. Geochemical behavior of rare earth elements and other trace elements in the Amazon River

    NASA Astrophysics Data System (ADS)

    Merschel, Gila; Bau, Michael; Dantas, Elton Luiz

    2014-05-01

    Rivers transport large amounts of dissolved and suspended particulate material from the catchment area to the oceans and are a major source of trace metals to seawater. The Amazon River is the world's largest river and supplies approximately 20% of the oceans' freshwater (Molinier et al., 1997). However, the behavior of trace elements, especially particle-reactive elements such as the rare earth elements (REE), within the river as well as in the estuary is not well constrained and rather little is known about their transport mechanisms. This study aims at understanding the transport properties of particle-reactive elements in the Amazon River and some of its major tributaries, including the Rio Solimões, Rio Negro, Tapajos, Xingu and Jari Rivers. Samples were taken at 12 stations, seven of which were located in the Amazon mainstream, while the other five stations sampled its tributaries. To account for the effects of variable discharge, the samples were collected during periods of high and low discharge. We present data for major and trace elements, including REE, of the dissolved and suspended load of these samples. First results indicate that the shale-normalized REE pattern of the dissolved load (filtered through 0.2 µm membranes) of the Amazon mainstream and the Rio Solimões confirm earlier studies (Elderfield et al., 1990; Gerard et al., 2003) and show an enrichment of the middle REE relative to the light and heavy REE (LaSN/GdSN: 0.25 - 0.32; GdSN/YbSN: 1.54 - 1.78). In contrast to the Amazon mainstream and the Rio Solimões, which are considered to be whitewater rivers, blackwater rivers, such as the Rio Negro, have a flat REE pattern with higher REE concentrations than whitewater rivers. The third water-type found in the Amazon Basin is clearwater, e.g. Rio Tapajos, with REE patterns in between those of the other two types, i.e. LaSN/GdSN: 0.55 - 0.70; GdSN/YbSN: 1.26 - 1.55. A similar behavior can be identified for other major and trace elements. While

  7. Effects of spraying rare earths on contents of rare Earth elements and effective components in tea.

    PubMed

    Wang, Dongfeng; Wang, Changhong; Ye, Sheng; Qi, Hongtao; Zhao, Guiwen

    2003-11-01

    Rare earth (RE) fertilizer is widely applied in China to increase the yield and the quality of crops including tea. However, the effects of spraying RE fertilizer on the contents of rare earth elements (REE) and effective components in tea are unknown. The results from basin and field experiments show that the values of the REE concentrations in new shoots of tea plants and the concentration of REE in the soil (REE/REEs) either from control basins or from treatment basins were smaller than those in other parts of tea plant and similar between control and treatment. The longer the interval between spraying RE fertilizer and picking the shoots of tea plants, the less the effects from spraying. About 80% summation operator REE (the sum of the concentrations of 15 REE) in tea, whether it came from spraying or not, was insoluble in the infusion. About 10% the soluble REE of summation operator REE in tea infusion was bound to polysaccharide, and the amount of REE bound polysaccharide decreased over time. At least a 25 day safety interval is needed between spraying and picking if the microelement fertilizer is used, in order to enhance tea output and to ensure tea safety. PMID:14582968

  8. Rare-earth element based permanent magnets: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Chouhan, Rajiv K.; Paudyal, Durga

    Permanent magnetic materials with large magnetization and high magnetocrystalline anisotropy are important for technical applications. In this context rare-earth (R) element based materials are good candidates because of their localized 4 f electrons. The 4 f crystal field splitting provides large part of magnetic anisotropy depending upon the crystal environment. The d spin orbit coupling of alloyed transition metal component provides additional anisotropy. RCo5 and its derivative R2Co17 are known compounds for large magnetic anisotropy. Here we have performed electronic structure calculations to predict new materials in this class by employing site substitutions. In these investigations, we have performed density functional theory including on-site electron correlation (DFT +U) and L-S coupling calculations. The results show that the abundant Ce substitution in R sites and Ti/Zr substitutions in some of the Co sites help reduce criticality without substantially affecting the magnetic moment and magnetic anisotropy in these materials. This work is supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office.

  9. β-decay of neutron-rich Z∼60 nuclei and the origin of rare earth elements

    SciTech Connect

    Wu, J.; Nishimura, S.; Lorusso, G.; Baba, H.; Doornenbal, P.; Isobe, T.; Söderström, P. A.; Sakurai, H.; Xu, Z. Y.; Browne, F.; Daido, R.; Fang, Y. F.; Yagi, A.; Nishibata, H.; Odahara, A.; Yamamoto, T.; Ideguchi, E.; Aoi, N.; Tanaka, M.; Collaboration: EURICA Collaboration; and others

    2014-05-02

    A large fraction of the rare-earth elements observed in the solar system is produced in the astrophysical rapid neutron capture process (r-process). However, current stellar models cannot completely explain the relative abundance of these elements partially because of nuclear physics uncertainties. To address this problem, a β-decay spectroscopy experiment was performed at RI Beam Factory (RIBF) at RIKEN, aimed at studying a wide range of very neutron-rich nuclei with Z∼60 that are progenitors of the rare-earth elements with mass number A∼460. The experiment provides a test of nuclear models as well as experimental inputs for r-process calculations. This contribution presents the experimental setup and some preliminary results of the experiment.

  10. β-decay of neutron-rich Zâ¼60 nuclei and the origin of rare earth elements

    NASA Astrophysics Data System (ADS)

    Wu, J.; Nishimura, S.; Lorusso, G.; Xu, Z. Y.; Baba, H.; Browne, F.; Daido, R.; Doornenbal, P.; Fang, Y. F.; Ideguchi, E.; Isobe, T.; Li, Z.; Patel, Z.; Rice, S.; Simpson, G.; Sinclair, L.; Söderström, P. A.; Sumikama, T.; Watanabe, H.; Yagi, A.; Yokoyama, R.; Aoi, N.; Garrote, F. L. Bello; Benzoni, G.; Gey, G.; Gottardo, A.; Nishibata, H.; Odahara, A.; Sakurai, H.; Tanaka, M.; Taprogge, J.; Yamamoto, T.; Eurica Collaboration

    2014-05-01

    A large fraction of the rare-earth elements observed in the solar system is produced in the astrophysical rapid neutron capture process (r-process). However, current stellar models cannot completely explain the relative abundance of these elements partially because of nuclear physics uncertainties. To address this problem, a β-decay spectroscopy experiment was performed at RI Beam Factory (RIBF) at RIKEN, aimed at studying a wide range of very neutron-rich nuclei with Z˜60 that are progenitors of the rare-earth elements with mass number A˜460. The experiment provides a test of nuclear models as well as experimental inputs for r-process calculations. This contribution presents the experimental setup and some preliminary results of the experiment.

  11. Rare earth element components in atmospheric particulates in the Bayan Obo mine region.

    PubMed

    Wang, Lingqing; Liang, Tao; Zhang, Qian; Li, Kexin

    2014-05-01

    The Bayan Obo mine, located in Inner Mongolia, China, is the largest light rare earth body ever found in the world. The research for rare earth elements (REEs) enrichment in atmospheric particulates caused by mining and ore processing is fairly limited so far. In this paper, atmospheric particulates including total suspended particulate (TSP) matter and particles with an equivalent aerodynamic diameter less than 10 μm (PM10) were collected around the Bayan Obo mine region, in August 2012 and March 2013, to analyze the levels and distributions of REEs in particles. The total concentrations of REEs for TSP were 149.8 and 239.6 ng/m(3), and those for PM10 were 42.8 and 68.9 ng/m(3), in August 2012 and March 2013, respectively. Enrichment factor was calculated for all 14 REEs in the TSP and PM10 and the results indicated that REEs enrichment in atmosphere particulates was caused by anthropogenic sources and influenced by the strong wind in springtime. The spatial distribution of REEs in TSP showed a strong gradient concentration in the prevailing wind direction. REE chondrite normalized patterns of TSP and PM10 were similar and the normalized curves inclined to the right side, showing the conspicuous fractionation between the light REEs and heavy REE, which supported by the chondrite normalized concentration ratios calculated for selected elements (La(N)/Yb(N), La(N)/Sm(N), Gd(N)/Yb(N)). PMID:24657942

  12. Refractory element fractionation in the Allende meteorite: Implications for solar nebula condensation and the chondritic composition of planetary bodies

    NASA Astrophysics Data System (ADS)

    Stracke, Andreas; Palme, Herbert; Gellissen, Marko; Münker, Carsten; Kleine, Thorsten; Birbaum, Karin; Günther, Detlef; Bourdon, Bernard; Zipfel, Jutta

    2012-05-01

    fractionated group II rare earth element patterns, i.e., variable enrichment of the more volatile refractory elements (Ta, U, Nb, Sr, Tm, Nd) over the strongly refractory elements (Lu, Zr, Hf). Admixture of group II CAI can also account for the sub-chondritic Nb/Ta and Zr/Nb ratios in CV chondrites. The total average of all 37 samples has a clear group II-type rare earth element pattern. If this fractionated refractory element pattern is representative of the Allende parent body, this observation suggests that bulk planetary bodies, possibly including the Earth-forming planetary embryos, may have refractory element patterns that are fractionated relative to those of CI chondrites.

  13. Skeleton versus fine earth: what information is stored in the mobile extracellular soil DNA fraction?

    NASA Astrophysics Data System (ADS)

    Ascher, Judith; Ceccherini, Maria Teresa; Agnelli, Alberto; Corti, Guiseppe; Pietramellara, Giacomo

    2010-05-01

    The soil genome consists of an intracellular and an extracellular fraction. Recently, soil extracellular DNA (eDNA) has been shown to be quantitatively relevant, with a high survival capacity and mobility, playing a crucial role in the gene transfer by transformation, in the formation of bacterial biofilm and as a source of nutrients for soil microorganisms. The eDNA fraction can be discriminated and classified by its interaction with clay minerals, humic acids and Al/Fe oxihydroxides, resulting in differently mobile components. The eDNA extractable in water, classified as DNA free in the extracellular soil environment or adsorbed on soil colloids (eDNAfree/adsorbed), is hypothesized to be the most mobile DNA in soil. Challenging to assess the information stored in this DNA fraction, eDNAfree/adsorbed was recovered from fine earth (< 4 mm) and highly altered rock fragments or skeleton (4-10 mm) of six consecutive horizons (A1-BCb2) of a forest soil profile by washing the two soil fractions with H2O. Quantitative analysis have been conducted in terms of DNA yields (fluorimeter and spectrophotometer), molecular weight and fragment length distribution (gel electrophoresis), and qualitative analysis in terms of the composition and distribution of fungal and bacterial communities (Denaturing Gradient Gel Electrophoresis- fingerprinting). The mobile soil eDNA, extracted from each horizon, was characterised by low molecular weight (< 2 kb) and amounts ranging from 3.96 (±0.179) to 0.17 (±0.023) µg g-1 for the fine earth and from 1.42 (±0.111) to 0.11 (±0.007) µg g-1 for the skeleton. Genetic fingerprinting of eDNA recovered from fine earth and skeleton revealed characteristic fungal and bacterial communities of each horizon, but also similarities among the microbial communities of both soil fractions and horizons. This could be interpreted also as a result of the movement of eDNA along the soil profile and from fine earth to skeleton. The molecular characterization

  14. The geochemistry of rare earth elements in the Amazon River estuary

    SciTech Connect

    Shokovitz, E.R. )

    1993-05-01

    The estuarine geochemistry of rare earth elements (REEs) was studied using samples collected in the Amazon River estuary from the AmasSeds (Amazon Shelf SEDiment Study) cruise of August 1989. Extensive removal of dissolved (0.22 [mu]m filtered) trivalent REEs from river water occurs in the low (0--6) salinity region. Removal by the salt-induced coagulation of river colloids leads to fractionation among the REE(III) series; the order of removal is light REEs > middle REEs > heavy REEs. There also is the enhanced removal of Ce (relative to trivalent La and Nd) in the low salinity (0--6) zone and in the zone of high biological activity. This is the first field observation of strong Ce removal associated with coagulation of river colloids and biological productivity. The argument is made that the decrease in the Ce anomaly across a biological front is caused by biologically mediated oxidation of Ce(III) to Ce(IV). Coagulation of river colloids and biologically mediated oxidation of Ce(III) lead to fractionation of REE(III) and redox modification of Ce. These processes result in the REE composition becoming fractionated relative to the Amazon River water and crust and more evolved toward the REE composition of the oceans. This study implies that reactions in estuaries play significant, yet poorly understood roles in controlling the REE composition and Ce anomaly of the oceans. 46 refs., 9 figs., 2 tabs.

  15. Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

    SciTech Connect

    Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John; Hakala, J. Alexandra; Karamalidis, Athanasios K.

    2015-06-26

    In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In these samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.

  16. A method for predicting bioavailability of rare earth elements in soils to maize.

    PubMed

    Wang, Wei-Sheng; Shan, Xiao-Quan; Wen, Bei; Zhang, Shu-Zhen

    2004-03-01

    A single-extraction procedure using low-molecular-weight organic acids (LMWOAs) as extractant and the first and second steps of a three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now European Community Standards, Measurement and Testing Programme, Brussels, Belgium) were performed to extract the light rare earth elements (LREEs) La, Ce, Pr, and Nd from wet rhizosphere soil. The extracted soil solutions were successively filtered through membranes with a pore size of less than 0.45 microm and a molecular weight cutoff of less than 1 kDa, which were termed colloidal and truly dissolved fractions, respectively. Apoplastically and symplastically bound LREEs in maize roots were experimentally distinguished by ultrasound-assisted desorption with 1 mM CaCl2 solution at 0 degrees C in ice-cooled water bath. When the LMWOAs extraction method was used, a good correlation was obtained between LREEs in soil colloidal and truly dissolved fractions and LREEs bound to apoplasm and symplasm of maize root. Both apoplastically and symplastically bound LREEs are the result of bioavailability. However, a poor correlation was obtained between LREEs in fractions water soluble, exchangeable and carbonate bound (B1) and Fe-Mn oxide bound (B2) of the BCR method and LREEs in apoplasm and symplasm and in intact roots. Hence, the LMWOAs extraction method is recommended for measuring the bioavailability of LREEs in soils. PMID:15285371

  17. Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

    DOE PAGESBeta

    Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John; Hakala, J. Alexandra; Karamalidis, Athanasios K.

    2015-06-26

    In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In thesemore » samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.« less

  18. Binary rare earth element-Ni/Co metallic glasses with distinct β-relaxation behaviors

    SciTech Connect

    Zhu, Z. G.; Wang, Z.; Wang, W. H.

    2015-10-21

    We report the formation of a series of rare earth element (RE)-Ni/Co binary metallic glasses (MGs) with unusual distinct β-relaxation peak compared with that of most of the reported MGs which usually exhibit as an excess wing or a shoulder. The β-relaxation behavior of RE-Ni/Co MGs is sensitive to the composition and the atomic radii of the RE and can be tuned through changing the fraction of RE-Ni (or Co) atomic pairs. The novel RE-Ni/Co MGs with distinct β-relaxation can serve as model system to investigate the nature of the β-relaxation as well as its relations with other physical and mechanical properties of MGs.

  19. Geochemistry of rare earth elements in a passive treatment system built for acid mine drainage remediation.

    PubMed

    Prudêncio, Maria Isabel; Valente, Teresa; Marques, Rosa; Sequeira Braga, Maria Amália; Pamplona, Jorge

    2015-11-01

    Rare earth elements (REE) were used to assess attenuation processes in a passive system for acid mine drainage treatment (Jales, Portugal). Hydrochemical parameters and REE contents in water, soils and sediments were obtained along the treatment system, after summer and winter. A decrease of REE contents in the water resulting from the interaction with limestone after summer occurs; in the wetlands REE are significantly released by the soil particles to the water. After winter, a higher water dynamics favors the AMD treatment effectiveness and performance since REE contents decrease along the system; La and Ce are preferentially sequestered by ochre sludge but released to the water in the wetlands, influencing the REE pattern of the creek water. Thus, REE fractionation occurs in the passive treatment systems and can be used as tracer to follow up and understand the geochemical processes that promote the remediation of AMD. PMID:26247412

  20. β-Decay of Neutron-Rich Nuclei around 158Nd and the Origin of Rare-Earth Elements

    NASA Astrophysics Data System (ADS)

    Wu, J.; Nishimura, S.; Lorusso, G.; Xu, Z. Y.; Ideguchi, E.; Simpson, G. S.; Baba, H.; Browne, F.; Daido, R.; Doornenbal, P.; Fang, Y. F.; Isobe, T.; Li, Z.; Patel, Z.; Rice, S.; Sinclair, L.; Söderström, P.-A.; Sumikama, T.; Watanabe, H.; Yagi, A.; Yokoyama, R.; Aoi, N.; Bello Garrote, F. L.; Benzoni, G.; Gey, G.; Gottardo, A.; Nishibata, H.; Odahara, A.; Sakurai, H.; Tanaka, M.; Taprogge, J.; Yamamoto, T.

    A large fraction of the rare-earth elements around mass number A = 160 observed in the solar system are produced in the astrophysical rapid (r-) neutron capture process. However, current stellar models cannot completely explain the relative abundance of these elements partially because of nuclear physics uncertainties. To address this problem, a β-decay spectroscopy experiment was performed at the RI Beam Factory (RIBF), aimed at studying a wide region of very neutron-rich nuclei around 158Nd. The data from this experiment provides a test of nuclear models as well as experimental inputs for r-process calculations.

  1. Determination of element affinities by density fractionation of bulk coal samples

    USGS Publications Warehouse

    Querol, X.; Klika, Z.; Weiss, Z.; Finkelman, R.B.; Alastuey, A.; Juan, R.; Lopez-Soler, A.; Plana, F.; Kolker, A.; Chenery, S.R.N.

    2001-01-01

    A review has been made of the various methods of determining major and trace element affinities for different phases, both mineral and organic in coals, citing their various strengths and weaknesses. These include mathematical deconvolution of chemical analyses, direct microanalysis, sequential extraction procedures and density fractionation. A new methodology combining density fractionation with mathematical deconvolution of chemical analyses of whole coals and their density fractions has been evaluated. These coals formed part of the IEA-Coal Research project on the Modes of Occurrence of Trace Elements in Coal. Results were compared to a previously reported sequential extraction methodology and showed good agreement for most elements. For particular elements (Be, Mo, Cu, Se and REEs) in specific coals where disagreement was found, it was concluded that the occurrence of rare trace element bearing phases may account for the discrepancy, and modifications to the general procedure must be made to account for these.

  2. Rare earth element components in atmospheric particulates in the Bayan Obo mine region

    SciTech Connect

    Wang, Lingqing Liang, Tao Zhang, Qian; Li, Kexin

    2014-05-01

    The Bayan Obo mine, located in Inner Mongolia, China, is the largest light rare earth body ever found in the world. The research for rare earth elements (REEs) enrichment in atmospheric particulates caused by mining and ore processing is fairly limited so far. In this paper, atmospheric particulates including total suspended particulate (TSP) matter and particles with an equivalent aerodynamic diameter less than 10 μm (PM{sub 10}) were collected around the Bayan Obo mine region, in August 2012 and March 2013, to analyze the levels and distributions of REEs in particles. The total concentrations of REEs for TSP were 149.8 and 239.6 ng/m{sup 3}, and those for PM{sub 10} were 42.8 and 68.9 ng/m{sup 3}, in August 2012 and March 2013, respectively. Enrichment factor was calculated for all 14 REEs in the TSP and PM{sub 10} and the results indicated that REEs enrichment in atmosphere particulates was caused by anthropogenic sources and influenced by the strong wind in springtime. The spatial distribution of REEs in TSP showed a strong gradient concentration in the prevailing wind direction. REE chondrite normalized patterns of TSP and PM{sub 10} were similar and the normalized curves inclined to the right side, showing the conspicuous fractionation between the light REEs and heavy REE, which supported by the chondrite normalized concentration ratios calculated for selected elements (La{sub N}/Yb{sub N}, La{sub N}/Sm{sub N}, Gd{sub N}/Yb{sub N}). - Highlights: • TSP and PM{sub 10} samples were collected to analyze the levels and distributions of REE. • Enrichment factors indicated that REE enrichment was caused by anthropogenic sources. • The distribution of REEs showed a strong gradient in the prevailing wind direction. • Obvious fractionation between LREEs and HREEs is observed in atmospheric particulates.

  3. Enhanced phytoextraction of germanium and rare earth elements - a rhizosphere-based approach

    NASA Astrophysics Data System (ADS)

    Wiche, Oliver

    2016-04-01

    with white lupin and cereals like barley (Hordeum vulgare) and millet (Panicum miliaceum) significantly enhanced the uptake of all investigated elements in co-cultured species due to interspecific root interactions. Concentrations of the investigated rare earth elements in shoots were significantly correlated to concentrations of Fe, Mn and P in shoots. Enhanced uptake of the mentioned elements corresponded to a depletion of elements in the rhizosphere soil of white lupin. Accordingly, processes in the rhizosphere of plants seem to play a key role controlling availability of REEs in the soil-plant system, since presence of white lupin clearly increased the uptake of REEs in shoots of barley and millet even to a level comparable with white lupin and this was most probably caused by attacking fractions of elements in soil hardly accessible for barley and millet. These studies have been carried out in the framework of the PhytoGerm project financed by the Federal Ministry of Education and Research, Germany.

  4. Elemental Fractionation During Rapid Accretion of the Moon Triggered by a Giant Impact

    NASA Technical Reports Server (NTRS)

    Abe, Y.; Zahnle, K. J.; Hashimoto, A.

    1998-01-01

    Recently, Ida et al. made an N-body simulation of lunar accretion from a protolunar disk formed by a giant impact. One of their important conclusions is that the accretion time of the Moon is as short as one month. Such rapid accretion is a necessary consequence of the high surface density of a lunar mass disk accreting just beyond the Roche limit (about 3Re); the Safronov accretion time (a few days) is even shorter. The energy of accretion always exceeds the gravitational binding energy of newly arriving matter. Hence, without an energy sink, the accreting body is thermally unstable. For the Earth and other planets, radiation acts as the sink. However, in such a short accretion time, the Moon cannot radiate the accretional energy. Even radiating at a silicate cloudtop temperature of roughly 2000 K, it would take more than 100 yr to radiatively cool the Moon. The plausible alternative heat sinks are heat capacity, latent heat of vaporization, and thermal escape of the gas to space (i.e., hydrodynamic blowoff). The latter becomes plausible for the Moon because the scale height at 2000 K (about 300 km) is a significant fraction of the lunar radius. The early stages of lunar (or "lunatesimal") growth release relatively little energy and can occur simply by heating the material, especially if the accreting material is originally cold. However, the material is unlikely to be cold, because the disk itself is hot and cooling time is long, while the lunar accretion time iss very short. Therefore, the moon is likely to accrete condensed material just after it condenses. Accordingly, the newly accreted material will be on the verge of vaporization and will have very little heat capacity to spare. The immediate heat sink is the latent heat of vaporization. Most of the vapor will escape from the moon, because the thermal energy in the gas can be used to drive escape. However, vaporization is generally incomplete. the latent heat of vaporization exceeds the energy of accretion

  5. Recovery and Separation of Rare Earth Elements Using Salmon Milt

    PubMed Central

    Takahashi, Yoshio; Kondo, Kazuhiro; Miyaji, Asami; Watanabe, Yusuke; Fan, Qiaohui; Honma, Tetsuo; Tanaka, Kazuya

    2014-01-01

    Recycling rare earth elements (REEs) used in advanced materials such as Nd magnets is important for the efficient use of REE resources when the supply of several REEs is limited. In this work, the feasibility of using salmon milt for REE recovery and separation was examined, along with the identification of the binding site of REEs in salmon milt. Results showed that (i) salmon milt has a sufficiently high affinity to adsorb REEs and (ii) the adsorption capacity of the milt is 1.04 mEq/g, which is comparable with that of commercial cation exchange resin. Heavier REEs have higher affinity for milt. A comparison of stability constants and adsorption patterns of REEs discussed in the literature suggests that the phosphate is responsible for the adsorption of REE in milt. The results were supported by dysprosium (Dy) and lutetium (Lu) LIII-edge extended x-ray absorption fine structure (EXAFS) spectroscopy. The REE-P shell was identified for the second neighboring atom, which shows the importance of the phosphate site as REE binding sites. The comparison of REE adsorption pattern and EXAFS results between the milt system and other adsorbent systems (cellulose phosphate, Ln-resin, bacteria, and DNA-filter hybrid) revealed that the coordination number of phosphate is correlated with the slope of the REE pattern. The separation column loaded with milt was tested to separate REE for the practical use of salmon milt for the recovery and separation of REE. However, water did not flow through the column possibly because of the hydrophobicity of the milt. Thus, sequential adsorption–desorption approach using a batch-type method was applied for the separation of REE. As an example of the practical applications of REE separation, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste by a batch-type method using salmon milt. PMID:25490035

  6. Volatile elements in chondrites - Metamorphism or nebular fractionation

    NASA Technical Reports Server (NTRS)

    Takahashi, H.; Gros, J.; Higuchi, H.; Morgan, J. W.; Anders, E.

    1978-01-01

    Three of the most highly metamorphosed meteorites of their respective classes, Shaw (LL7), Karoonda (C5), and Coolidge (C4), were analyzed by radiochemical neutron activation analysis for Ag, Au, Bi, Br, Cd, Cs, Ge, In, Ir, Ni, Os, Pd, Rb, Re, Sb, Se, Te, Tl, U, and Zn. Comparison with data by Lipschutz and coworkers (1977) on artificially heated primitive meteorites shows that the natural metamorphism of meteorites cannot have taken place in a system open to volatiles. Shaw, metamorphosed at 1300 C for more than 1 million yr, is less depleted in In, Bi, Ag, Te, Zn, and Tl than Krymka heated at 1000 C for 1 week. Karoonda, metamorphosed at 600 C for many millennia, is less depleted in Bi and Tl than Allende heated at 600 C for 1 week. Data on primordial noble gases also show that the volatile-element patterns of ordinary and carbonaceous chondrites were established by nebular condensation and changed little, if at all, during metamorphism. For enstatite chondrites, the evidence is still incomplete but seems to favor a nebular origin of the volatile pattern.

  7. Distribution of 28 elements in size fractions of lunar mare and highlands soils

    NASA Technical Reports Server (NTRS)

    Boynton, W. V.; Wasson, J. T.

    1977-01-01

    Four volatile, six siderophile and 18 generally lithophile elements were determined in six sieve fractions of mare soil 15100 (moderately mature) and seven sieve fractions of highlands soil 66080 (highly mature). Previous work (Boynton et al., 1976) showed that the volatile elements in lunar soils were enriched in the finest size fraction relative to the coarsest factors by up to about 20. The present investigation tests Boynton's interpretation that the distribution pattern of the volatiles indicates the presence of two components: a volume-correlated component having volatile concentrations independent of grain size and a surface-correlated component with concentration increasing with decreasing grain size.

  8. Rare earth element distributions in recent and fossil apatite: implications for paleoceanography and stratigraphy

    SciTech Connect

    Wright, J.

    1985-01-01

    Rare earth element (REE) distributions in biogenic apatite were determined in over 200 samples from Cambrian to the Recent. Nondestructive instrumental neutron activation analysis techniques were adapted for analysis of low-mass microfossil samples. Tests for chemical contamination, interspecies, interlaboratory and interexperiment variations show that there is no fractionation of REE, so that ratios of rare earths are consistent throughout the entire group of samples. The REE signature of biogenic apatite is acquired after deposition but only at the sediment-water interface and is characteristic of the redox state of the environment of deposition. This original environmental signature is retained through subsequent burial and diagenesis. Cerium has been shown to be the rare earth element that is sensitive to oxidation-reduction variations in marine waters. This cerium variation is stated mathematically and called Ce/sub anom/. Comparison of Ce/sub anom/ in fish debris from different modern redox environments shows that values > -0.10 occur in fish debris deposited under reducing conditions, whereas Ce/sub anom/ values <-0.10 are obtained under oxidizing conditions. Paleoredox studies of Ce/sub anom/ of fossil apatite of conodonts, fish debris and inarticulate brachiopods indicate that significant shifts in the overall redox balance of seawater occurred in ancient oceans. Cambrian through Silurian seas were dominated by anoxia, followed by a gradual change to oxidizing conditions in the Devonian. Oceans remained generally oxidizing throughout the Carboniferous and Lower Permian. In the Upper Permian and Lower Triassic anoxic conditions were again prevalent. This was followed by a return to an oxidizing oceanic environment in the Upper Triassic.

  9. Rare earth element geochemistry and petrogenesis of miles (IIE) silicate inclusions

    NASA Astrophysics Data System (ADS)

    Hsu, Weibiao

    2003-12-01

    An ion probe study of rare earth element (REE) geochemistry of silicate inclusions in the Miles IIE iron meteorite was carried out. Individual mineral phases among inclusions have distinct REE patterns and abundances. Most silicate grains have homogeneous REE abundances but show considerable intergrain variations between inclusions. A few pyroxene grains display normal igneous REE zoning. Phosphates (whitlockite and apatite) are highly enriched in REEs (50 to 2000 × CI) with a relatively light rare earth element (LREE)-enriched REE pattern. They usually occurred near the interfaces between inclusions and Fe host. In Miles, albitic glasses exhibit two distinctive REE patterns: a highly fractionated LREE-enriched (CI normalized La/Sm ˜15) pattern with a large positive Eu anomaly and a relatively heavy rare earth element (HREE)-enriched pattern (CI-normalized Lu/Gd ˜4) with a positive Eu anomaly and a negative Yb anomaly. The glass is generally depleted in REEs relative to CI chondrites. The bulk REE abundances for each inclusion, calculated from modal abundances, vary widely, from relatively depleted in REEs (0.1 to 3 × CI) with a fractionated HREE-enriched pattern to highly enriched in REEs (10 to 100 × CI) with a relatively LREE-enriched pattern. The estimated whole rock REE abundances for Miles are at ˜ 10 × CI with a relatively LREE-enriched pattern. This implies that Miles silicates could represent the product of a low degree (˜10%) partial melting of a chondritic source. Phenocrysts of pyroxene in pyroxene-glassy inclusions were not in equilibrium with coexisting albitic glass and they could have crystallized from a parental melt with REEs of ˜ 10 × CI. Albitic glass appears to have formed by remelting of preexisting feldspar + pyroxene + tridymite assemblage. Yb anomaly played an important role in differentiation processes of Miles silicate inclusions; however, its origin remains unsolved. The REE data from this study suggest that Miles, like

  10. Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model

    USGS Publications Warehouse

    Verplanck, Philip L.; Van Gosen, Bradley S.

    2011-01-01

    The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

  11. Carbon isotope fractionation between Fe-carbide and diamond; a light C isotope reservoir in the deep Earth and Core?

    NASA Astrophysics Data System (ADS)

    Mikhail, S.; Jones, A. P.; Hunt, S. A.; Guillermier, C.; Dobson, D. P.; Tomlinson, E.; Dan, H.; Milledge, H.; Franchi, I.; Wood, I.; Beard, A.; Verchovsky, S.

    2010-12-01

    The largest accessible reservoir for terrestrial carbon is the mantle; however the core may yield even more. Carbon is commonly proposed as the light element (or one of) to make up the observed density deficit in the earth’s metallic core (NAKAJIMA et al., 2009). The potential isotopic effects of carbon incorporation into the core have not yet been investigated. In-situ ion probe (nanoSIMS) mapping and imaging of carbon isotope variations across rare sub-mm-scale Fe-rich carbide inclusions in mantle diamond (from Jagersfontein, South Africa) show the carbide to be significantly depleted in 13C relative to their diamond host. Distinctive textures suggest metallic liquid precipitates similar in geometry to (giant) nitrogen platelets, controlled by the octahedral symmetry of diamond, which we interpret as syngenic formation. The difference in δ13C values between the two natural phases for diamond-Fe carbide, gives an isotopic fractionation factor (ΔC) which agrees well with HPHT multi-anvil experiments (5-9 GPa and >1400°C). Our measured ΔC between Fe-carbide and diamond may only have local significance, but the measured isotopic values represent characterization of the highest PT carbide known (i.e. > minimum depth of the diamond stability field ≈ 150 km). The direction and magnitude of ΔC agrees with observations of the ΔC between cohenite-graphite in iron meteorites (DEINES and WICKMAN, 1975) and both agree with HPHT experiments, thus suggesting that carbon in the deep Earth, and particularly in the core, may be similarly fractionated (i.e. depleted in the 13C). Since metallic liquid drained from the silicate mantle to form the core during the early Earth, we can use our values as a proxy to constrain evolution of deep carbon reservoirs such as the core and bulk silicate Earth. For example, we can test the suggestion of Grady et al (2004) that the upper mantle value of δ13C ≈ -5 ‰ may not be representative of the bulk Earth, since solar system

  12. PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

    DOEpatents

    Baybarz, R.D.; Lloyd, M.H.

    1963-02-26

    This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

  13. Core-Mantle Partitioning of Volatile Siderophile Elements and the Origin of Volatile Elements in the Earth

    NASA Technical Reports Server (NTRS)

    Nickodem, K.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

    2012-01-01

    There are currently several hypotheses on the origin of volatile siderophile elements in the Earth. One hypothesis is that they were added during Earth s accretion and core formation and mobilized into the metallic core [1], others claim multiple stage origin [2], while some hypothesize that volatiles were added after the core already formed [3]. Several volatile siderophile elements are depleted in Earth s mantle relative to the chondrites, something which continues to puzzle many scientists. This depletion is likely due to a combination of volatility and core formation. The Earth s core is composed of Fe and some lighter constituents, although the abundances of these lighter elements are unknown [4]. Si is one of these potential light elements [5] although few studies have analyzed the effect of Si on metal-silicate partitioning, in particular the volatile elements. As, In, Ge, and Sb are trace volatile siderophile elements which are depleted in the mantle but have yet to be extensively studied. The metal-silicate partition coefficients of these elements will be measured to determine the effect of Si. Partition coefficients depend on temperature, pressure, oxygen fugacity, and metal and silicate composition and can constrain the concentrations of volatile, siderophile elements found in the mantle. Reported here are the results from 13 experiments examining the partitioning of As, In, Ge, and Sb between metallic and silicate liquid. These experiments will examine the effect of temperature, and metal-composition (i.e., Si content) on these elements in or-der to gain a greater understanding of the core-mantle separation which occurred during the Earth s early stages. The data can then be applied to the origin of volatile elements in the Earth.

  14. Siderophile element fractionation in meteor crater impact glasses and metallic spherules

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.; See, T. H.; Scott, E. R. D.

    1993-01-01

    Meteor Crater, Arizona provides an opportunity to study, in detail, elemental fractionation processes occurring during impacts through the study of target rocks, meteorite projectile and several types of impact products. We have performed EMPA and INAA on target rocks, two types of impact glass and metallic spherules from Meteor Crater. Using literature data for the well studied Canyon Diablo iron we can show that different siderophite element fractionations affected the impact glasses than affected the metallic spherules. The impact glasses primarily lost Au, while the metallic spherules lost Fe relative to other siderophile elements.

  15. Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain).

    PubMed

    Olías, M; Cerón, J C; Fernández, I; De la Rosa, J

    2005-05-01

    This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe. PMID:15701392

  16. Quantifying Surface Kinetic Fractionations for Isotopes and Trace Elements in Calcite Precipitated from Aqueous Solution

    NASA Astrophysics Data System (ADS)

    DePaolo, D. J.; Nielsen, L. C.; Hofmann, A. E.; DeYoreo, J.; Gagnon, A. C.; Watkins, J. M.; Ryerson, F. J.; Brown, S. T.

    2011-12-01

    The isotopic ratios and trace element concentrations in calcite and other carbonate minerals form the basis for several paleoenvironmental indicators that are relied upon to reconstruct past Earth climates and ocean processes. Most of these carbonate minerals form at low temperatures (0 to 30C) and consequently are unlikely to have precipitated from aqueous solutions at equilibrium. The non-equilibrium nature of the precipitation process is well illustrated by the experimentally demonstrated precipitation rate-dependence of parameters such as the Ca and O isotopic composition, and the Sr, Mg, and Mn concentrations of calcite. We have been focused on understanding how to predict the magnitude and controls on these kinetic effects using a general transition-state theory approach, as well as models of ion-by-ion growth, molecular dynamics simulations of the desolvation step required for addition of cations to a mineral surface, and further experiments that involve carefully controlled solution compositions and crystal growth rates. Although models have been proposed that invoke diffusion as the primary control on the non-equilibrium aspects of calcite precipitation, it is relatively easy to show that diffusion is not likely to be the primary controlling process. We have focused on understanding the kinetic effects operating at and near the mineral surface, which are undeniably present and important, and appear to be of the correct magnitude and direction to account for observations in both laboratory and natural calcites. The approach we are using is also applicable to higher temperature aqueous precipitation. There are indications from Ca isotopes that similar surface kinetic effects occur at temperatures of 300 to 400C. Kinetic isotope and trace element effects are critically dependent on molecular exchange rates between the mineral surface and the aqueous solution, and the ratio of these rates to the net crystal growth rate. The challenge is to predict and

  17. Rare Earth elements as sediment tracers in Mangrove ecosystems

    NASA Astrophysics Data System (ADS)

    Ramanathan, A. L.; Swathi, S.

    2013-05-01

    Rare earth elements have been widely used as geochemical source fingerprints of rocks and sediments to study processes involving cosmo-chemistry, igneous petrology, tectonic setting and for investigations of water-rock interactions and weathering processes including transport of weathering products to the oceans.Many studies have addressed the use of REEs in investigating the environmental impact of human activity and demonstrated that the REE natural distribution in sediment from densely industrialised and populated regions can be altered by anthropogenic influences.The coastal wetlands like Mangroves are ultimate sinks for all the material derived from the terrestrial and marine environment.The high productivity and low ratio of sediment respiration to net primary production gives mangrove sediments the potential for long-term sequestration of these pollutants/metals before reaching the coastal ocean. Geochemical study of REE in these sedimentary systems is useful for determining the nature of the biogeochemical processes. In particular, REE show a great sensitivity to pH changes, redox conditions and adsorption/ desorption reactions. So, they may be used as markers of discharge provenance, weathering processes, changes in environmental conditions in the water and sediments of Mangrove/wetland systems. Our study aims to establish the abundance, distribution and enrichment of REEs to track the sediment sources and biogeochemical processes occurring in the mangrove environment.Core sediments were collected from the different environmental settings within the Pichavaram mangrove area.Higher REE concentration in Pichavaram sediments indicated greater input from sources like terrestrial weathering and anthropogenic activities which in turn are affected by saline mixing and dynamic physico-chemical processes occurring in the mangrove environment. REE enrichment order was attributed to the alkaline pH (7-8.5) and reducing conditions prevailing in the mangrove

  18. Composition of the earth's upper mantle-I. Siderophile trace elements in ultramafic nodules

    USGS Publications Warehouse

    Morgan, J.W.; Wandless, G.A.; Petrie, R.K.; Irving, A.J.

    1981-01-01

    Seven siderophile elements (Au, Ge, Ir, Ni, Pd, Os, Re) were determined by radiochemical neutron activation analysis in 19 ultramafic rocks, which are spinel lherzollites-xenoliths from North and Central America, Hawaii and Australia, and garnet Iherzolitexenoliths from Lesotho. Abundances of the platinum metals are very uniform in spinel lherzolites averaging 3.4 ?? 1.2 ppb Os, 3.7 ?? 1.1 ppb Ir, and 4.6 ?? 2.0 ppb Pd. Sheared garnet lherzolite PHN 1611 has similar abundances of these elements, but in 4 granulated garnet lherzolites, abundances are more variable. In all samples, the Pt metals retain cosmic ( Cl-chondrite) ratios. Abundances of Au and Re vary more than those of Pt metals, but the Au/Re ratio remains close to the cosmic value. The fact that higher values of Au and Re approach cosmic proportions with respect to the Pt metals, suggests that Au and Re have been depleted in some ultramafic rocks from an initially chondrite-like pattern equivalent to about 0.01 of Cl chondrite abundances. The relative enrichment of Au and Re in crustal rocks is apparently the result of crust-mantle fractionation and does not require a special circumstance of core-mantle partitioning. Abundances of moderately volatile elements Ni, Co and Ge are very uniform in all rocks, and are much higher than those of the highly siderophile elements Au, Ir, Pd, Os and Re. When normalized to Cl chondrites, abundances of Ni and Co are nearly identical, averaging 0.20 ?? 0.02 and 0.22 ?? 0.02, respectively; but Ge is only 0.027 ?? 0.004. The low abundance of Ge relative to Ni and Co is apparently a reflection of the general depletion of volatile elements in the Earth. The moderately siderophile elements cannot be derived from the same source as the highly siderophile elements because of the marked difference in Cl chondrite-normalized abundances and patterns. We suggest that most of the Ni, Co and Ge were enriched in the silicate by the partial oxidation of pre-existing volatile-poor Fe

  19. Potentially toxic element fractionation in technosoils using two sequential extraction schemes.

    PubMed

    Qasim, Bashar; Motelica-Heino, Mikael

    2014-04-01

    This study reports the chemical fractionation of several potentially toxic elements (Zn, Pb, Cd, As, and Sb) in contaminated technosoils of two former smelting and mining areas using two sequential extraction schemes. The extraction schemes used in this study were the Tessier's scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidizable, and residual to compare the results obtained from two sequential extraction schemes. Surface soils were samples from a waste landfill contaminated with Zn, Pb, and Cd located at Mortagne-du-Nord (MDN; North France) and from a settling basin contaminated with PTE such as As, Pb, and Sb located at La Petite Faye (LPF; Limoges, France). The study of the Zn, Pb, Cd, As, and Sb partitioning in the acid soluble, reducible, oxidizable, and residual fractions of the technosoils revealed that Zn, Cd, and Pb were mainly associated with the acid soluble and reducible fractions for MDN site, while As, Sb, and Pb were associated with residual fraction for LPF site. Fractionation results indicate that the percentages of Zn, Pb, Cd, As, and Sb extracted in Fe-Mn oxide bound fraction of Tessier's scheme were always higher than those extracted by modified BCR scheme. This may be attributed to the stronger Tessier's scheme conditions used to extract this fraction. In contrast the percentages of Zn, Pb, Cd, As, and Sb extracted in the organic fraction of the modified BCR scheme were always higher than those of the Tessier's scheme. The order of mobility of PTE was as follows: Cd > Zn > Pb in MDN site and As > Sb > Pb in LPF site. PTE were distributed in all soil fractions, with the most relevant enrichments in extractable and residual fractions. A significant amount of Cd, Pb, and Zn were rather mobile, which suggests that these elements can be readily available to plants and soil organisms. PMID:24371008

  20. Minor and trace element geochemistry of volcanic rocks dredged from the Galapagos spreading center: role of crystal fractionation and mantle heterogeneity.

    USGS Publications Warehouse

    Clague, D.A.; Frey, F.A.; Thompson, G.; Rindge, S.

    1981-01-01

    A wide range of rock types (abyssal tholeiite, Fe-Ti-rich basalt, andesite, and rhyodacite) were dredged from near 95oW and 85oW on the Galapagos spreading center. Computer modeling of major element compositions has shown that these rocks could be derived from common parental magmas by successive degrees of fractional crystallization. However, the P2O5/K2O ratio implies distinct mantle source compositions for the two areas. These source regions also have different rare earth element (REE) abundance patterns. The sequence of fractionated lavas differs for the two areas and indicates earlier fractionation of apatite and titanomagnetite in the lavas from 95oW. The mantle source regions for these two areas are interpreted to be depleted in incompatible (and volatile?) elements, although the source region beneath 95oW is less severely depleted in La and K. -Authors

  1. Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

    NASA Astrophysics Data System (ADS)

    Tang, Jianwu; Johannesson, Karen H.

    2010-12-01

    The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH 3COO -) or strong (i.e., CO32-) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE

  2. RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

    EPA Science Inventory

    Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

  3. The role of chondrules in nebular fractionations of volatiles and other elements

    NASA Technical Reports Server (NTRS)

    Grossman, J. N.

    1994-01-01

    For at least 30 years, cosmochemists have been grappling with the question of how and why groups of geochemically and volatility related elements became fractionated in the major chondrite groups. At least five relatively independent fractionations are known. Virtually everyone who has thought about these facts has been attempted to attribute at least some of the fractionations to the physical separation or mixing of the visible components. By far the most abundant of these components in meteorites is chondrules, and indeed chondrules have long been suspected of playing a direct role in fractionation of volatile elements. The question addressed here is whether chondrules formed before or after chemical components became separated is of fundamental importance to our understanding of the early solar system, as the answer constrains how, when, where, and from what chondrules formed, and tells us about how materials were processed in the nebula.

  4. A New Mixed Element Method for a Class of Time-Fractional Partial Differential Equations

    PubMed Central

    Li, Hong; Gao, Wei; He, Siriguleng; Fang, Zhichao

    2014-01-01

    A kind of new mixed element method for time-fractional partial differential equations is studied. The Caputo-fractional derivative of time direction is approximated by two-step difference method and the spatial direction is discretized by a new mixed element method, whose gradient belongs to the simple (L2(Ω)2) space replacing the complex H(div; Ω) space. Some a priori error estimates in L2-norm for the scalar unknown u and in (L2)2-norm for its gradient σ. Moreover, we also discuss a priori error estimates in H1-norm for the scalar unknown u. PMID:24737957

  5. Rare-earth elements in the Permian Phosphoria Formation: Paleo proxies of ocean geochemistry

    USGS Publications Warehouse

    Piper, D.Z.; Perkins, R.B.; Rowe, H.D.

    2007-01-01

    The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km2, is ascertained from its rare earth element (REE) composition. Ratios of REE:Al2O3 suggest two sources-seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O2-depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni???Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O2-depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO43-, a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is

  6. Size fractionation of trace elements in the surface water and groundwater of the Ganjiang River and Xiushui River basins, China

    NASA Astrophysics Data System (ADS)

    Soldatova, E. A.; Guseva, N. V.; Sun, Z.; Mazurova, I. S.

    2015-11-01

    The research of trace element behaviour and size fractionation is significant to understand the processes in the water-rock system. Moreover, the aqueous speciation of trace elements is strongly related to their distribution and toxicity. In this research, trace elements behaviour and their size fractionation are investigated in the natural water (the surface water and shallow groundwater) of the Ganjiang River and Xiushui River basins. Trace element concentrations were measured by ICP-MS. The authors estimated the size fractionation of the trace elements between suspended forms (>0.45μm) and dissolved fractions, which included truly dissolved (1 kDa) and colloidal particles (0.45μm-1 kDa)), after filtration through a 0.45 μm acetate cellulose membrane filter. The distinct features of the trace element size fractionation were identified. The size fractionation of the trace elements under different conditions (in the surface water and shallow groundwater) was studied.

  7. Rare Earth Element Partition Coefficients from Enstatite/Melt Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Schwandt, Craig S.; McKay, Gordon A.

    1997-01-01

    Enstatite (En(80)Fs(19)Wo(01)) was synthesized from a hypersthene normative basaltic melt doped at the same time with La, Ce, Nd, Sm, Eu, Dy, Er, Yb and Lu. The rare earth element concentrations were measured in both the basaltic glass and the enstatite. Rare earth element concentrations in the glass were determined by electron microprobe analysis with uncertainties less than two percent relative. Rare earth element concentrations in enstatite were determined by secondary ion mass spectrometry with uncertainties less than five percent relative. The resulting rare earth element partition signature for enstatite is similar to previous calculated and composite low-Ca pigeonite signatures, but is better defined and differs in several details. The partition coefficients are consistent with crystal structural constraints.

  8. Fluorescent lifetime measurements of rare-earth elements in gallium arsenide. Master's thesis

    SciTech Connect

    Topp, D.J.

    1990-12-01

    Lifetime measurements of the excited states of three GaAs semiconductors doped with the rare earth elements Erbium (Er), Praseodymium (Pr), and Thulium (Tm) has been studied using a pulsed nitrogen laser and germanium detector. The measurements were made with an experimental set up with a system response time of 0.34 microseconds. A 330 milliwatt nitrogen laser with a wavelength of 3370 angstroms was used to excite transitions of the rare earth elements.

  9. Experimental Parameters Affecting Stripping of Rare Earth Elements from Loaded Sorptive Media in Simulated Geothermal Brines

    DOE Data Explorer

    Dean Stull

    2016-05-24

    Experimental results from several studies exploring the impact of pH and acid volume on the stripping of rare earth elements (REEs) loaded onto ligand-based media via an active column. The REEs in this experiment were loaded onto the media through exposure to a simulated geothermal brine with known mineral concentrations. The data include the experiment results, rare earth element concentrations, and the experimental parameters varied.

  10. SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

    DOEpatents

    Kohman, T.P.

    1961-11-21

    A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

  11. Fractional Snowcover Estimates from Earth Observing System (EOS) Terra and Aqua Moderate Resolution Imaging Spectroradiometer (MODIS)

    NASA Technical Reports Server (NTRS)

    Salomonson, Vincent V.

    2002-01-01

    The Moderate Resolution Imaging Spectroradiometer (MODIS) on the NASA Earth Observing System (EOS) Terra and Aqua missions has shown considerable capability for mapping snowcover. The typical approach that has used, along with other criteria, the Normalized Snow Difference Index (NDSI) that takes the difference between 500 meter observations at 1.64 micrometers (MODIS band 6) and 0.555 micrometers (MODIS band 4) over the sum of these observations to determine whether MODIS pixels are snowcovered or not in mapping the extent of snowcover. For many hydrological and climate studies using remote sensing of snowcover, it is desirable to assess if the MODIS snowcover observations could not be enhanced by providing the fraction of snowcover in each MODIS observation (pixel). Pursuant to this objective studies have been conducted to assess whether there is sufficient "signal%o in the NDSI parameter to provide useful estimates of fractional snowcover in each MODIS 500 meter pixel. To accomplish this objective high spatial resolution (30 meter) Landsat snowcover observations were used and co-registered with MODIS 500 meter pixels. The NDSI approach was used to assess whether a Landsat pixel was or was not snowcovered. Then the number of snowcovered Landsat pixels within a MODIS pixel was used to determine the fraction of snowcover within each MODIS pixel. The e results were then used to develop statistical relationships between the NDSI value for each 500 meter MODIS pixel and the fraction of snowcover in the MODIS pixel. Such studies were conducted for three widely different areas covered by Landsat scenes in Alaska, Russia, and the Quebec Province in Canada. The statistical relationships indicate that a 10 percent accuracy can be attained. The variability in the statistical relationship for the three areas was found to be remarkably similar (-0.02 for mean error and less than 0.01 for mean absolute error and standard deviation). Independent tests of the relationships were

  12. An improved description of the interactions between rare earth elements and humic acids by modeling: PHREEQC-Model VI coupling

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Davranche, Mélanie; Gruau, Gérard; Bouhnik-Le Coz, Martine; Dia, Aline

    2011-10-01

    The Humic Ion Binding Model VI (Model VI) - previously used to model the equilibrium binding of rare earth elements (REE) by humic acid (HA) - was modified to account for differences in the REE constant patterns of the HA carboxylic and phenolic groups, and introduced into PHREEQC to calculate the REE speciation on the HA binding sites. The modifications were shown to greatly improve the modeling. They allow for the first time to both satisfactorily and simultaneously model a large set of multi-REE experimental data with the same set of equations and parameters. The use of PHREEQC shows that the light rare earth elements (LREE) and heavy rare earth elements (HREE) do not bind to HA by the same functional groups. The LREE are preferentially bound to carboxylic groups, whereas the HREE are preferentially bound to carboxy-phenolic and phenolic groups. This binding differentiation might lead to a fractionation of REE-HA patterns when competition between REE and other metals occur during complexation. A survey of the available data shows that competition with Al 3+ could lead to the development of HREE-depleted HA patterns. This new model should improve the hydrochemical modeling of the REE since PHREEQC takes into account chemical reactions such as mineral dissolution/precipitation equilibrium and redox reactions, but also models kinetically controlled reactions and one-dimensional transport.

  13. Siderophile elements and metal-silicate fractionation in the solar nebula

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.

    1994-01-01

    The most important nebular fractionation affecting the siderophile elements is the metal-silicate fractionation process and its relationship to the chondrule formation process is poorly understood. Understanding these processes is important in terms of understanding the expected compositional range for planetary building blocks. In a general way the composition of chondrites can be derived from the composition of the CI chondrites by addition or subtraction of a refractory component similar to CAI's (in some cases with a Mg2SiO4 component) and by addition or subtraction of Fe metal. Thus normalization to Fe produces the least spread in the normalized abundances of most siderophile elements relative to CI abundances. Detailed bulk chemical studies of chondrules have shown that their siderophile elements have refractory-element siderophile-element signatures (for example, Ir/Ni) that are similar to the bulk meteorites, but distinct among the different chondrite groups. This data suggests that the chondrules were not supplied to the chondrule groups from a single homogeneous source, and that each chondrite group's characteristic siderophile-element signature was established before chondrule formation. These authors make a further inference that all siderophile-lithophile-element fractionation occurred before chondrule formation, but recent discoveries and observations suggest this is not true. The discovery of the metal-rich CH meteorites, the recognition of the role of aerodynamic forces in the solar nebula, and the possible role of metal-silicate segregation during the chondrule formation process suggests that metal-silicate fractionation occurred before, during and after chondrule formation.

  14. Rare earth and high field strength element partitioning between iron-rich clinopyroxenes and felsic liquids

    NASA Astrophysics Data System (ADS)

    Olin, P. H.; Wolff, J. A.

    2010-11-01

    Rare earth elements are commonly assumed to substitute only for Ca in clinopyroxene because of the similarity of ionic radii for REE3+ and Ca2+ in eightfold coordination. The assumption is valid for Mg-rich clinopyroxenes for which observed mineral/melt partition coefficients are readily predicted by the lattice strain model for substitution onto a single site (e.g., Wood and Blundy 1997). We show that natural Fe-rich pyroxenes in both silica-undersaturated and silica-oversaturated magmatic systems deviate from this behavior. Salites (Mg# 48-59) in phonolites from Tenerife, ferrohedenbergites (Mg# 14.2-16.2) from the rhyolitic Bandelier Tuff, and ferroaugites (Mg# 9.6-32) from the rhyolitic Rattlesnake Tuff have higher heavy REE contents than predicted by single-site substitution. The ionic radius of Fe2+ in sixfold coordination is substantially greater than that of Mg2+; hence, we propose that, in Fe-rich clinopyroxenes, heavy REE are significantly partitioned between eightfold Ca sites and sixfold Fe and Mg sites such that Yb and Lu exist dominantly in sixfold coordination. We also outline a REE-based method of identifying pyroxene/melt pairs in systems with multiple liquid and crystal populations, based upon the assumption that LREE and MREE reside exclusively in eightfold coordination in pyroxene. Contrary to expectations, interpolation of mineral/melt partition coefficient data for heavy REE does not predict the behavior of Y. We speculate that mass fractionation effects play a role in mineral/melt lithophile trace element partitioning that is detectable among pairs of isovalent elements with near-identical radii, such as Y and Ho, Zr and Hf, and Nb and Ta.

  15. Rare earth element recycling from waste nickel-metal hydride batteries.

    PubMed

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

    With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. PMID:25089667

  16. Lack of chemical fractionation in major and minor elements during agglutinate formation. [in lunar soil

    NASA Technical Reports Server (NTRS)

    Hu, H.-N.; Taylor, L. A.

    1977-01-01

    Rhodes et al. (1975, 1976) and Adams et al. (1975) have reported that the agglutinate fraction of the soils on the lunar surface displays a marked enrichment in Fe, Mg, Ti, K, and La, and a depletion in Ca, Na, Al, and Eu, relative to the bulk soils. The reported investigation is concerned with a testing of the theory of chemical fractionation involving magnetic separation which was developed in connection with these findings. Soils 64421 and 71501 were sieved and the magnetic fractions separated according to the method developed by Adams and McCord (1973). Analyses of agglutinitic glass did not indicate any appreciable chemical fractionation for the major and minor elements accompanying the agglutination process. It was found that most, if not all fractionations reported can be accounted for completely by the magnetic nonagglutinate impurities in the agglutinate fraction. It is, therefore, concluded that there appears to be no reason to make use of any chemical fractionation theory, whose validity remains to be demonstrated.

  17. The leaching behaviour and geochemical fractionation of trace elements in hydraulically disposed weathered coal fly ash.

    PubMed

    Nyale, Sammy M; Eze, Chuks P; Akinyeye, Richard O; Gitari, Wilson M; Akinyemi, Segun A; Fatoba, Olanrewaju O; Petrik, Leslie F

    2014-01-01

    A five-step sequential extraction (SE) procedure was used to investigate the leaching behaviour and geochemical partitioning of the trace elements As, Zn, Pb, Ni, Mo, Cr and Cu in a 20-year-old fly ash (FA) dump. The weathered FA, which was hydraulically co-disposed with salt laden brine in slurry form (FA: brine ratio of 1:5), was analyzed and compared with fresh FA. The weathered FA samples were collected from three cores, drilled at a coal-fired power station in the Republic of South Africa while the fresh FA sample was collected from the hoppers in the ash collection system at the power station. The FA samples were sequentially leached using: ultrapure water; ammonium acetate buffer solution (pH 7); ammonium acetate buffer solution (pH 5); hydroxylamine hydrochloride in nitric acid (pH 2) and finally the residues were digested using a combination of HClO4: HF: HNO3 acids. Digestion of as received (unleached) FA samples was also done using a combination of HClO4: HF: HNO3 acids in order to determine the total metal content. The trace element analysis was done using ICP-OES (Varian 710-ES). The SE procedure revealed that the trace elements present in the fresh FA and the weathered FA samples obtained from the three cores could leach upon exposure to different environmental conditions. The trace elements showed continuous partitioning between five geochemical phases i.e., water soluble fraction, exchangeable fraction, carbonate fraction, Fe and Mn fraction and residual fraction. Although the highest concentration of the trace elements (ranging 65.51%-86.34%) was contained in the residual fraction, a considerable amount of each trace element (ranging 4.42%-27.43%) was released from the labile phases (water soluble, exchangeable and carbonate fractions), indicating that the trace species readily leach from the dumped FA under environmental conditions thus pose a danger to the receiving environment and to groundwater. PMID:24171424

  18. Aquifer-specific Rare Earth Element patterns in groundwater of the Thuringian basin, Germany

    NASA Astrophysics Data System (ADS)

    Lonschinski, M.; Merten, D.; Büchel, G.

    2012-04-01

    The Thuringian basin is the major geological structural unit in the federal state of Thuringia, Germany. It consists of sandstones, limestones, clays, gypsum and salts, that were deposited from the Upper Permian until the Lower Jurassic (approximately 250 to 180 million years ago). The largest deposits are Buntsandstein, Muschelkalk and Keuper, all of Triassic age. Important aquifers are located in the Buntsandstein formations, which are cropping out widespread in the southeastern part and the northeastern part of the basin. These aquifers contain large resources of drinking water for the region. The hydrochemical properties of the groundwater with special emphasis on Rare Earth Elements (REE) are the main focus of this study. To investigate possible interactions between aquifers in the Buntsandstein with aquifers in adjoining formations, waters from Zechstein and Muschelkalk are considered, additionally. Since the REE in water in many case are originated from the minerals of the host rocks, REE fractionation pattern could provide information regarding the lithology of the solid aquifer material (Möller, 2002). Furthermore, interaction processes between solid and liquid phases or complexation in the water phase could be identified by REE fractionations (Ingri et al., 2000). Nevertheless, waters in circumneutral pH conditions could feature many different fractionation patterns (Johannesson & Zhou, 1997) making the interpretation difficult. Due to very low concentrations of REE in water at neutral pH condition, an enrichment procedure is necessary prior to REE determination by inductively coupled plasma mass spectroscopy (ICP-MS). The used method is based on the procedure of Shabani et al. (1990) and yields enrichment factors of about 500. REE fractionation patterns were determined for different water types such as Na-Cl type originating from Zechstein, Ca-Mg-HCO3-SO4 and Ca-SO4 from Buntsandstein or Ca-HCO3 from Muschelkalk aquifers. The patterns are specific for

  19. Experimental productivity rate optimization of rare earth element separation through preparative solid phase extraction chromatography.

    PubMed

    Knutson, Hans-Kristian; Max-Hansen, Mark; Jönsson, Christian; Borg, Niklas; Nilsson, Bernt

    2014-06-27

    Separating individual rare earth elements from a complex mixture with several elements is difficult and this is emphasized for the middle elements: Samarium, Europium and Gadolinium. In this study we have accomplished an overloaded one-step separation of these rare earth elements through preparative ion-exchange high-performance liquid chromatography with an bis (2-ethylhexyl) phosphoric acid impregnated column and nitric acid as eluent. An inductively coupled plasma mass spectrometry unit was used for post column element detection. The main focus was to optimize the productivity rate, subject to a yield requirement of 80% and a purity requirement of 99% for each element, by varying the flow rate and batch load size. The optimal productivity rate in this study was 1.32kgSamarium/(hmcolumn(3)), 0.38kgEuropium/(hmcolumn(3)) and 0.81kgGadolinium/(hmcolumn(3)). PMID:24835593

  20. Vanadium oxide bronzes containing rare-earth elements

    SciTech Connect

    Volkov, V.L.; Zubkov, V.G.; Fedyukov, A.S.; Zainulin, Yu.G.

    1988-05-01

    We attempted to make phases having the general formula Ln/sub x/V/sub 2/O/sub 5/ (Ln = La, Eu, Yb) without success; the specimens usually consisted of three phases: the rare-earth orthovanadate LnVO/sub 4/, vanadium(V) oxide, and VO/sub 2/. To shift the process to give Ln/sub x/V/sub 2/O/sub 5/, heat treatment was applied to mixtures of the initial high-purity substances. The x-ray patterns were recorded with a DRON-UM1 apparatus with Cr K..cap alpha.. radiation and were processed by the Poroshok program. The IR spectra were recorded with UR-20 spectrometer with oil mulls.

  1. Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

    USGS Publications Warehouse

    Verplanck, P.L.; Nordstrom, D.K.; Taylor, H.E.; Kimball, B.A.

    2004-01-01

    Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

  2. Mass-Independent Fractionation of Oxygen Isotope in Earth Wind: First Principle Calculations for Photodissociation

    NASA Astrophysics Data System (ADS)

    Yamada, A.; Nanbu, S.; Kasai, Y.; Ozima, M.

    2009-12-01

    Mass-independently fractionated oxygen isotope were reported on metal particles extracted from Apollo lunar soils [1, 2], but these origins are still unknown. Since the substantial fraction of Earth-escaping O+ flux (Earth Wind, EW hereafter), comparable to the amount of the anomalous oxygen implanted on the metal particles, could reach the lunar surface [3], Ozima et al. [4] suggested that EW may be responsible to the anomalous oxygen. The purpose is to test this EW hypothesiss, we study oxygen isotopic ratios of O+ at the upper atmosphere. From quantum chemical calculations of photo-dissociation of O2, we show the results in mass-independent isotopic fractionation of oxygen, thereby in conformity with the EW hypothesis. First principles reaction dynamics simulations were performed to compute the photolysis rate for the B3Σu- ← X3Σg- electronic transition, for Schumann-Runge band. With the assumption of the Born-Oppenheimer approximation, we performed the wave-packet dynamics for the nuclei-motion in the potential energy curves determined by the first step calculation. Quantum chemical program package [5] was used for the first step calculation, and the quantum dynamics was carried out by our own program package. Assuming the quantum yield of the corresponding photolysis is unity, the photo-absorption cross section can be correlated with the photolysis rate. Therefore, following the time dependent approach, the autocorrelation function (A(t) = <φ(0)|φ(t)>) was numerically computed by the second step calculation. Finally, the theoretical spectrum as a function of wavelength of excitation light was estimated by the Fourier transform of the autocorrelation function A(t) [6]. Calculated absorption cross sections for C16O showed similar wavelength dependence with experiment [7], although the absolute magnitude was yet to be calibrated for a quantitative comparison. Assuming Boltzmann distribution at 1200 K, we estimated enrichment factors defined as σι(λ)/σ16

  3. Enrichment of trace elements in the clay size fraction of mining soils.

    PubMed

    Gomes, Patrícia; Valente, Teresa; Braga, M Amália Sequeira; Grande, J A; de la Torre, M L

    2016-04-01

    Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps. PMID:25712883

  4. Experimental investigations of trace element fractionation in iron meteorites. III - Elemental partitioning in the system Fe-Ni-S-P

    NASA Technical Reports Server (NTRS)

    Malvin, D. J.; Jones, J. H.; Drake, M. J.

    1986-01-01

    Measurements of solid metal/liquid metal trace element partition coefficients, which are used to interpret the crystallization history of magmatic iron meteorite groups differ greatly between different research groups, using different experimental techniques. Specifically, partition coefficients measured utilizing 'static' experiments which approach equilibrium cannot be reconciled with the results of 'dynamic' experiments which mimic fractional crystallization. We report new tests of our 'static' experimental technique and demonstrate that our methodology yields reliable equilibrium values for Ni, P and Ge partition coefficients. Partition coefficients in the Fe-Ni-S-P system are well matched by interpolation between the Fe-Ni-S and Fe-Ni-P subsystems. In contrast, the predictions of 'dynamic' experiments do not agree with our measurements and, consequently, the ability of 'dynamic' experiments to reproduce iron meteorite Ge vs. Ni fractionation trends successfully must be regarded as fortuitous.

  5. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    NASA Astrophysics Data System (ADS)

    Chen, Heng; Savage, Paul S.; Teng, Fang-Zhen; Helz, Rosalind T.; Moynier, Frédéric

    2013-05-01

    The zinc stable isotope system has been successfully applied to many and varied fields in geochemistry, but to date it is still not completely clear how this isotope system is affected by igneous processes. In order to evaluate the potential application of Zn isotopes as a proxy for planetary differentiation and volatile history, it is important to constrain the magnitude of Zn isotopic fractionation induced by magmatic differentiation. In this study we present high-precision Zn isotope analyses of two sets of chemically diverse, cogenetic samples from Kilauea Iki lava lake, Hawaii, and Hekla volcano, Iceland, which both show clear evidence of having undergone variable and significant degrees of magmatic differentiation. The Kilauea Iki samples display small but resolvable variations in Zn isotope composition (0.26‰<δ66Zn<0.36‰; δ66Zn defined as the per mille deviation of a sample's 66Zn/64Zn compositional ratio from the JMC-Lyon standard), with the most differentiated lithologies exhibiting more positive δ66Zn values. This fractionation is likely a result of the crystallization of olivine and/or Fe-Ti oxides, which can both host Zn in their crystal structures. Samples from Hekla have a similar range of isotopic variation (0.22‰<δ66Zn<0.33‰), however, the degree of fractionation caused by magmatic differentiation is less significant (only 0.07‰) and no correlation between isotope composition and degree of differentiation is seen. We conclude that high temperature magmatic differentiation can cause Zn isotope fractionation that is resolvable at current levels of precision, but only in compositionally-evolved lithologies. With regards to primitive (ultramafic and basaltic) material, this signifies that the terrestrial mantle is essentially homogeneous with respect to Zn isotopes. Utilizing basaltic and ultramafic sample analyses, from different geologic settings, we estimate that the average Zn isotopic composition of Bulk Silicate Earth is δ66Zn=0.28

  6. [Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

    PubMed

    Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

    2015-11-01

    In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha. PMID:26978935

  7. Trends in the Rare Earth Element Content of U.S.-Based Coal Combustion Fly Ashes.

    PubMed

    Taggart, Ross K; Hower, James C; Dwyer, Gary S; Hsu-Kim, Heileen

    2016-06-01

    Rare earth elements (REEs) are critical and strategic materials in the defense, energy, electronics, and automotive industries. The reclamation of REEs from coal combustion fly ash has been proposed as a way to supplement REE mining. However, the typical REE contents in coal fly ash, particularly in the United States, have not been comprehensively documented or compared among the major types of coal feedstocks that determine fly ash composition. The objective of this study was to characterize a broad selection of U.S. fly ashes of varied geological origin in order to rank their potential for REE recovery. The total and nitric acid-extractable REE content for more than 100 ash samples were correlated with characteristics such as the major element content and coal basin to elucidate trends in REE enrichment. Average total REE content (defined as the sum of the lanthanides, yttrium, and scandium) for ashes derived from Appalachian sources was 591 mg kg(-1) and significantly greater than in ashes from Illinois and Powder River basin coals (403 and 337 mg kg(-1), respectively). The fraction of critical REEs (Nd, Eu, Tb, Dy, Y, and Er) in the fly ashes was 34-38% of the total and considerably higher than in conventional ores (typically less than 15%). Powder River Basin ashes had the highest extractable REE content, with 70% of the total REE recovered by heated nitric acid digestion. This is likely due to the higher calcium content of Powder River Basin ashes, which enhances their solubility in nitric acid. Sc, Nd, and Dy were the major contributors to the total REE value in fly ash, based on their contents and recent market prices. Overall, this study shows that coal fly ash production could provide a substantial domestic supply of REEs, but the feasibility of recovery depends on the development of extraction technologies that could be tailored to the major mineral content and origins of the feed coal for the ash. PMID:27228215

  8. Research of the entry of rare earth elements Eu3+ and La3+ into plant cell.

    PubMed

    Gao, Yongsheng; Zeng, Fuli; Yi, An; Ping, Shi; Jing, Lanhua

    2003-03-01

    Whether rare earth elements can enter into plant cells remains controversial. This article discusses the ultracellular structural localization of lanthanum (La(3+)) and europium (Eu(3+)) in the intact plant cells fed by rare earth elements Eu(3+) and La(3+). Eu-TTA fluorescence analysis of the plasmalemma, cytoplast, and mitochondria showed that Eu(3+) fluorescence intensities in such structures significantly increased. Eu(3+) can directly enter or be carried by the artificial ion carrier A23187 into plant cells through the calcium ion (Ca(2+)) channel and then partially resume the synthesis of amaranthin in the Amaranthus caudatus growing in the dark. Locations of rare earth elements La(3+) and Eu(3+) in all kinds of components of cytoplasmatic organelles were determined with transmission electron microscope, scanning electron microscope, and energy-dispersive X-ray microanalysis. The results of energy-dispersive X-ray microanalysis indicated that Eu(3+) and La(3+) can be absorbed into plant cells and bind to the membranes of protoplasm, chloroplast, mitochondrion, cytoplast, and karyon. These results provide experimental evidence that rare earth elements can be absorbed into plant cells, which would be the basis for interpreting physiological and biochemical effects of rare earth elements on plant cells. PMID:12663949

  9. Molecular Polyarsenides of the Rare-Earth Elements.

    PubMed

    Arleth, Nicholas; Gamer, Michael T; Köppe, Ralf; Konchenko, Sergey N; Fleischmann, Martin; Scheer, Manfred; Roesky, Peter W

    2016-01-22

    Reduction of [Cp*Fe(η(5)-As5)] with [Cp''2Sm(thf)] (Cp''=η(5)-1,3-(tBu)2C5H3) under various conditions led to [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] and [(Cp''2Sm)2As7(Cp*Fe)]. Both compounds are the first polyarsenides of the rare-earth metals. [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] is also the first d/f-triple decker sandwich complex with a purely inorganic planar middle deck. The central As4(2-) unit is isolobal with the 6π-aromatic cyclobutadiene dianion (CH)4(2-). [(Cp''2Sm)2As7(Cp*Fe)] contains an As7(3-) cage, which has a norbornadiene-like structure with two short As-As bonds in the scaffold. DFT calculations confirm all the structural observations. The As-As bond order inside the cyclo As4 ligand in [(Cp''2Sm)(μ,η(4):η(4)-As4)(Cp*Fe)] was estimated to be in between an As-As single bond and a formally aromatic As4(2-) system. PMID:26676537

  10. Chemical fractionation of siderophile elements in impactites from Australian meteorite craters

    NASA Technical Reports Server (NTRS)

    Attrep, A., Jr.; Orth, C. J.; Quintana, L. R.; Shoemaker, C. S.; Shoemaker, E. M.; Taylor, S. R.

    1991-01-01

    The abundance pattern of siderophile elements in terrestrial and lunar impact melt rocks was used extensively to infer the nature of the impacting projectiles. An implicit assumption made is that the siderophile abundance ratios of the projectiles are approximately preserved during mixing of the projectile constituents with the impact melts. As this mixture occurs during flow of strongly shocked materials at high temperatures, however there are grounds for suspecting that the underlying assumption is not always valid. In particular, fractionation of the melted and partly vaporized material of the projectile might be expected because of differences in volatility, solubility in silicate melts, and other characteristics of the constituent elements. Impactites from craters with associated meteorites offer special opportunities to test the assumptions on which projectile identifications are based and to study chemical fractionation that occurred during the impact process.

  11. Finite element method combined with second-order time discrete scheme for nonlinear fractional Cable equation

    NASA Astrophysics Data System (ADS)

    Wang, Yajun; Liu, Yang; Li, Hong; Wang, Jinfeng

    2016-03-01

    In this article, a Galerkin finite element method combined with second-order time discrete scheme for finding the numerical solution of nonlinear time fractional Cable equation is studied and discussed. At time t_{k-α/2} , a second-order two step scheme with α -parameter is proposed to approximate the first-order derivative, and a weighted discrete scheme covering second-order approximation is used to approximate the Riemann-Liouville fractional derivative, where the approximate order is higher than the obtained results by the L1-approximation with order (2-α in the existing references. For the spatial direction, Galerkin finite element approximation is presented. The stability of scheme and the rate of convergence in L^2 -norm with O(Δ t^2+(1+Δ t^{-α})h^{m+1}) are derived in detail. Moreover, some numerical tests are shown to support our theoretical results.

  12. U.S. trade dispute with China over rare earth elements

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2012-03-01

    The U.S. government has brought a new trade case against China over rare earth elements (REE) as well as tungsten and molybdenum, President Barack Obama announced on 13 March. Japan and the European Union also have taken similar actions against China about REEs, which are a group of 17 chemically similar metallic elements that are used in a variety of electronic, optical, magnetic, and catalytic applications. REEs are plentiful in the Earth's crust, although China currently has about 37% of the world's reserves and accounts for more than 95% of the world's production of the elements, according to the British Geological Survey. The United States has requested consultations with China at the World Trade Organization (WTO) concerning "China's unfair export restraints on rare earths, as well as tungsten and molybdenum," the Office of the United States Trade Representative announced in a 13 March statement.

  13. Alkali element depletion by core formation and vaporization on the early Earth

    NASA Technical Reports Server (NTRS)

    Lodders, K.; Fegley, B., Jr.

    1994-01-01

    The depletion of Na, K, Rb, and Cs in the Earth's upper mantle and crust relative to their abundances in chondrites is a long standing problem in geochemistry. Here we consider two commonly invoked mechanisms, namely core formation, and vaporization, for producing the observed depletions. Our models predict that a significant percentage of the Earth's bulk alkali element inventory is in the core (30 percent for Na, 52 percent for K, 74 percent for Rb, and 92 percent for Cs). These predictions agree with independent estimates from nebular volatility trends and (for K) from terrestrial heat flow data. Our models also predict that vaporization and thermal escape during planetary accretion are unlikely to produce the observed alkali element depletion pattern. However, loss during the putative giant impact which formed the Moon cannot be ruled out. Experimental, observational, and theoretical tests of our predictions are also described. Alkali element partitioning into the Earth's core was modeled by assuming that alkali element partitioning during core formation on the aubrite parent body (APB) is analogous to that on the early Earth. The analogy is reasonable for three reasons. First, the enstatite meteorites are the only known meteorites with the same oxygen isotope systematics as the Earth-Moon system. Second, the large core size of the Earth and the V depletion in the mantle requires accretion from planetesimals as reduced as the enstatite chondrites. Third, experimental studies of K partitioning between silicate and metal plus sulfide show that more K goes into the metal plus sulfide at higher pressures than at one atmosphere pressure. Thus partitioning in the relatively low pressure natural laboratory of the APB is a good guide to alkali elemental partitioning during the growth of the Earth.

  14. The estuarine geochemistry of rare earth elements and indium in the Chao Phraya River, Thailand

    NASA Astrophysics Data System (ADS)

    Nozaki, Yoshiyuki; Lerche, Dorte; Alibo, Dia Sotto; Snidvongs, Anond

    2000-12-01

    A new filtration method using a 0.04 μm hollow fiber filter was applied to the river, estuarine, and coastal waters in the Chao Phraya estuary for geochemical investigation. The filtered waters were analyzed for all the lanthanides, Y and In by using inductively coupled plasma mass spectrometry (ICPMS). The dissolved concentrations of rare earth elements (REEs) are significantly lower than those reported previously for other rivers, presumably because of effective removal of river colloids by the ultra-filtration. The variation of dissolved REEs in the estuary is dependent on the season. The light REEs vary considerably in the low salinity ( S < 3) zone presumably due to adsorption-desorption interaction with suspended particles. In January when the river discharge is low, the REEs show maxima in the mid salinity ( S = 5-12) zone suggesting that dissolved REEs are supplied to the waters by either desorption from suspended loads or remineralization of underlying sediments. The rapid removal of the REEs is also taking place in the turbid-clear water transition zone ( S = 12-15), presumably due to biological uptake associated with blooming of Noctilca occurred at the time of January sampling. In the medium to high discharge season (July and November), the dissolved REE(III)s at S > 3 show almost conservative trends being consistent with some of the previous works. Europium is strongly enriched in the river and estuarine waters compared to the South China Sea waters. Thus, the REE source of the Chao Phraya River must be fractionated and modified in entering to the South China Sea. Dissolved In and Ce in the high salinity ( S = 20-25) zone of the estuary are lower than those of the offshore waters, and therefore, the dissolved flux of the Chao Phraya River cannot account for the higher concentrations of dissolved In and Ce in the surface waters of the South China Sea. The negative Ce anomaly is progressively developed with increasing salinity, being consistent with

  15. Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

    NASA Astrophysics Data System (ADS)

    Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

    2014-09-01

    Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

  16. Addressing Rare-Earth Element Criticality: An Example from the Aviation Industry

    NASA Astrophysics Data System (ADS)

    Ku, Anthony Y.; Dosch, Christopher; Grossman, Theodore R.; Herzog, Joseph L.; Maricocchi, Antonio F.; Polli, Drew; Lipkin, Don M.

    2014-11-01

    Rare-earth (RE) elements are enablers for a wide range of technologies, including high-strength permanent magnets, energy-efficient lighting, high-temperature thermal barrier coatings, and catalysts. While direct material substitution is difficult in many of these applications because of the specific electronic, optical, or electrochemical properties imparted by the individual rare-earth elements, we describe an example from the aviation industry where supply chain optimization may be an option. Ceramic matrix composite engine components require environmental barrier coatings (EBCs) to protect them from extreme temperatures and adverse reactions with water vapor in the hot gas path. EBC systems based on rare-earth silicates offer a unique combination of environmental resistance, thermal expansion matching, thermal conductivity, and thermal stability across the service temperature window. Several pure rare-earth silicates and solid solutions have been demonstrated in EBC applications. However, all rely on heavy rare-earth elements (HREEs) for phase stability. This article considers the possibility of using separation tailings containing a mixture of HREEs as a source material in lieu of using the high-purity HREE oxides. This option arises because the desired properties of RE-silicate EBCs derive from the average cation size rather than the electronic properties of the individual rare-earth cations. Because separation tailings have not incurred the costs associated with the final stages of separation, they offer an economical alternative to high-purity oxides for this emerging application.

  17. Precious metals and rare earth elements in municipal solid waste--sources and fate in a Swiss incineration plant.

    PubMed

    Morf, Leo S; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Di Lorenzo, Fabian; Böni, Daniel

    2013-03-01

    In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process. PMID:23085306

  18. Concentrations of Elements in Sediments and Selective Fractions of Sediments, and in Natural Waters in Contact with Sediments from Lake Roosevelt, Washington, September 2004

    USGS Publications Warehouse

    Paulson, Anthony J.; Wagner, Richard J.; Sanzolone, Richard F.; Cox, Steven E.

    2006-01-01

    Twenty-eight composite and replicate sediment samples from 8 Lake Roosevelt sites were collected and analyzed for 10 alkali and alkaline earth elements, 2 non-metals, 20 metals, and 4 lanthanide and actinide elements. All elements were detected in all sediment samples except for silver (95 percent of the elements detected for 1,008 analyses), which was detected only in 4 samples. Sequential selective extraction procedures were performed on single composite samples from the eight sites. The percentage of detections for the 31 elements analyzed ranged from 76 percent for the first extraction fraction using a weak extractant to 93 percent for the four-acid dissolution of the sediments remaining after the third sequential selective extraction. Water samples in various degrees of contact with the sediment were analyzed for 10 alkali and alkaline earth elements, 5 non-metals, 25 metals, and 16 lanthanide and actinide elements. The filtered water samples included 10 samples from the reservoir water column at 8 sites, 32 samples of porewater, 55 samples from reservoir water overlying sediments in 8 cores from the site incubated in a field laboratory, and 24 water samples that were filtered after being tumbled with sediments from 8 sites. Overall, the concentrations of only 37 percent of the 6,776 analyses of the 121 water samples were greater than the reporting limit. Selenium, bismuth, chromium, niobium, silver, and zirconium were not detected in any water samples. The percentage of concentrations for the water samples that were above the reporting limit ranged from 14 percent for the lanthanide and actinide elements to 77 percent for the alkali and alkaline earth elements. Concentrations were greater than reporting limits in only 23 percent of the analyses of reservoir water and 29 percent of the analyses of reservoir water overlying incubation cores. In contrast, 47 and 48 percent of the concentrations of porewater and water samples tumbled with sediments, respectively

  19. Fractionation of highly siderophile and chalcogen elements in components of EH3 chondrites

    NASA Astrophysics Data System (ADS)

    Kadlag, Yogita; Becker, Harry

    2015-07-01

    Abundances of highly siderophile elements (HSE: Re, platinum group elements and Au), chalcogens (Te, Se and S), 187Os/188Os and the major and minor elements Mg, Ca, Mn, Fe, Ni and Co were determined in the components of Sahara 97072 (EH3, find) and Kota Kota (EH3, find) in order to understand the element fractionation processes. In a 187Re-187Os isochron diagram, most magnetic components lie close to the 4.56 Ga IIIA iron meteorite isochron, whereas most other components show deviations from the isochron caused by late redistribution of Re, presumably during terrestrial weathering. Metal- and sulfide rich magnetic fractions and metal-sulfide nodules are responsible for the higher 187Os/188Os in bulk rocks of EH chondrites compared to CI chondrites. The HSE and chalcogens are enriched in magnetic fractions relative to slightly magnetic and nonmagnetic fractions and bulk compositions, indicating that Fe-Ni metal is the main host phase of the HSE in enstatite chondrites. HSE abundance patterns indicate mixing of two components, a CI chondrite like end member and an Au-enriched end member. Because of the decoupled variations of Au from those of Pd or the chalcogens, the enrichment of Au in EH metal cannot be due to metal-sulfide-silicate partitioning processes. Metal and sulfide rich nodules may have formed by melting and reaction of pre-existing refractory element rich material with volatile rich gas. A complex condensation and evaporation history is required to account for the depletion of elements having very different volatility than Au in EH chondrites. The depletions of Te relative to HSE, Se and S in bulk EH chondrites are mainly caused by the depletion of Te in metal. S/Se and S/Mn are lower than in CI chondrites in almost all components and predominantly reflect volatility-controlled loss of sulfur. The latter most likely occurred during thermal processing of dust in the solar nebula (e.g., during chondrule formation), followed by the non-systematic loss of S

  20. Elemental and spectroscopic characterization of fractions of an acidic extract of oil sands process water.

    PubMed

    Jones, D; Scarlett, A G; West, C E; Frank, R A; Gieleciak, R; Hager, D; Pureveen, J; Tegelaar, E; Rowland, S J

    2013-11-01

    'Naphthenic acids' (NAs) in petroleum produced water and oil sands process water (OSPW), have been implicated in toxicological effects. However, many are not well characterized. A method for fractionation of NAs of an OSPW was used herein and a multi-method characterization of the fractions conducted. The unfractionated OSPW acidic extract was characterized by elemental analysis, electrospray ionization-Orbitrap-mass spectrometry (ESI-MS), and an esterified extract by Fourier Transform infrared (FTIR) and ultraviolet-visible (UV) absorption spectroscopy and by comprehensive multidimensional gas chromatography-MS (GCxGC-MS). Methyl esters were fractionated by argentation solid phase extraction (Ag(+) SPE) and fractions eluting with: hexane; diethyl ether: hexane and diethyl ether, examined. Each was weighed, examined by elemental analysis, FTIR, UV, GC-MS and GCxGC-MS (both nominal and high resolution MS). The ether fraction, containing sulfur, was also examined by GCxGC-sulfur chemiluminescence detection (GCxGC-SCD). The major ions detected by ESI-MS in the OSPW extract were assigned to alicyclic and aromatic 'O2' acids; sulfur was also present. Components recovered by Ag(+) SPE were also methyl esters of alicyclic and aromatic acids; these contained little sulfur or nitrogen. FTIR spectra showed that hydroxy acids and sulfoxides were absent or minor. UV spectra, along with the C/H ratio, further confirmed the aromaticity of the hexane:ether eluate. The more minor ether eluate contained further aromatics and 1.5% sulfur. FTIR spectra indicated free carboxylic acids, in addition to esters. Four major sulfur compounds were detected by GCxGC-SCD. GCxGC-high resolution MS indicated these were methyl esters of C18 S-containing, diaromatics with ≥C3 carboxylic acid side chains. PMID:23856466

  1. Chemical Weathering of Black Shales and Rare Earth Element Composition of Surface Waters and Groundwater

    NASA Astrophysics Data System (ADS)

    Hannigan, R. E.; Johannesson, K. H.

    2001-05-01

    Weathering processes dominate the dissolved and suspended loads of most of the world's major rivers. Among sedimentary rocks, black shales are particularly sensitive to chemical weathering. Therefore, shale systems are useful for investigating the partitioning of chemical elements during chemical weathering. Recent studies, such as those by Peucker-Ehrenbrink, Ravizza and others, link chemical weathering of black shales to changes in marine isotopic composition. Rare earth elements (REE) have a unique chemistry and are ideal for such tracer studies. We explored the effect of modern chemical weathering of black shales on the hydrochemistry of surface and groundwaters in the Mohawk Valley of New York State. This region provides an ideal site for the investigation of trace element remobilization during the chemical weathering of black shales. In this region, surface and groundwaters, in intimate contact with black shales and have high dissolved metal concentrations presumably due to water-rock interactions. The extent to which the dissolved REE composition of the surface and ground waters retains the rock signature is, in someway related to the length of time that the water remains in contact with the rock. We compared the REE compositions of surface and groundwaters in areas draining black shale to those of waters draining regions of dolostone-limestone to explore the extent of metal release due to chemical weathering. Shale normalized REE patterns for stream waters exhibit slight heavy REE enrichments and, at some locations, LREE depletion. REE patterns of the waters normalized to their respective sediments show some LREE depletion. However, waters associated with the Little Falls dolomite show fractionation predominantly enriched in the heavy REEs. Differences between the black shale sites, recorded as light REE depletion and/or middle REE enrichment, may be related to the discharge of the streams and the total dissolved solids. The dissolved REE chemistry of

  2. Elemental fractionation in 785 nm picosecond and femtosecond laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shaheen, M. E.; Gagnon, J. E.; Fryer, B. J.

    2015-05-01

    Elemental fractionation and ICP-MS signal response were investigated for two different pulse width laser beams originating from the same laser system. Femtosecond and picosecond laser beams at pulse widths of 130 fs and 110 ps, respectively, and wavelength of 785 nm were used to ablate NIST 610 synthetic glass and SRM 1107 Naval Brass B at the same spot for 800 to 1000 laser pulses at different repetition rates (5 to 50 Hz). Elemental fractionation was found to depend on repetition rate and showed a trend with femtosecond laser ablation that is opposite to that observed in picosecond laser ablation for most measured isotopes. ICP-MS signal intensity was higher in femtosecond than picosecond LA-ICP-MS in both NIST 610 and naval brass when ablation was conducted under the same fluence and repetition rate. The differences in signal intensity were partly related to differences in particle size distribution between particles generated by femtosecond and picosecond laser pulses and the consequent differences in transport and ionization efficiencies. The main reason for the higher signal intensity resulting from femtosecond laser pulses was related to the larger crater sizes compared to those created during picosecond laser ablation. Elemental ratios measured using 66Zn/63Cu, 208Pb/238U, 232Th/238U, 66Zn/232Th and 66Zn/208Pb were found to change with the number of laser pulses with data points being more scattered in picosecond than femtosecond laser pulses. Reproducibility of replicate measurements of signal intensities, fractionation and elemental ratios was better for fs-LA-ICP-MS (RSD ~ 3 to 6%) than ps-LA-ICP-MS (RSD ~ 7 to 11%).

  3. Statistical Constraints from Siderophile Elements on Earth's Accretion, Differentiation, and Initial Core Stratification

    NASA Astrophysics Data System (ADS)

    O'Rourke, J. G.; Stevenson, D. J.

    2015-12-01

    Abundances of siderophile elements in the primitive mantle constrain the conditions of Earth's core/mantle differentiation. Core growth occurred as Earth accreted from collisions between planetesimals and larger embryos of unknown original provenance, so geochemistry is directly related to the overall dynamics of Solar System formation. Recent studies claim that only certain conditions of equilibration (pressure, temperature, and oxygen fugacity) during core formation can reproduce the available data. Typical analyses, however, only consider the effects of varying a few out of tens of free parameters in continuous core formation models. Here we describe the Markov chain Monte Carlo method, which simultaneously incorporates the large uncertainties on Earth's composition and the parameterizations that describe elemental partitioning between metal and silicate. This Bayesian technique is vastly more computationally efficient than a simple grid search and is well suited to models of planetary accretion that involve a plethora of variables. In contrast to previous work, we find that analyses of siderophile elements alone cannot yield a unique scenario for Earth's accretion. Our models predict a wide range of possible light element contents for the core, encompassing all combinations permitted by seismology and mineral physics. Specifically, we are agnostic between silicon and oxygen as the dominant light element, and the addition of carbon or sulfur is also permissible but not well constrained. Redox conditions may have remained roughly constant during Earth's accretion or relatively oxygen-rich material could have been incorporated before reduced embryos. Pressures and temperatures of equilibration, likewise, may only increase slowly throughout accretion. Therefore, we do not necessarily expect a thick (>500 km), compositionally stratified layer that is stable against convection to develop at the top of the core of Earth (or, by analogy, Venus). A thinner stable layer

  4. Authigenic phase formation and microbial activity control Zr, Hf, and rare earth element distributions in deep-sea brine sediments

    NASA Astrophysics Data System (ADS)

    Censi, P.; Saiano, F.; Zuddas, P.; Nicosia, A.; Mazzola, S.; Raso, M.

    2014-02-01

    Sediments collected from hypersaline and anoxic deep-sea basins in the eastern Mediterranean (Thetis, Kryos, Medee, and Tyro) were characterised in terms of their mineralogical composition, the distributions of rare earth elements (REE), Zr, and Hf and their content of microbial DNA. We identified two major mineralogical fractions: one fraction of detritic origin was composed of quartz, gypsum, and low-Mg calcite bioclasts (with 0 < Mg < 0.07%) and another fraction of authigenic origin constituted of halite, dolomite, high-Mg calcite (with a Mg content of up to 22%) and rare bischofite and showed a textural evidence of microbial assemblages. We found that in the Medee and Tyro sediments, the shale-normalised REE pattern of these sediments is strongly enriched in middle REE (MREE), whereas in the Thetis and Tyro basins, a positive Gd anomaly in the residue was obtained after the removal of the water-soluble fraction. In all investigated basins, Y / Ho ratio clustered around chondritic values, whereas Zr / Hf ratio ranged from slightly subchondritic to superchondritic values. Subchondritic Y / Ho and Zr / Hf values were mainly found in the high-Mg carbonate having a microbial origin. The observed preferential removal of Zr with respect to Hf without significant partitioning of Y with respect to Ho indicates that the Zr / Hf ratio and Y-Ho fractionations are influenced by the microbial activity in the sediments. We propose that the concurrent Y-Ho and Zr-Hf fractionations are a suitable tracer of microbial activity in marine sediments.

  5. Rare earth element content of thermal fluids from Surprise Valley, California

    DOE Data Explorer

    Andrew Fowler

    2015-09-23

    Rare earth element measurements for thermal fluids from Surprise Valley, California. Samples were collected in acid washed HDPE bottles and acidified with concentrated trace element clean (Fisher Scientific) nitric acid. Samples were pre-concentratated by a factor of approximately 10 using chelating resin with and IDA functional group and measured on magnetic sector ICP-MS. Samples include Seyferth Hot Springs, Surprise Valley Resort Mineral Well, Leonard's Hot Spring, and Lake City Mud Volcano Boiling Spring.

  6. Potential toxic element fractionation and phytoavailability assessment in technosoils from former smelting and mining areas

    NASA Astrophysics Data System (ADS)

    Qasim, Bashar; Motelica-Heino, Mikael

    2014-05-01

    High metal and metalloid concentrations in soils have negative effects on terrestrial ecosystems and generate potential health risk. Mining and smelting activities are the major source of metal contamination by release a huge amounts of these potentially toxic elements (PTE) into the environment. Since the determination of the total concentration of PTE in soils does not give sufficient information about their mobility and toxicity, additional information on their bioavailability and their chemical speciation is required. Our study aimed at reporting the chemical fractionation and phytoavailability assessment of several PTE (Zn, Pb, Cd, As and Sb) in contaminated technosoils of two former smelting and mining areas. Soil samples were taken from a metallophyte grassland contaminated with Zn, Pb and Cd located at Mortagne - du -Nord (MDN) (North France) and from a former mining settling basin contaminated with As, Pb and Sb located at la Petite Faye (LPF) (Limoges district, France). Two sequential extraction schemes were used to evaluate the PTE speciation in various technosoils as operationally defined fractions. The extraction schemes used in this study were the Tessier's scheme and a modified BCR scheme. The fractions were rearranged into four equivalent fractions defined as acid soluble, reducible, oxidisable and residual fraction. To assess the metals and metalloids phytoavailability a series of selective single extraction procedures (CaCl2, NaNO3, NH4NO3, DTPA and EDTA) were used together with short-term germination tests with dwarf beans whose primary leaves were analyzed for their PTE concentration after 21 days of sowing under controlled conditions (16h light/8h darkness regime, 25°C/21°C, relative humidity of 55 - 65% and photon flux of 150 μE m-2s-1). Our results indicates that Zn, Cd and Pb were mainly associated with the acid soluble and reducible fractions for the MDN site, while As, Sb and Pb were mostly associated with residual fraction for the LPF

  7. Sulfur isotope fractionation during the reduction of elemental sulfur and thiosulfate by Dethiosulfovibrio spp.

    NASA Astrophysics Data System (ADS)

    Surkov, A. V.; Böttcher, M. E.; Kuever, J.

    2009-04-01

    Thiosulfate and elemental sulfur are typical by-products of the oxidation of dissolved sulfide and important sulfur intermediates in the biogeochemical sulfur cycle of natural sediments where they can be further transformed by microbial or chemical oxidation, reduction, or disproportionation. Due to the often superimposing reaction pathways of the sulfur intermediates in natural environments specific tracers are needed to better resolve the complex microbial and biogeochemical reactions. An important fingerprint for sulfur cycling is provided by the microbial fractionation of the stable sulfur isotopes S-34 and S-32. Proper interpretation of isotope signals in nature, however, is only possible by the calibration with results obtained with pure cultures under defined experimental conditions. In addition, sulfur isotope discrimination may provide informations about specific encymatic biochemical pathways within the bacterial cells. In this study, we report the results for the discrimination of stable sulfur isotopes S-32 and S-34 during reduction of thiosulfate and elemental sulfur by non-sulfate, but sulfur- and thiosulfate-reducing bacteria which are phylogenetically not related to sulfate-reducing bacteria. Experiments with were conducted at known cell-specific thiosulfate reduction rates. Stable sulfur isotope fractionation was investigated during reduction of thiosulfate and elemental sulfur at 28°C by growing batch cultures of Dethiosulfovibrio marinus WS100 (type strain DSM 12537) and Dethiosulfovibrio russensis (type strain DSM 12538) using citrate as carbon and energy source. The cell-specific reduction rates were 0.3 to 2.4 fmol cell-1 d-1 (thiosulfate) and 31 to 38 fmol cell-1 d-1 (elemental sulphur), respectively. The sulfide produced was depleted in S-34 by 12 per mil compared to total thiosulfate sulfur, close to previous results observed for sulfate-reducing bacteria, indicating that the thiosulfate-reducing mechanism of sulfate reducers is similar to

  8. Radioluminescence and thermoluminescence of rare earth element and phosphorus-doped zircon

    SciTech Connect

    Karali, T.; Can, N.; Townsend, P.D.; Rowlands, A.P.; Hanchar, J.M.

    2000-06-01

    The radioluminescence and thermoluminescence spectra of synthetic zircon crystals doped with individual trivalent rare earth element (REE) ions (Pr, Sm, Eu, Gd, Dy, Ho, Er, and Yb) and P are reported in the temperature range 25 to 673 K. Although there is some intrinsic UV/blue emission from the host lattice, the dominant signals are from the rare-earth sites, with signals characteristic of the REE{sup 3+} states. The shapes of the glow curves are different for each dopant, and there are distinct differences between glow peak temperatures for different rare-earth lines of the same element. Within the overall set of signals there are indications of linear trends in which some glow peak temperatures vary as a function of the ionic size of the rare earth ions. The temperature shifts of the peaks are considerable, up to 200{degree}, and much larger than those cited in other rare-earth-doped crystals of LaF{sub 3} and Bi{sub 4}Ge{sub 3}O{sub 12}. The data clearly suggest that the rare-earth ions are active both in the trapping and luminescence steps, and hence the TL occurs within localized defect complexes that include REE{sup 3+} ions.

  9. Factors affecting the rare earth element compositions in massive sulfides from deep-sea hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Zeng, Zhigang; Ma, Yao; Yin, Xuebo; Selby, David; Kong, Fancui; Chen, Shuai

    2015-09-01

    To reconstruct the evolution of ore-forming fluids and determine the physicochemical conditions of deposition associated with seafloor massive sulfides, we must better understand the sources of rare earth elements (REEs), the factors that affect the REE abundance in the sulfides, and the REE flux from hydrothermal fluids to the sulfides. Here we examine the REE profiles of 46 massive sulfide samples collected from seven seafloor hydrothermal systems. These profiles feature variable total REE concentrations (37.2-4092 ppb) and REE distribution patterns (LaCN/LuCN ratios = 2.00-73.8; (Eu/Eu*)CN ratios = 0.34-7.60). The majority of the REE distribution patterns in the sulfides are similar to those of vent fluids, with the sulfides also exhibiting light REE enrichment. We demonstrate that the variable REE concentrations, Eu anomalies, and fractionation between light REEs and heavy REEs in the sulfides exhibit a relationship with the REE properties of the sulfide-forming fluids and the massive sulfide chemistry. Based on the sulfide REE data, we estimate that modern seafloor sulfide deposits contain approximately 280 t of REEs. According to the flux of hydrothermal fluids at mid-ocean ridges (MORs) and an average REE concentration of 3 ng/g in these fluids, hydrothermal vents at MORs alone transport more REEs (>360 t) to the oceans over the course of just 2 years than the total quantity of REEs in seafloor sulfides. The excess REEs (i.e., the quantity not captured by massive sulfides) may be transported away from the systems and become bound in sulfate deposits and metalliferous sediments.

  10. The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

    NASA Technical Reports Server (NTRS)

    DeWitt, H. Langley; Hasenkopf, Christa A.; Trainer, Melissa G.; Farmer, Delphine K.; Jimenez, Jose L.; McKay, Christopher P.; Toon, Owen B.; Tolbert, Margaret A.

    2010-01-01

    The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

  11. Evolution of the lithosphere beneath Oahu, Hawaii: rare earth element abundances in mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Sen, Gautam; Frey, Frederick A.; Shimizu, Nobumichi; Leeman, William P.

    1993-08-01

    Rare earth element contents of clinopyroxenes in Hawaiian mantle xenoliths from Oahu were determined with an ion microprobe. The analyzed xenoliths are from four vents of the alkali Honolulu Volcanics (HV). Three (Kaau, Pali and Kalihi—KPK) are located close to the caldera of the extinct Koolau shield volcano, and the fourth, Salt Lake Crater (SLC), is on the periphery of the shield volcano. Systematic differences exist in REE contents between clinopyroxenes of the KPK and SLC xenoliths: (1) KPK pyroxenes are typically zoned in REE contents whereas SLC pyroxenes are homogeneous, (2) the LREE-depleted (chondrite-normalized) patterns that characterize many of the KPK xenoliths are not found in SLC xenoliths, and (3) the convex-upward REE patterns that are characteristic of SLC xenoliths are not found in KPK xenoliths. Relative to abyssal peridotites, the LREE-depleted Hawaiian lherzolite pyroxenes (interpreted to be residual oceanic lithosphere) have higher contents of REE, Na 2O, TiO 2 and FeO, and more modal clinopyroxene. These LREE-depleted Hawaiian xenoliths represent deeper, less-depleted parts of the melting column, whereas the abyssal peridotites represent the uppermost, more strongly depleted part of the mantle. The spoon-shaped, LREE-enriched and convex-upward REE patterns in the xenoliths have resulted from metasomatic enrichment of the lithosphere caused by reaction with magmas that formed the Honolulu Volcanics. A model for the evolution of the oceanic lithosphere is presented in which fractures were the main mode of transport of the Honolulu Volcanics. Metasomatic enrichment resulted from interaction between percolating Honolulu Volcanics magmas and wallrock. The differences between SLC and KPK xenoliths are attributed to chromatographic fractionation effects: SLC xenoliths are postulated to have come from a greater depth where they equilibrated to a larger extent with the percolating magmas than the KPK rocks.

  12. Composition of the earth's upper mantle. I - Siderophile trace elements in ultramafic nodules

    NASA Technical Reports Server (NTRS)

    Morgan, J. W.; Wandless, G. A.; Petrie, R. K.; Irving, A. J.

    1981-01-01

    The considered investigation is concerned with a reexamination of the question of the distribution of siderophile elements in the earth's upper mantle, taking into account a more unified data base which is now available. A comprehensive suite of ultramafic inclusions was collected as part of the Basaltic Volcanism Study Project and has been analyzed by instrument neutron activation analysis for major, minor, and some lithophile trace elements. In addition, 18 of these rocks and the important sheared garnet lherzolite PHN 1611 have been analyzed by means of radiochemical neutron activation analysis for 7 siderophile elements (Au, Ge, Ir, Ni, Os, Pd, and Re) and 9 volatile elements (Ag, Bi, Cd, In, Sb, Se, Te, Tl, and Zn). The siderophile element data reveal interesting inter-element correlations, which were not apparent from the compiled abundance tables of Ringwood and Kesson (1976) and Chou (1978).

  13. Preliminary study on using rare earth elements to trace non-point source phosphorous loss

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The environmental fate of phosphorus (P) is of concern as P is a primary cause of freshwater eutrophication. Rare earth elements (REEs) have been successfully used in the analysis of soil erosion and pollutant sources, as well as in the analysis of mineral genesis. To better understand the potential...

  14. Undecaprenyl Pyrophosphate Involvement in Susceptibility of Bacillus subtilis to Rare Earth Elements

    PubMed Central

    Ochi, Kozo

    2012-01-01

    The rare earth element scandium has weak antibacterial potency. We identified a mutation responsible for a scandium-resistant phenotype in Bacillus subtilis. This mutation was found within the uppS gene, which encodes undecaprenyl pyrophosphate synthase, and designated uppS86 (for the Thr-to-Ile amino acid substitution at residue 86 of undecaprenyl pyrophosphate synthase). The uppS86 mutation also gave rise to increased resistance to bacitracin, which prevents cell wall synthesis by inhibiting the dephosphorylation of undecaprenyl pyrophosphate, in addition to enhanced amylase production. Conversely, overexpression of the wild-type uppS gene resulted in increased susceptibilities to both scandium and bacitracin. Moreover, the mutant lacking undecaprenyl pyrophosphate phosphatase (BcrC) showed increased susceptibility to all rare earth elements tested. These results suggest that the accumulation of undecaprenyl pyrophosphate renders cells more susceptible to rare earth elements. The availability of undecaprenyl pyrophosphate may be an important determinant for susceptibility to rare earth elements, such as scandium. PMID:22904278

  15. Tracing sediment movement on semi-arid watershed using Rare Earth Elements 1988

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A multi-tracer method employing rare earth elements (REE) was used to determine sediment yield and to track sediment movement in a small semiarid watershed. A 0.33 ha watershed near Tombstone, AZ was divided into five morphological units, each tagged with one of five REE oxides. Relative contributi...

  16. A LOW-COST RARE EARTH ELEMENTS RECOVERY TECHNOLOGY - PHASE I

    EPA Science Inventory

    Physical Sciences, Inc., and the University of Kentucky Center for Applied Energy Research propose to develop a unique enabling technology to significantly reduce U.S. dependency for Rare Earth Elements (REE) on foreign suppliers and our global competitors. Our innovation...

  17. Interactions between exogenous rare earth elements and phosphorus leaching in packed soil columns

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rare earth elements (REEs) increasingly used in agriculture as an amendment for crop growth may help to lessen environmental losses of phosphorus (P) from heavily fertilized soils. The vertical transport characteristics of P and REEs, lanthanum (La), neodymium (Nd), samarium (Sm), and cerium (Ce), w...

  18. SEDIMENT REWORKING AND TRANSPORT IN EASTERN LAKE SUPERIOR: IN SITU RARE EARTH ELEMENT TRACER STUDIES

    EPA Science Inventory

    A rare earth element (REE) tracer pellet was deployed at the floor of the Ile Parisienne basin of eastern Lake Superior to measure representative sediment reworking and transport processes in the benthic boundary layer of the prnfundal Great Lakes. Samarium oxide, a high neutron-...

  19. Catalytic Graphitization of Coal-Based Carbon Materials with Light Rare Earth Elements.

    PubMed

    Wang, Rongyan; Lu, Guimin; Qiao, Wenming; Yu, Jianguo

    2016-08-30

    The catalytic graphitization mechanism of coal-based carbon materials with light rare earth elements was investigated using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, selected-area electron diffraction, and high-resolution transmission electron microscopy. The interface between light rare earth elements and carbon materials was carefully observed, and two routes of rare earth elements catalyzing the carbon materials were found: dissolution-precipitation and carbide formation-decomposition. These two simultaneous processes certainly accelerate the catalytic graphitization of carbon materials, and light rare earth elements exert significant influence on the microstructure and thermal conductivity of graphite. Moreover, by virtue of praseodymium (Pr), it was found that a highly crystallographic orientation of graphite was induced and formed, which was reasonably attributed to the similar arrangements of the planes perpendicular to (001) in both graphite and Pr crystals. The interface between Pr and carbon was found to be an important factor for the orientation of graphite structure. PMID:27482724

  20. Fluid rare earth element anlayses from wells RN-12 and RN-19, Reykjanes, Iceland

    DOE Data Explorer

    Andrew Fowler

    2015-07-24

    Results for fluid rare earth elment analyses from Reykjanes wells RN-12 and RN-19. The data have not been corrected for flashing. Samples preconcetrated using chelating resin with IDA functional group (InertSep ME-1). Analyzed using and Element magnetic sctor ICP-MS.

  1. Technical Information Resource on Rare Earth Elements Now Available to Public and Private Sector Stakeholders

    EPA Science Inventory

    A new EPA technical information resource, “Rare Earth Elements: A Review of Production, Processing, Recycling, and Associated Environmental Issues” has been produced as an introductory resource for those interested in learning more about REE mining and alternatives to meet demand...

  2. Studying the volatility of pyrazolone complexes of rare-earth elements by means of Knudsen effusion

    NASA Astrophysics Data System (ADS)

    Lazarev, N. M.; Petrov, B. I.; Bochkarev, L. N.; Safronova, A. V.; Abakumov, G. A.; Arapova, A. V.; Bessonova, Yu. A.

    2014-08-01

    The temperature dependences of the pressure of saturated vapor of pyrazolone complexes of rare-earth elements Ln(PMIP)3 (where Ln = Y, Ho, Er, Tm, Lu; PMIP = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) are studied via Knudsen effusion, and the enthalpy of their sublimation is determined. Mass spectra and differential scanning calorimetry data are obtained.

  3. Compilation of Rare Earth Element Analyses from US Geothermal Fields and Mid Ocean Ridge Hydrothermal Vents

    DOE Data Explorer

    Andrew Fowler

    2015-10-01

    Compilation of rare earth element and associated major and minor dissolved constituent analytical data for USA geothermal fields and global seafloor hydrothermal vents. Data is in original units. Reference to and use of this data should be attributed to the original authors and publications according to the provisions outlined therein.

  4. Method to Recover Media Ligand Losses During Sorption of Rare Earth Elements from Simulated Geothermal Brines

    DOE Data Explorer

    Dean Stull

    2016-05-24

    This document describes the method and results of an in-situ experiment used to confirm that ligand bleed from a sorptive media can be contained. The experiment focused on maintaining the media's sorption of rare earth elements (REE) obtained from a simulated geothermal brine doped with known mineral concentrations.

  5. Scanning Electron Microscope-Cathodoluminescence Analysis of Rare-Earth Elements in Magnets.

    PubMed

    Imashuku, Susumu; Wagatsuma, Kazuaki; Kawai, Jun

    2016-02-01

    Scanning electron microscope-cathodoluminescence (SEM-CL) analysis was performed for neodymium-iron-boron (NdFeB) and samarium-cobalt (Sm-Co) magnets to analyze the rare-earth elements present in the magnets. We examined the advantages of SEM-CL analysis over conventional analytical methods such as SEM-energy-dispersive X-ray (EDX) spectroscopy and SEM-wavelength-dispersive X-ray (WDX) spectroscopy for elemental analysis of rare-earth elements in NdFeB magnets. Luminescence spectra of chloride compounds of elements in the magnets were measured by the SEM-CL method. Chloride compounds were obtained by the dropwise addition of hydrochloric acid on the magnets followed by drying in vacuum. Neodymium, praseodymium, terbium, and dysprosium were separately detected in the NdFeB magnets, and samarium was detected in the Sm-Co magnet by the SEM-CL method. In contrast, it was difficult to distinguish terbium and dysprosium in the NdFeB magnet with a dysprosium concentration of 1.05 wt% by conventional SEM-EDX analysis. Terbium with a concentration of 0.02 wt% in an NdFeB magnet was detected by SEM-CL analysis, but not by conventional SEM-WDX analysis. SEM-CL analysis is advantageous over conventional SEM-EDX and SEM-WDX analyses for detecting trace rare-earth elements in NdFeB magnets, particularly dysprosium and terbium. PMID:26739864

  6. Uranium and rare earth elements in CO 2-rich waters from Vals-les-Bains (France)

    NASA Astrophysics Data System (ADS)

    Michard, Annie; Beaucaire, Catherine; Michard, Gil

    1987-04-01

    Waters from springs at Vals-les-Bains result from the mixing of a CO 2-rich, highly mineralized water with dilute, shallow subsurface water. Total content of dissolved species vary from 5 mmol/1 to 100 mmol/1. For many elements, mixing of these waters is non-linear (non-conservative) and further water-rock reactions take place. The pH is controlled by CO 2 outgassing, redox conditions are controlled by both the iron hydroxide-siderite buffer and the introduction of oxygen with shallow subsurface waters. Among the major elements, concentrations of Ca, Mg, Mn, Fe, are related to mixing, CO 2 outgassing and carbonate precipitation. Uranium shows a complex behaviour controlled by carbonate complexing, redox conditions, mixing of waters and leaching from the rocks. The 234U /238U activity ratio is near secular equilibrium. In the more dilute waters, dissolved rare earth element (REE) patterns are almost flat with a slight negative Eu anomaly. In the concentrated waters, heavy rare earth elements (Gd-Yb, HREE) are strongly enriched relative to light rare earth elements (Ce-Eu, LREE). We relate the enrichment in HREE to water chemistry and to complexing with carbonate species.

  7. The Sun-Earth connect 1: A fractional d-matrix of solar emissions compared to spectral analysis evidence of solar measurements and climate proxies

    NASA Astrophysics Data System (ADS)

    Baker, Robert G. V.

    2016-02-01

    The possibility that there is a constant ratio underpinning published solar cycles provides an opportunity to explore the harmonics within emission processes. This idea is initially developed by a phenomenological matrix where the elements or emission phases are underpinned by a cyclic fractional dimension d (0.39807) which is shown here to include the fine structure constant (1/137.0356). The Sun's Carrington synodic rotation (27.275d) multiplied by the inverse of the fine structure constant creates elements of this d-matrix which yields possible sequences of self-similar phase periods between harmonic elements of solar emissions. The periodicities of the Carrington rotation is defined by row 1 (R1) and subsequent rows R2,R3,R4 are the potential phase periods of possible twisting permutations of the tachocline. For solar measurements, the first four rows of the matrix predict at least 98% of the top hundred significant periodicities determined from multi-taper spectral analysis of solar data sets (the satellite ACRIM composite irradiance; the terrestrial 10.7cm Penticton Adjusted Daily Radio Flux, Series D; and the historical mean monthly International Sunspot Number). At centennial and millennial time scales, the same matrix predicts 'average' significant periodicities (greater than 95%) reported in 23 published climate data sets. This discovery suggests there is strong empirical evidence for a d-cyclic fractional 'solar clock', where the corresponding spectrum of cycles and switching events are embedded into the historical, climatic and geological records of the Earth.

  8. Rare earth and trace elements of fossil vertebrate bioapatite as palaeoenvironmental and sedimentological proxies

    NASA Astrophysics Data System (ADS)

    Žigaitė, Živilė; Fadel, Alexandre; Pérez-Huerta, Alberto; Jeffries, Teresa

    2015-04-01

    Rare earth (REE) and trace element compositions of fossil vertebrate dental microremains have been studied in Silurian and Devonian vertebrate dental scales and spines in-situ, using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Samples were selected from the well-known Silurian bone beds of Vesiku and Ohesaare in Saaremaa island of Estonia, and a number of Lower Devonian localities from Spitsbergen (Svalbard), Andrée Land group. Biomineral preservation was assessed using spot semi-quantitative elemental chemistry (SEM-EDS) and electron back-scatter difractometry (EBSD) for cristallinity imaging. The obtained PAAS shale-normalised REE concentrations were evaluated using basic geochemical calculations and quantifications. The REE patterns from the Lower Devonian vertebrate apatite from Andrée Land, Spitsbergen (Wood Bay and Grey Hœk formations) did not show any recognisable taxon-specific behavior, but had rather well expressed differences of REE compositions related to biomineral structure and sedimentary settings, suggesting REE instead to reflect burial environments and sedimentological history. The Eu anomaly recorded in two of the studied localities but not in the other indicate different taphonomic conditions and palaeoenvironment, while La/Sm, La/Yb ratios sugeest considerable influence of terrestrial freshwater during the early diagenesis. The La/Yb and La/Sm plots also agree with the average REE concentrations, reflecting domination of the adsoption over substitution as principal REE uptake mechanism in the fossils which had significantly lower overall REE concentrations, and vice versa. Vesiku (Homerian, Wenlock) microremains yielded very uniform REE patterns with slightly lower overall REE concentrations in enameloid than in dentine, with strong enrichment in middle REE and depletion in heavy REE. Negative Europium (Eu) anomaly was pronounced in all the profiles, but Cerium (Ce) anomalies were not detected suggesting possible

  9. Rare Earth Element Measurements of Melilite and Fassaite in Allende Cai by Nanosims

    NASA Technical Reports Server (NTRS)

    Ito, M.; Messenger, Scott

    2009-01-01

    The rare earth elements (REEs) are concentrated in CAIs by approx. 20 times the chondritic average [e.g., 1]. The REEs in CAIs are important to understand processes of CAI formation including the role of volatilization, condensation, and fractional crystallization [1,2]. REE measurements are a well established application of ion microprobes [e.g., 3]. However the spatial resolution of REE measurements by ion microprobe (approx.20 m) is not adequate to resolve heterogeneous distributions of REEs among/within minerals. We have developed methods for measuring REE with the NanoSIMS 50L at smaller spatial scales. Here we present our initial measurements of REEs in melilite and fassaite in an Allende Type-A CAI with the JSC NanoSIMS 50L. We found that the key parameters for accurate REE abundance measurements differ between the NanoSIMS and conventional SIMS, in particular the oxide-to-element ratios, the relative sensitivity factors, the energy distributions, and requisite energy offset. Our REE abundance measurements of the 100 ppm REE diopside glass standards yielded good reproducibility and accuracy, 0.5-2.5 % and 5-25 %, respectively. We determined abundances and spatial distributions of REEs in core and rim within single crystals of fassaite, and adjacent melilite with 5-10 m spatial resolution. The REE abundances in fassaite core and rim are 20-100 times CI abundance but show a large negative Eu anomaly, exhibiting a well-defined Group III pattern. This is consistent with previous work [4]. On the other hand, adjacent melilite shows modified Group II pattern with no strong depletions of Eu and Yb, and no Tm positive anomaly. REE abundances (2-10 x CI) were lower than that of fassaite. These patterns suggest that fassaite crystallized first followed by a crystallization of melilite from the residual melt. In future work, we will carry out a correlated study of O and Mg isotopes and REEs of the CAI in order to better understand the nature and timescales of its

  10. Rare earth element evidence for the petrogenesis of the banded series of the Stillwater Complex, Montana, and its anorthosites

    USGS Publications Warehouse

    Loferski, P.J.; Arculus, R.J.; Czamanske, G.K.

    1994-01-01

    A rare earth element (REE) study was made by isotope-dilution mass spectrometry of plagioclase separates from a variety of cumulates stratigraphically spanning the Banded series of the Stillwater Complex, Montana. Evaluation of parent liquid REE patterns, calculated on the basis of published plagioclase-liquid partition coefficients, shows that the range of REE ratios is too large to be attributable to fractionation of a single magma type. At least two different parental melts were present throughout the Banded series. This finding supports hypotheses of previous workers that the Stillwater Complex formed from two different parent magma types, designated the anorthosite- or A-type liquid and the ultramafic- or U-type liquid. -from Authors

  11. Study on Orbital Decay of Near Earth Satellites with KS Orthogonal Elements

    NASA Astrophysics Data System (ADS)

    Ps, Sandeep

    STUDY ON ORBITAL DECAY OF NEAR EARTH SATELLITES WITH KS ORTHOGONAL ELEMENTS SANDEEP P S The knowledge of satellite orbit decay and its expected life prior to launch is necessary for mission planning purpose. Several sets of data for various parametric studies is sought quite often, it is necessary to minimize computational time involved for generating decay predictions, keeping the prediction accuracy normally good. A number of factors play dominant role in perturbation modelling for near earth satellites such as oblateness of the Earth, presence of the atmosphere, luni-solar attraction and solar radiation pressure. This paper concerns with the study of orbital decay of near earth satellites with KS orthogonal elements, which provide accurate orbit predictions at low computational time. Perturbations considered are due to oblateness of the Earth and the atmospheric drag. The Earth’s zonal harmonic terms J2 to J6 are included and the drag is modeled with an analytical diurnally oblate atmosphere. Effect of Earth’s geomagnetic and solar activity is included in density and density scale height computations. JACCHIA77 atmospheric model is utilized. The developed software is validated with the orbital data of decayed objects taken from www.space-track.org.

  12. Origin of the earth's moon - Constraints from alkali volatile trace elements

    NASA Technical Reports Server (NTRS)

    Kreutzberger, M. E.; Drake, M. J.; Jones, J. H.

    1986-01-01

    Although the moon is depleted in volatile elements compared to the earth, these depletions are not in accord with simple volatility. For example, the Cs/Rb ratios of the earth and moon inferred from basalt are approximately one seventh and one half of the CI ratio, respectively. Volatility considerations alone predict that the lunar Cs/Rb ratio should be equal to or lower than the terrestrial ratio if the moon was derived entirely from earth mantle material. Thus hypotheses such as rotational fission which invoke derivation of lunar material entirely from the earth's mantle may be excluded. The collisional ejection hypothesis of lunar origin requires at least 18 percent of lunar material to be derived from a projectile with dehydrated CI composition to match the lunar Cs/Rb ratio, and 25-50 percent to match both the lunar Cs/Rb ratio and absolute concentrations of Cs and Rb. It remains to be demonstrated that this relatively large contribution of projectile material is consistent with other elemental abundances and element ratios in the moon.

  13. Trace Element and Pb Isotope Constraints on Dynamic Evolution of Earth Reservoirs

    NASA Astrophysics Data System (ADS)

    Collerson, K.; Kamber, B.

    2001-12-01

    U/Pb fractionation. Recent discovery of LM baddeleyite provides the mineralogical rationale for this scenario. Subducted oceanic crust and continental sediment are unlikely candidates for OIB HIMU source, as trace element fractionation during subduction induced dehydration lowers U/Pb ratio of residual slabs. This has important consequences for genesis of lamproites and minettes. In an speculative model by [5], and supported by seismic tomography, TZ was interpreted as a graveyard for slabs containing high pressure mineralogies such as majorite, NAL phases and hollandite. Partial melts derived from such an environment yield alkaline rocks with Pb isotopic compositions plotting to the left of the Geochron. Significantly, this interpretation is now supported by Pb isotopic data for TZ macrocryst suite xenoliths. An unrelated, now extinct HIMU reservoir, is inferred from Pb isotopes in TTG gneisses in some Archean cratons. Evolution of this source is reflected in Pb isotopic data for galena from Isua that require source separation before 4.3 Ga. The only conceivable long-lived source would have been Hadean crust. Rare examples of pre-plate tectonics TTG gneisses with this isotopic memory occur in the NAC where feldspar Pb isotopes define rotated isochrons that intersect the transient HIMU evolution vector at the time of zircon crystallization of the gneiss protoliths. This transient early Archean HIMU reservoir was subsequently destroyed by subduction. 1Collerson&Kamber (1999) Science 283, 1519. 2Kramers&Tolstikhin (1997) Chem. Geol. 139, 75. 3Reymer&Schubert (1984) Tectonics 3, 63. 4Kamber&Collerson (1999) JGR 105, 25479. 5Ringwood (1994) Phys. Earth Planet. Int. 86, 5.

  14. Heavy metals and rare earth elements source-sink in some Egyptian cigarettes as determined by neutron activation analysis.

    PubMed

    Nada, A; Abdel-Wahab, M; Sroor, A; Abdel-Haleem, A S; Abdel-Sabour, M F

    1999-07-01

    Heavy metals and rare earth elements in two types of cigarettes were studied. The contents of trace elements were determined by using delayed neutron activation analysis. In the present study 11 elements have been detected in popular and fine brand cigarettes marketed in Egypt. Evaluation of these elements with their potential hazards for smokers is briefly discussed. The material balance (source and sink) for each element was determined. Also the ratio of element recovery to the total amount was assessed. PMID:10376325

  15. The group separation of the rare-earth elements and yttrium from geologic materials by cation-exchange chromatography

    USGS Publications Warehouse

    Crock, J.G.; Lichte, F.E.; Wildeman, T.R.

    1984-01-01

    Demand is increasing for the determination of the rare-earth elements (REE) and yttrium in geologic materials. Due to their low natural abundance in many materials and the interferences that occur in many methods of determination, a separation procedure utilizing gradient strong-acid cation-exchange chromatography is often used to preconcentrate and isolate these elements from the host-rock matrix. Two separate gradient strong-acid cation-exchange procedures were characterized and the major elements as well as those elements thought to provide the greatest interference for the determination of the REE in geologic materials were tested for separation from the REE. Simultaneous inductively coupled argon plasma-atomic emission spectroscopy (ICAP-AES) measurements were used to construct the chromatograms for the elution studies, allowing the elution patterns of all the elements of interest to be determined in a single fraction of eluent. As a rock matrix, U.S. Geological Survey standard reference BCR-1 basalt was digested using both an acid decomposition procedure and a lithium metaborate fusion. Hydrochloric and nitric acids were tested as eluents and chromatograms were plotted using the ICAP-AES data; and we observed substantial differences in the elution patterns of the REE and as well as in the solution patterns of Ba, Ca, Fe and Sr. The nitric acid elution required substantially less eluent to elute the REE and Y as a group when compared to the hydrochloric acid elution, and provided a clearer separation of the REE from interfering and matrix elements. ?? 1984.

  16. Structural Responses and Finite Element Modeling of Hakka Tulou Rammed Earth Structures

    NASA Astrophysics Data System (ADS)

    Sranislawski, Daniel

    Hakka Tulous are rammed earth structures that have survived the effects of aging and natural elements upwards of even over a thousand years. These structures have housed the Hakka people of the Fujian Province, China in natural yet modern housing that has provided benefits over newer building materials. The key building material, rammed earth, which is used for the walls of the Hakka Tulou structures, has provided structural stability along with thermal comfort to the respective inhabitants of the Hakka Tulous. Through material testing and analysis this study has examined how the Tulou structures have maintained their structural stability while also providing thermal comfort. Reports of self healing cracks in the rammed earth walls were also analyzed for their validity in this study. The study has found that although the story of the self healing crack cannot be validated, there is reason to believe that with the existence of lime, some type of autogenous healing could occur on a small scale. The study has also found, through the use of nondestructive testing, that both the internal wooden systems (flooring, roof, and column support) and the rammed earth walls, are still structurally sound. Also, rammed earth's high thermal mass along with the use of sufficient shading has allowed for a delay release of heat energy from the walls of the Tulous, thus providing thermal comfort that can be felt during both night and day temperatures. The Hakka Tulou structures have been found to resist destruction from natural disasters such as strong earthquakes even when more modern construction has not. Through finite element modeling, this study has shown that the high volume of rammed earth used in the construction of the Hakka Tulous helps dissipate lateral force energy into much lower stresses for the rammed earth wall. This absorption of lateral force energy allows the rammed earth structures to survive even the strongest of earthquakes experienced in the region. The Hakka

  17. Fractionation and mobilization of toxic elements in floodplain soils from Egypt, Germany, and Greece: A comparison study

    NASA Astrophysics Data System (ADS)

    Shaheen, Sabry M.; Rinklebe, Jörg; Tsadilas, Christos D.

    2015-12-01

    Determining the chemical fractions of toxic elements (TEs) in soils is important to evaluate their mobilization and bioavailability. In this study, samples from three representative floodplain soils located close to the Rivers Nile (Egypt), Elbe (Germany), and Pinios (Greece) were used to link the soil formation and properties to the geochemical fractions and mobilization of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in these soils. The Elbe soil showed the highest total concentration of the elements except for Ni, in which the Pinios soil had the highest amount. A significant amount (55-94%) of the elements was present in the Elbe soil in the potentially mobile (non-residual) fraction, while the amount of this fraction ranged between 9 and 39% in the Pinios soil and between 9 and 34% in the Nile soil. In the Elbe soil, most of the non-residual Ni, Pb, and Zn was associated with the Fe-Mn oxide fraction, while Cd was distributed in the soluble plus exchangeable fraction and Cu in the organic fraction. In the Nile and Pinios soils the Fe-Mn oxide fraction was the abundant pool for Cu, Ni, Pb, and Zn whereas Cd had the highest amount in the soluble plus exchangeable as well as in the carbonate fractions.

  18. Inter-element fractionation of highly siderophile elements in the Tonga Arc due to flux melting of a depleted source

    NASA Astrophysics Data System (ADS)

    Dale, Christopher W.; Macpherson, Colin G.; Pearson, D. Graham; Hammond, Samantha J.; Arculus, Richard J.

    2012-07-01

    Highly siderophile element concentrations (HSEs: Os, Ir, Ru, Pt, Pd, and Re) have been determined for a suite of fresh, submarine mafic lavas from the northern Tonga Arc front and the nascent backarc Fonualei Spreading Centre (FSC). Prior melt depletion of the Tongan mantle wedge combined with a high degree of fluid fluxed melting is thought to have produced boninitic magmas at several arc and FSC locations. As such, this arc system provides an opportunity to assess the fluid mobility of HSEs and to investigate the effects of fluid-induced melting and prior melt depletion on HSE behaviour during both mantle melting and magma evolution. Tongan lavas display extreme enrichment of Pt (2.5-32 ng/g) and Pd over Os (0.002-0.6 ng/g), Ir, and Ru, significantly greater than basalts from mid-ocean ridges. Magma evolution increases the degree of fractionation, resulting in the highest recorded Pt/Ru ratios (>300) in arc front samples with MgO <8 wt.%. This increasing fractionation is due to the mild incompatibility of Pt and Pd, and concurrent compatibility of Ru, during sulphide undersaturated magma evolution. However, the fractionation of Pt and Pd from Os, Ir, and Ru is observed in the highest MgO samples, indicating source inheritance. Prior melt depletion of the mantle and elevated oxygen fugacity both increase the likelihood of complete consumption of sulphide in the source during melting, which typically leads to melts with high concentrations of all the HSE. Indeed, modelling indicates that 25% aggregate partial melting of a depleted MORB-mantle source, proposed for the Tonga Arc, will lead to complete base-metal sulphide consumption unless there is considerable addition of S by the slab flux (at least 200 μg/g). Although source enrichment of Pt, Pd, and Re by slab fluids may take place, the fractionation of Pt and Pd from Os, Ir, and Ru can largely be explained by relatively low-temperature, yet high-degree, melting of fluid-fluxed melt-depleted mantle. The high Pt

  19. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    SciTech Connect

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

  20. Accurate projected augmented wave (PAW) datasets for rare-earth elements (RE=La-Lu)

    NASA Astrophysics Data System (ADS)

    Topsakal, Mehmet; Wentzcovitch, Renata

    2015-03-01

    We provide accurate projected augmented wave (PAW) datasets for rare-earth (RE) elements with some suggested Hubbard U values allowing efficient plane-wave calculations. Solid state tests of generated datasets were performed on rare-earth nitrides. Through density of state (DOS) and equation of state (EoS) comparisons, generated datasets were shown to yield excellent results comparable to highly accurate all-electron full-potential linearized augmented plane-wave plus local orbital (FLAPW+LO) calculations. Hubbard U values for trivalent RE ions are determined according to hybrid functional calculations. We believe that these new and open-source PAW datasets will allow further studies on rare-earth materials. NSF/EAR 1319361

  1. Highly siderophile elements were stripped from Earth's mantle by iron sulfide segregation.

    PubMed

    Rubie, David C; Laurenz, Vera; Jacobson, Seth A; Morbidelli, Alessandro; Palme, Herbert; Vogel, Antje K; Frost, Daniel J

    2016-09-01

    Highly siderophile elements (HSEs) are strongly depleted in the bulk silicate Earth (BSE) but are present in near-chondritic relative abundances. The conventional explanation is that the HSEs were stripped from the mantle by the segregation of metal during core formation but were added back in near-chondritic proportions by late accretion, after core formation had ceased. Here we show that metal-silicate equilibration and segregation during Earth's core formation actually increased HSE mantle concentrations because HSE partition coefficients are relatively low at the high pressures of core formation within Earth. The pervasive exsolution and segregation of iron sulfide liquid from silicate liquid (the "Hadean matte") stripped magma oceans of HSEs during cooling and crystallization, before late accretion, and resulted in slightly suprachondritic palladium/iridium and ruthenium/iridium ratios. PMID:27609889

  2. Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

    SciTech Connect

    Morf, Leo S.; Gloor, Rolf; Haag, Olaf; Haupt, Melanie; Skutan, Stefan; Lorenzo, Fabian Di; Böni, Daniel

    2013-03-15

    Highlights: ► We carefully addressed all the very valuable comments and suggestions of the reviewers. ► We also have shortened the size of the paper and tried simplify it substantially, as requested by the reviewers (introduction 25% reduced!). ► We have decided to take the chance and have replaced the data for the “additional” elements (Cu, Cd, Zn, Pb, Sn, Cr, Ni, Fe, Al) of the earlier MFA (Morf, 2011) with data that belong to the samples of this study. ► We are convinced that with the revision the paper has significantly improved in quality and attractiveness. - Abstract: In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are

  3. Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements

    SciTech Connect

    Hashida, Masaki; Sakabe, Shuji; Izawa, Yasukazu

    2011-03-15

    Symmetric charge-transfer cross sections of IIIa rare-earth-metal elements (Sc, Y, and Gd) in the impact energy range of 30 to 1000 eV were measured for the first time. The experiments were performed with a crossed-beam apparatus that featured primary ion production by photoionization with a tunable dye laser. Comparing the cross sections of IIIa rare-earth-metal elements ({sigma}{sub Sc}, {sigma}{sub Y}, and {sigma}{sub Gd}) with those of alkali metals or helium {sigma}{sub 0}, we found that {sigma}{sub 0{approx_equal}{sigma}Sc}<{sigma}{sub Y}<{sigma}{sub Gd{approx_equal}}2{sigma}{sub 0}at an impact energy of 1000 eV.

  4. Extraction of rare-earth elements from nitric solutions by phosphoryl-containing podands

    SciTech Connect

    Turanov, A.N.; Karandashev, V.K.; Baulin, V.E.

    1999-11-01

    The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO{sub 3} solutions by phosphoryl-containing podands of various structures has been studied.. It has been found that the maximum extraction of rare earth elements is exhibited by reagents containing one ether oxygen atom in the molecule, bound to diphenylphosphoryl or ditolylphosphoryl groups by methylene and o-phenylene fragments. The structure of these reagents is best suited for the polydentate coordination of the ligand and the conditions of a chelate complex formation. The effect of HNO{sub 3} concentration in the aqueous phase and that of the nature of an organic diluent on the extraction of rare earth elements and Y are considered. Stoichiometric of the extracted complexes has been determined and the extraction constants calculated.

  5. Anomalous abundance and redistribution patterns of rare earth elements in soils of a mining area in Inner Mongolia, China.

    PubMed

    Wang, Lingqing; Liang, Tao

    2016-06-01

    The Bayan Obo Mine, the largest rare earth element (REE) deposit ever found in the world, has been mined for nearly 60 years for iron and rare earth elements. To assess the influences of mining activities on geochemical behavior of REEs in soils, 27 surface soil samples and three soil profile samples were collected from different directions in the vicinity of the mine area. The total concentrations of REEs in surface soils varied from 149.75 to 18,891.81 mg kg(-1) with an average value of 1906.12 mg kg(-1), which was apparently higher than the average values in China (181 mg kg(-1)). The order of the average concentrations of individual REEs in surface soils was similar to that in Bayan Obo ores, which confirmed that the concentration and distribution of REEs in the soils was influenced by the mining activities. The concentrations of single REE in the soil profiles showed a similar trend with depth with an increase at 0-25 cm section, then decreased and remained relatively stable in the deep part. The normalized curves inclined to the right side, showing the conspicuous fractionation between the light and heavy REEs, which supported by the North American Shale Composite (NASC) and Post-Archean Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La N /Yb N , La N /Sm N , Gd N /Yb N ). Slight positive Ce anomaly and negative Eu anomaly were also observed. PMID:26931660

  6. Geochemical fractions and risk assessment of trace elements in soils around Jiaojia gold mine in Shandong Province, China.

    PubMed

    Cao, Feifei; Kong, Linghao; Yang, Liyuan; Zhang, Wei

    2015-09-01

    Soils located adjacent to the Jiaojia gold mine were sampled and analyzed to determine the degree of which they were contaminated by trace elements (Hg, As, Cd, Pb, Cu, and Zn) in Shandong Province, China. All 18 samples exhibited mean Hg, As, Cd, and Pb concentrations in excess of local background values, while the mean concentrations of Cu and Zn were below the background values. In addition, the concentrations of trace elements in gold smelter (GS) soils were higher than in the gold mine (GM) soils. The result from a modified Tessier sequential extraction procedure was that with the exception of Cu in soils near the smelter, the trace elements were predominantly associated with the residual fraction. After residual fraction, most Hg was mainly humic acid and strong organic fraction, while most As was the humic acid. Cd was associated with the water soluble, ion exchange, and carbonate fractions compared with the other trace elements. Furthermore, Cu, Pb, and Zn were more concentrated in the humic acid and Fe/Mn oxide fraction. The fractions of trace elements were affected by soil pH and Ec (Electrical conductivity). The humic acid fraction of Hg as well as the ion exchange fraction of Cd and Zn displayed negative correlations with soil pH. The strong organic fraction of Hg, the Fe/Mn oxide fraction of Cd, and the carbonate fraction of Zn were positively related to the soil Ec. The strong organic fraction and ion exchange fraction of Zn were negatively related to soil Ec. However, the ion exchange and carbonate fractions of As showed significant positive correlations with soil pH. A calculated individual availability factor (A f (i) ) is used; the values of each trace element in the soils are in the following order: Cu > Cd > Pb > Zn > As > Hg. When combined with a risk assessment code, data suggest that Hg, As, Pb, and Zn levels showed low risk for the environment, whereas Cd levels in soils adjacent to the GM and Cu levels in soils adjacent to the GS showed

  7. Transport of rare earth element-tagged soil particles in response to thunderstorm runoff.

    PubMed

    Matisoff, G; Ketterer, M E; Wilson, C G; Layman, R; Whiting, P J

    2001-08-15

    The downslope transport of rare earth element-tagged soil particles remobilized during a spring thunderstorm was studied on both a natural prairie and an agricultural field in southwestern Iowa (U.S.A.). A technique was developed for tagging natural soils with the rare earth elements Eu, Tb, and Ho to approximately 1,000 ppm via coprecipitation with MnO2. Tagged material was replaced in target locations; surficial soil samples were collected following precipitation and runoff; and rare earth element concentrations were determined by inductively coupled plasma mass spectrometry. Diffusion and exponential models were applied to the concentration-distance data to determine particle transport distances. The results indicate that the concentration-distance data are well described by the diffusion model, butthe exponential model does not simulate the rapid drop-off in concentrations near the tagged source. Using the diffusion model, calculated particle transport distances at all hillside locations and at both the cultivated and natural prairie sites were short, ranging from 3 to 73 cm during this single runoff event. This study successfully demonstrates a new tool for studying soil erosion. PMID:11529577

  8. Evaluating rare earth element availability: a case with revolutionary demand from clean technologies.

    PubMed

    Alonso, Elisa; Sherman, Andrew M; Wallington, Timothy J; Everson, Mark P; Field, Frank R; Roth, Richard; Kirchain, Randolph E

    2012-03-20

    The future availability of rare earth elements (REEs) is of concern due to monopolistic supply conditions, environmentally unsustainable mining practices, and rapid demand growth. We present an evaluation of potential future demand scenarios for REEs with a focus on the issue of comining. Many assumptions were made to simplify the analysis, but the scenarios identify some key variables that could affect future rare earth markets and market behavior. Increased use of wind energy and electric vehicles are key elements of a more sustainable future. However, since present technologies for electric vehicles and wind turbines rely heavily on dysprosium (Dy) and neodymium (Nd), in rare-earth magnets, future adoption of these technologies may result in large and disproportionate increases in the demand for these two elements. For this study, upper and lower bound usage projections for REE in these applications were developed to evaluate the state of future REE supply availability. In the absence of efficient reuse and recycling or the development of technologies which use lower amounts of Dy and Nd, following a path consistent with stabilization of atmospheric CO(2) at 450 ppm may lead to an increase of more than 700% and 2600% for Nd and Dy, respectively, over the next 25 years if the present REE needs in automotive and wind applications are representative of future needs. PMID:22304002

  9. Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel-metal-hydride batteries

    NASA Astrophysics Data System (ADS)

    Rodrigues, Luiz Eduardo Oliveira Carmo; Mansur, Marcelo Borges

    The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.2-10.9%), cobalt (5.1-5.5%), rare earth elements (15.3-29.0%) and cadmium (2.8%). The presence of cadmium reveals that some Ni-Cd batteries are possibly labeled as NiMH ones. The leaching of nickel and cobalt from the NiMH battery powder with sulfuric acid is efficient; operating variables temperature and concentration of H 2O 2 has no significant effect for the conditions studied. A mixture of rare earth elements is separated by precipitation with NaOH. Finally, solvent extraction with D2EHPA (di-2-ethylhexyl phosphoric acid) followed by Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) can separate cadmium, cobalt and nickel from the leach liquor. The effect of the main operating variables of both leaching and solvent extraction steps are discussed aiming to maximize metal separation for recycling purposes.

  10. Rare earth elements in coastal sediments of the northern Galician shelf: Influence of geological features

    NASA Astrophysics Data System (ADS)

    Prego, Ricardo; Caetano, Miguel; Bernárdez, Patricia; Brito, Pedro; Ospina-Alvarez, Natalia; Vale, Carlos

    2012-03-01

    The Northern coast of Galicia, NW Iberian Peninsula, exhibits a variety of geological features: Ortegal allochthonous complex, Ollo-de-Sapo autochthonous domain and massifs of Bares, Barqueiro and San-Ciprian. In order to examine the influence of terrestrial lithologies on coastal sediments, 103 samples were collected in the Rias of Ortigueira, Barqueiro and Viveiro, their neighbouring shelf and the estuaries of Mera, Sor and Landro rivers. Aluminium, Fe, Sc, particulate inorganic and organic carbon and rare earth elements (REE) were determined in the <2 mm fraction. In addition, calcite, muscovite, quartz and riebeckite minerals were identified and quantified in 33 selected samples. The distributions of riebeckite and Fe reflect the influence of Ortegal complex on the coastal areas around the Cape Ortegal. The highest concentrations of ΣREE were found in fine sediments from confined inner parts of the Rias (up to 233 mg kg-1), while most of the sands contained 11-70 mg kg-1. ΣREE normalised to European Shale (ES) highlights the relative abundance of lanthanides (ΣREEN>6) near Cape Ortegal and the innermost ria zones. The ratio between light and heavy REE (L/H) showed lower values (4-11) around Cape Ortegal and the shelf while higher ratios (15-23) were detected in west of the Cape Estaca-de-Bares and in the inner Viveiro Ria due to elevated contributions of La and Ce. The L/H values normalised to ES reflects the importance of HREE in the adjacent area to Ortegal Complex (LN/HN<0.8) and the LREE (LN/HN>1.4) in the inner estuaries and west Cape Estaca-de-Bares. The highest REE individual ES normalised were measured in fine-grained sediments of the Mera and Sor estuaries. Sediments from the eastern shelf of Cape Ortegal presented enhanced ratios only for HREE. These results indicate that distribution of REE in the northern Galician region is highly depending on the neighbouring lithological pattern, contrasting with the situation found in the western Galician