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Sample records for earth element fractionation

  1. 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-rich inclusions, which have large negative Ce and small negative Pr anomalies [7], probably formed by extremely rapid evaporation in the solar nebula or by evaporation in an environment much poorer in hydrogen. Normal CAIs do not have Ce anomalies. If they experienced evaporation in the solar nebula, the process must have occurred slowly enough to maintain reducing conditions in the residue. References: [1] Davis A. M. et al. (1990) Nature, 347, 655-658. [2] Boynton W. V. (1975) GCA, 39, 569-584. [3] Davis A. M. and Grossman L. (1979) GCA, 43, 1611-1632. [4] Hashimoto A. (1990) Nature, 347, 53-55. [5] Hashimoto A. (1983) Geochem. J., 17, 111-145. [6] Davis A. M. et al. (1982) GCA, 46, 1627-1651. [7] Ireland T. R. et al. (1992) GCA, 56, 2503-2520. Figure 1, which appears in the hard copy, shows fraction remaining vs. percent evaporated for vacuum evaporation of material of chondritic composition.

  2. 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

  3. Bioavailable concentrations of germanium and rare earth elements in soil fractions

    NASA Astrophysics Data System (ADS)

    Hentschel, Werner; Wiche, Oliver

    2015-04-01

    As there is an increasing demand for germanium and the rare earth elements due to their diverse application in modern technologies (optical cables, permanent magnets in wind power stations), there is an interest to investigate a new approach to extract these ubiquitous but disperse existing elements - via Phytomining. But before this method can be established, a thorough understanding of processes regarding the intake of germanium (Ge) and the rare earth elements (REEs) is necessary. The aim of this work was to get insights or hints on correlations between the concentrations and the fractionation of Ge and REEs in the soil and the concentrations in plants - in other words we wanted to conduct research on bioavailable concentrations of Ge and REEs in soil fractions. On 18 sites situated around Freiberg, Saxony we took samples of soil and plants. To extract the elements from the plant material a decomposition with hydrofluoric acid was used. The soil samples was examined by a sequential extraction with seven steps (mobile, carbonatic, oxidisable, amorphic oxides, crystalline oxides, phytoliths and secondary clay minerals, residual or siliceous). The amounts of the REEs showed a high correlation between each other, so neodymium can be regarded as a proxy for all REEs. The average total amount of Ge in the soil samples was around 1.45 mg/kg, the one of neodymium (Nd) was around 25 mg/kg. Both values equal the overall average in the earth crust. Concerning the Ge concentration in soil the residual siliceous fractions constituted for 70% of total, whereas the fractions V and VI - dedicated as crystalline oxides and phytoliths/secondary clay minerals - made out for 25%. Only 5% of the total amount of Ge in soil accounted for the fractions I to IV. There was found a statistical significant correlation between the absolute Ge concentrations in these latter soil fractions with the Ge concentration in plant material of the same site. Therefore it seems that the fractions I to IV could be regarded as a proxy for the bioavailable pool of Ge in soils. Concerning Nd the residual siliceous fractions made out for 60% of the total, whereas the fraction III (oxidisable) constitutes for 30%. The remaining 10% accounted for the other soil fractions. No correlation between the concentration in one soil fraction and the concentration in plant material from the same site could be found. There was also no correlation between the total amount in soil and the concentration in plant material from the same site neither for the REEs nor for Ge. These results can give only hints on the processes regarding the mobilisation of the bioavailable pool of Ge and REEs. Further investigations are necessary and will be taken in the PhytoGerm project.

  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=17.44.3), 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 1.60.5 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-derived aqueous fluids have a significant contribution to the formation of REE-signatures in arc-magmas, especially at lower slab surface temperatures.

  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 ?m-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 refractory elements. A new reference composition relevant to inner solar system bodies (CI?) is calculated by subtracting 0.15% of group II refractory inclusions to CI. The observed Tm anomalies in ordinary and enstatite chondrites and terrestrial rocks, relative to carbonaceous chondrites, indicate that material akin to carbonaceous chondrites must have represented a small fraction of the constituents of the Earth. Tm anomalies may be correlated with Ca isotopic fractionation in bulk planetary materials as they are both controlled by addition or removal of refractory material akin to fine-grained group II refractory inclusions.

  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 ?m) were 5-15 times higher than those in four size fractions of zooplankton: 200-500 ?m, 500-1000 ?m, 1000-2000 ?m and >2000 ?m. 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. 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

  13. Rare earth elements in intertidal sediments of Bohai Bay, China: concentration, fractionation and the influence of sediment texture.

    PubMed

    Zhang, Yong; Gao, Xuelu; Arthur Chen, Chen-Tung

    2014-07-01

    Surface sediments from intertidal Bohai Bay were assessed using a four-step sequential extraction procedure to determine their concentrations of rare earth elements (REEs) and the chemical forms in which those elements were present. The normalized ratios La/Gd and La/Yb showed that LREE contents were not significantly higher than the middle REEs or HREE contents. A negative Ce anomaly and positive Eu were observed in sand and silty sand sediments, whereas no significant Ce or Eu anomaly was found in clayey silt sediments. Residual fraction of REEs accounted for the majority of their total concentrations. Middle REEs were more easily leached than other REEs, especially in clayey silt sediment. REEs contents in the surface sediment from the intertidal Bohai Sea were consistent with data from the upper continental crust and China shallow sea sediments, indicating that they were generally unaffected by heavily anthropogenic effects from adjacent areas. PMID:24793516

  14. 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 ?m (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.

  15. 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.

  16. 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 positive Gd anomaly. When grown on smectite, the REE concentrations of the leaves and the stems+roots were about 7.2 and 6.3 ?g/g, respectively. The REE distribution patterns for the leaves and the stems+roots normalized to the corresponding smectite substrate are very closely similar, each having a nearly flat pattern with a slight but not significant negative Ce anomaly and a similar positive Gd anomaly. When grown on the smectite substrate with a different porosity, the leaves and the stems+roots had significantly higher REE concentrations of 9.3 and 19.7 ?g/g, respectively. Relative to the substrate REE pattern, the two organs had nearly identical flat REE distribution patterns, with a slight negative Ce anomaly and positive Gd and Er anomalies, In summary, the REE take up is more plant species dependent than mineral composition dependent: R. raphanistrum takes up 3.5 to 6.7 times more REEs than R. sativus, depending on the substrate, its porosity and the considered plant segments. Increased substrate porosity favors the pick up of the REEs, but no particular uptake is observed in leaves relative to that in the combined stems and roots. The transfer of the REEs from minerals to plant organs does not appear to induce systematically identical patterns. The effect of the plant species in the elemental uptake suggests that the root exudates are different, with a varied control on the micro-organism activity in the rhizosphere and probably different microbial compounds. New questionings about the identification of the organic compounds that influence and control the process of elemental exchanges activated by the root exudates in the soils within the rhizosphere, are also raised.

  17. The Fractionation of Rare Earth and Other Trace Elements Accompanying the Oxidative Precipitation of Iron Oxide From Ferrous-Iron Rich Coastal Ground Waters

    NASA Astrophysics Data System (ADS)

    Sholkovitz, E.; Charette, M.; Morford, J.

    2001-05-01

    Ground water near the head of Waquoit Bay (Cape Cod, MA, USA) have high (45 uM) concentrations of dissolved (<0.2 um) ferrous iron. Exposure to air results in the complete and rapid oxidation of dissolved ferrous Fe to particulate ferric iron at the ambient pH of approximately 6.8. The co-precipitation of rare earth elements (REE) during the oxidation and precipitation of iron was studied in the laboratory by allowing the <0.2 um filtered ground water to air oxidize in an open bottle. The iron precipitate (>0.2 um fraction) and the oxidized solution <0.2 um fraction), as well as the initially filtered (<0.2 um) ground water, were analyzed for their REE compositions. The major observation is that large scale fractionation of REE accompanies the removal of dissolved REE during the oxidative precipitation of iron. That is, the extent of removal decreases from 100 % to 24 % across the REE series. Specifically, the three lightest REE (La, Ce and Nd) of the REE series are completely removed. Within the middle group, Sm, Eu and Gd show 94 % removal while the removal of Tb and Dy drops to 88 % and 81 % respectively. The extent of removal of the heaviest REE decreases significantly with Er, Yb and Lu at 40, 32 and 24 % respectively. The same experimental solutions were used to quantify the partitioning of other trace elements onto precipitating iron oxide particles. The extent of removal range from 77 % for V to 2 % for Mo. Other removal % are as follows: U (66), Cd (59), Cu (49), Co (30), Ba (17), Ni (15), Mn (8) and Re (4). The large scale fractionation of REE and other trace metals reflects their aquatic chemistry as co-precipitating and adsorbing surfaces of ferric hydroxyoxide compete for REE and trace metals in solution. Hence, the composition of REE and other trace elements in ground water can be greatly altered by redox processes.

  18. 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. Nearly-CI-chondritic Sn/Pb ratios are observed in Allende and other carbonaceous chondrites. Evaporation from a solid leads to a severe increase in this ratio. Similarly, Rb/Cs ratios (about 12) are approximately CI-like in all groups of carbonaceous chondrites, perhaps reflecting the inability of nebular processes to fractionate these ratios. In contrast, terrestrial, lunar, and eucritic rocks have much higher Rb/Cs ratios [5]. As volatile loss from molten magmas is excluded [2], their low Cs contents must be characteristic of the parent material. This may exclude carbonaceous chondrites as source materials of eucrites, the Earth, and the Moon. The low Cs in planetary precursor materials may have been produced by secondary heating of small fragments of solid matter at subsolidus temperatures before final accretion. Equilibrated chondrites also show high Rb/Cs ratios, perhaps indicating mobilization of Cs at metamorphic temperatures. References: [1] Palme H. et al. (1988) in Meteorites and the Early Solar System, 436-461, Univ. of Arizona. [2] Humayan M. and Clayton R. N. (1993) LPSC XXIV, 685-686. [3] Davis A. M. et al. (1990) Nature, 347, 655-658. [4] Wulf A. V. and Palme H. (1991) LPSC XXII, 1527-1528. [5] McDonough W. F. et al. (1992) GCA, 56, 1001-1012. Figure 1 appears here in the hard copy.

  19. 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 material and source rocks, respectively. Negative Ce anomaly is related to source rock material and influenced by lanthanum enrichment at certain sediment intervals.

  20. 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.

  1. 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, Bjrn; 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 ?m) 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 were associated with both the 0.5-3 nm fulvic rich and 4-40 nm iron rich nanocolloids and with larger >40 nm colloids. In a river sampled at higher altitude, the <8 nm organic/iron-rich and 4-40 nm iron-rich nanocolloids dominated the REE-binding also during the summer, which could be a result of persistent permafrost confining water flows to the upper organic-rich soil horizons.

  2. Are C1 chondrites chemically fractionated - A trace element study

    NASA Technical Reports Server (NTRS)

    Ebihara, M.; Wolf, R.; Anders, E.

    1982-01-01

    Six C1 chondrite samples and a C2 xenolith from the Plainview H5 chondrite were analyzed by radiochemical neutron activation for a large variety of elements, including rare earths. The sample processing is described, including the irradiation, chemical procedure, rare earths separation, counting techniques, radiochemical purity check, and chemical yields. The results of consistency checks on a number of elements are discussed. Abundances for siderophiles, volatiles, and rare earths are presented and discussed. Tests are presented for fractionation of rare earths and other refractories, compositional uniformity of C1's, and interelement correlations. There is no conclusive evidence for nebular fractionation affecting C1's. Three fractionation-prone rare earths have essentially the same relative abundances in C1's and all other chondrite classes, and hence are apparently not fractionated in C1's.

  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% SiO2. Silver on the other hand is essentially constant at 0.02 to 0.05ppm throughout the basalt to dacite compositional range. Several other compositional features of the Pacmanus and Valu Fa suites are also noteworthy. For example while S has an abundance maximum at 60wt% SiO2 (similar to Fe and Re), and then diminishes in concentration in more silica-rich magmas, Se is initially depleted at 60wt% SiO2 but then increases in abundance as SiO2 increases further. We suggest these features result from sulfide saturation coincidentally with (or shortly after) magnetite saturation. While Se is initially partitioned into the immiscible sulfide phase, moderate incompatibility remains between the overall fractionating assemblage of plagioclase-pyroxene- magnetite and minor sulfide. Pt on the other hand is likely being removed as a native element/alloy. Sun, W, Arculus, RJ, Kamenetsky, VS and Binns, RA, 2004, Release of gold-bearing fluids in convergent margin magmas prompted by magnetite crystallisation. Nature, v. 431, p. 975-978.

  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. 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.

  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 and REE in Mn ores from different geological settings and the geochemical processes promoting the metal accumulation. Results clearly showed that in the studied deposits only the contents of trace metals may be referred to uptake process on Mn mineral phases. On the contrary, REE are probably hosted in silicates, such as zircons and clay minerals, that also characterize the mineralization or their presence is due to redox processes not linked to Mn ore deposition. Sinisi R., Mameli P., Mongelli G., Oggiano G. (2012). Different Mn-ores in a continental arc setting: geochemical and mineralogical evidence from Tertiary deposits of Sardinia (Italy). Ore Geology Reviews, 47, 110-125.

  7. Rare earth elements: end use and recyclability

    USGS Publications Warehouse

    Goonan, Thomas G.

    2011-01-01

    Rare earth elements are used in mature markets (such as catalysts, glassmaking, lighting, and metallurgy), which account for 59 percent of the total worldwide consumption of rare earth elements, and in newer, high-growth markets (such as battery alloys, ceramics, and permanent magnets), which account for 41 percent of the total worldwide consumption of rare earth elements. In mature market segments, lanthanum and cerium constitute about 80 percent of rare earth elements used, and in new market segments, dysprosium, neodymium, and praseodymium account for about 85 percent of rare earth elements used. Regardless of the end use, rare earth elements are not recycled in large quantities, but could be if recycling became mandated or very high prices of rare earth elements made recycling feasible.

  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 Element Mines, Deposits, and Occurrences

    USGS Publications Warehouse

    Orris, Greta J.; Grauch, Richard I.

    2002-01-01

    Data on rare earth (including yttrium) mines, deposits, and occurrences were compiled as part of an effort by the USGS and the University of Arizona Center for Mineral Resources to summarize current knowledge on the supply and demand outlook and related topics for this group of elements. Economic competition and environmental concerns are increasingly constraining the mining and processing of rare earths from the Mountain Pass mine in California. For many years, the deposit at Mountain Pass was the world's dominant source of rare earth elements and the United States was essentially self-sufficient. Starting approximately 10 years ago, the U.S. has become increasingly dependent (> 90 percent of separated rare earths) upon imports from China, now the dominant source of rare earths. A knowledge of the known economic and noneconomic sources of rare earths is basic to evaluating the outlook for rare earth supply and associated issues.

  11. Moving KML geometry elements within Google Earth

    NASA Astrophysics Data System (ADS)

    Zhu, Liang-feng; Wang, Xi-feng; Pan, Xin

    2014-11-01

    During the process of modeling and visualizing geospatial information on the Google Earth virtual globe, there is an increasing demand to carry out such operations as moving geospatial objects defined by KML geometry elements horizontally or vertically. Due to the absence of the functionality and user interface for performing the moving transformation, it is either hard or impossible to interactively move multiple geospatial objects only using the existing Google Earth desktop application, especially when the data sets are in large volume. In this paper, we present a general framework and associated implementation methods for moving multiple KML geometry elements within Google Earth. In our proposed framework, we first load KML objects into the Google Earth plug-in, and then extract KML geometry elements from the imported KML objects. Subsequently, we interactively control the movement distance along a specified orientation by employing a custom user interface, calculate the transformed geographic location for each KML geometry element, and adjust geographic coordinates of the points in each KML objects. And finally, transformed KML geometry elements can be displayed in Google Earth for 3D visualization and spatial analysis. A key advantage of the proposed framework is that it provides a simple, uniform and efficient user interface for moving multiple KML geometry elements within Google Earth. More importantly, the proposed framework and associated implementations can be conveniently integrated into other customizable Google Earth applications to support interactively visualizing and analyzing geospatial objects defined by KML geometry elements.

  12. 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 rare-earth elements is not a simple unidirectional process. When a cerium-earth mineral undergoes replacement, its rare-earth elements may be fractionated into two parts, one forming a new mineral with ??? that is smaller, and the other a second new mineral with ??? that is larger than that of the original mineral. The complete analysis of a cerium-earth mineral to determine its ??? is time consuming. The discovery of a direct relationship between ??? and the Ce/(Nd + Y) atomic ratio in cerium earth minerals allows a rapid determination of ??? from spectrograms obtained in a previously described method for determining thorium in these minerals. ?? 1957.

  13. Mineral resource of the month: rare earth elements

    USGS Publications Warehouse

    U.S. Geological Survey

    2011-01-01

    The article provides information on rare earth elements, which are group of 17 natural metallic elements. The rare earth elements are scandium, yttrium and lanthanides and classified into light rare earth elements (LREE) and heavy rate earth elements (HREE). The principal ores of the rare earth elements are identified. An overview of China's production of 97 percent of the rare earths in the world is provided. Commercial applications of rare earths are described.

  14. 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.

  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.

    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

  17. 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.

  18. 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

  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 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.

  2. 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]). Similarities in textures, compositions, and fractionation patterns of the K-rich fragments suggest that they might be formed from related precursor materials with related processes. Complementarity of K-rich fragments and differentiated body alkali abundance patterns suggests that the fractionation could have occurred in the early solar nebula. Refs: [1] Wlotzka F. et al. (1983) Geochim. Cosmochim. Acta 47, 743. [2] Noonan A.F. et al. (1978) Geol. Survey Open File Report 78-701, 311. [3] Yanai K. et al. (1978) Mem. Natl. Inst. Polar Res. Spec. Issue 8, 110. [4] Ikeda Y. and Takeda H. (1979) Mem. Natl. Inst. Polar Res. Spec. Issue 15, 123. [5] Dodd R.T. (1981) Meteorites pp. 368, Cambridge Univ. Press. [6] Fodor R.V. and Keil K. (1978) Catalog of lithic fragments in LL-chondrites, Inst. Meteoritics Spec. Publ. No. 19, pp. 38, Univ. New Mexico, Albuquerque. [7] Humayun M. and Clayton R.N. (1995) Geochim. Cosmochim. Acta 59, 2131. [8] Kempe W. and Mueller O. (1969) Meteorite Res., pp. 418. [9] Nishiya N. et al. (1995) Okayama Univ. Earth Sci. Rep. 2, 91.

  3. 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

  4. 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.

  5. Leapfrog/finite element method for fractional diffusion equation.

    PubMed

    Zhao, Zhengang; Zheng, Yunying

    2014-01-01

    We analyze a fully discrete leapfrog/Galerkin finite element method for the numerical solution of the space fractional order (fractional for simplicity) diffusion equation. The generalized fractional derivative spaces are defined in a bounded interval. And some related properties are further discussed for the following finite element analysis. Then the fractional diffusion equation is discretized in space by the finite element method and in time by the explicit leapfrog scheme. For the resulting fully discrete, conditionally stable scheme, we prove an L (2)-error bound of finite element accuracy and of second order in time. Numerical examples are included to confirm our theoretical analysis. PMID:24955431

  6. Leapfrog/Finite Element Method for Fractional Diffusion Equation

    PubMed Central

    Zhao, Zhengang; Zheng, Yunying

    2014-01-01

    We analyze a fully discrete leapfrog/Galerkin finite element method for the numerical solution of the space fractional order (fractional for simplicity) diffusion equation. The generalized fractional derivative spaces are defined in a bounded interval. And some related properties are further discussed for the following finite element analysis. Then the fractional diffusion equation is discretized in space by the finite element method and in time by the explicit leapfrog scheme. For the resulting fully discrete, conditionally stable scheme, we prove an L 2-error bound of finite element accuracy and of second order in time. Numerical examples are included to confirm our theoretical analysis. PMID:24955431

  7. 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 mining to use to recycling quantifying the cycles for Japan, China and the U.S. as three representative types of consumers and paying attention to aspects of resource sustainability. Being well aware of the stages in the metal life cycle helps the sustainable development and policy making in long term. The goal is to consider REE resource availability, sustainability, and development strategies in the future that can sustain a reliable, steady, uninterrupted REE supply on the global market.

  8. 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.

  9. 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 oxidizing conditions at the surface of the Earth and setting the stage for the creation of an O2 atmosphere (Urey 1951, Catling et al 2001, Zahnle et al 2013). Catling, McKay, Zahnle (2001) Science 293, 839. Pujol, Marty, Burnard, Phillipot (2009) GCA 73, 6834. Pujol, Marty, Burgess (2011) EPSL 308, 298. Urey, H.C. (1952) PNAS 38, 351. Zahnle, Catling, Claire (2013) Ch. Geol. 362, 26.

  10. Tipping elements in the Earth's climate system

    PubMed Central

    Lenton, Timothy M.; Held, Hermann; Kriegler, Elmar; Hall, Jim W.; Lucht, Wolfgang; Rahmstorf, Stefan; Schellnhuber, Hans Joachim

    2008-01-01

    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 we introduce the term tipping element to describe large-scale components of the Earth system that may pass a tipping point. We 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 we 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 we explain how, in principle, early warning systems could be established to detect the proximity of some tipping points. PMID:18258748

  11. 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.

  12. Fractionation of elements during copper smelting

    SciTech Connect

    Germani, M.S.; Zoller, W.H.; Small, M.; Moyers, J.L.

    1981-03-01

    A recent study of the elemental composition of particulate material collected from the plumes of five copper smelters in southeastern Arizona indicated that arsenic, lead, selenium, cadmium, zinc, tungsten, indium, and other chalcophilic elements are highly enriched in the plume materials relative to the background aerosol. Enrichments are due to the volatilization of these elements during copper smelting. Significant differences in the elemental compositions of plumes from the various smelters appear to be due to differences in the feed material, smelting conditions, and equipment use by the smelters. (3 graphs, 13 references, 7 tables)

  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. Rare earth elements in weathering profiles and sediments of Minnesota: Implications for provenance studies

    USGS Publications Warehouse

    Morey, G.B.; Setterholm, D.R.

    1997-01-01

    The relative abundance of rare earth elements in sediments has been suggested as a tool for determining their source rocks. This correlation requires that weathering, erosion, and sedimentation do not alter the REE abundances, or do so in a predictable manner. We find that the rare earth elements are mobilized and fractionated by weathering, and that sediments derived from the weathered materials can display modifications of the original pattern of rare earth elements of some due to grain-size sorting of the weathered material. However, the REE distribution pattern of the provenance terrane can be recognized in the sediments.

  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. 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.

  17. 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.

  18. 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"

  19. The chemistry of rare earth elements in the solar nebula

    NASA Technical Reports Server (NTRS)

    Larimer, J. W.; Bartholomay, H. A.; Fegley, B.

    1984-01-01

    The high concentration of rare earth elements (REE) in primitive CaS suggests that the REE along with the other normally lithophile elements form stable sulfides under the unusual conditions which existed during the formation of enstatite chrondites. In order to acquire a more quantitative framework in which to interpret these data, the behavior of the REE in systems with solar, or slightly fractionated solar, composition is being studied. These new data introduce modest changes in the behavior of some of the REE when compared to previous studies. For example, the largest differences are in the stabilities of the gaseous monoxides of Ce, Eu, Tb, Ho, and Tm, all of which now appear to be less stable than previously thought, and YbO(g) which is somewhat more stable. Much more significant are the changes in REE distribution in the gas phase in fractionated systems, especially those made more reducing by changing the C/O ratio from the solar value of 0.6 to about 1.0. In almost all cases, the exceptions being Eu, Tm and Yb whose elemental gaseous species dominate, the monosulfides become more abundant. Moreover, the solid oxides of Eu, Tm and Yb become less stable under more reducing conditions which, in effect, should reduce the condensation temperature of all REE in more reduced systems.

  20. Rare earth element composition of precipitation, precipitation particles, and aerosols

    NASA Astrophysics Data System (ADS)

    Sholkovitz, Edward R.; Church, Thomas M.; Arimoto, Richard

    1993-11-01

    We report the rare earth element (REE) composition of aerosols and precipitation (dissolved and particle phases) from Bermuda, Lewes (Delaware), and Woods Hole (Massachusetts). There is large-scale fractionation of REEs between the continents, atmosphere, and the oceans. The REE compositions of atmospheric samples are highly fractionated relative to (1) each other (e.g., aerosol/precipitation pairs), (2) the upper crust of the Earth, and (3) seawater. Precipitation samples exhibit markedly convex-up shale-normalized patterns, large negative Eu anomalies and large and systematic depletions in the heavy REE (Lu greater than Yb greater than Er greater than Dy). Aerosols are strongly depleted in the heavy REE which dissolutions experiments show are attributable to the presence of HREE-enriched refactory minerals. We argue that in situ selective dissolution of mineral aerosol particles is responsible for the unusual REE composition of precipitation. This has major implications for the interpretation of the biogeochemical cycles of REEs in the oceans, particularly the partitioning between solution and particle phases, residence times, and the composition of seawater.

  1. 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's core-forming metal and silicate mantle, there should be an isotopic signature of Si in the core. Our experiments, combined with previous measurements of Si isotope ratios in meteorites and rocks representing the bulk silicate Earth, suggest that the formation of the Earth's core imparted a high 30Si/ 28Si signature to the bulk silicate Earth due to dissolution of ~ 6 wt% Si into the early core.

  2. 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.

  3. Rare earths and other trace elements in Luna 16 soil.

    NASA Technical Reports Server (NTRS)

    Helmke, P. A.; Haskin, L. A.

    1972-01-01

    An analysis has been made of four small samples of material brought to earth by the Luna 16 mission, with the aim to determine rare earths and other trace elements in these samples. The analytical results are tabulated, and the rare earth abundances are compared with the average for chondrites. A comparison is also made with the results of similar analyses of Apollo samples.

  4. 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, thus, their abundances in the bulk Earth likely reflect the average composition of Earth's building materials. Combined with evidence from nucleosynthetic isotope anomalies, the data suggest that Earth's main building materials originated from compartments of the inner solar system where volatile element abundances evolved differently from the formation area of known chondrites. The materials with nonchondritic volatile element composition may have been used up for building the terrestrial planets.

  5. 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.

  6. 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.

  7. 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.

  8. Fractionated space infrastructure for long-term earth observation missions

    NASA Astrophysics Data System (ADS)

    Chu, Jing; Guo, Jian; Gill, E. K. A.

    A fractionated spacecraft is a space system that distributes its functionalities, such as computation, communication, data storage, payload and even power generation, over several independent satellite modules that share those functionalities through a wireless link. This paper exploits this innovational architecture to design a space infrastructure that is able to accept and support multiple Earth Observation (EO) payload modules. In this paper the functional, physical and organizational architectures of the infrastructure are presented. To start with, EO programs utilizing monolithic spacecraft especially SPOT and Landsat programs are reviewed and analyzed to derive the inherent EO functional requirements. Then these functional requirements are integrated into an EO scenario based on a reference orbit typically for EO missions. Next, novel architectures of fractionated spacecraft are reviewed and the inherent non traditional attributes are summarized and classified in such a way to show their close interrelation with the EO functional requirements. Then four resources components: high bandwidth downlink component, data relay satellite communication component, mission data processor component and large volume data storage component are identified and designated to establish the EO space infrastructure. Based on those four components different physical architectures are designed for the specific scenario and then are evaluated using the Analytical Hierarchy Process (AHP) with eight selection criteria. Afterwards, the best option has been identified, which comprises four heterogeneous modules assigned to host those four resources components separately. Finally, this physical architecture is organized by means of the Multi-Agent System (MAS) theory, which fulfills best the EO non traditional requirements. The proposed organization is tailored for the autonomous operations of the fractionated infrastructure and is based on the peer-to-peer architecture. From a physica- and organizational perspective, the developed space infrastructure is able to self-adapt, self-optimize and self-configure to dynamic changes in various local environmental conditions.

  9. 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.

  10. Fractionation of moderately volatile elements in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Wasson, J. T.; Chou, C.-L.

    1974-01-01

    The CI chondrites are the most volatile-rich meteorites. Relative to the CI chondrites, the ordinary chondrites have lower abundances of refractory and volatile elements. Four types of fractionations are summarized in a table. Ordinary-chondrite/CI abundance ratios for moderately volatile elements in H- and L-group chondrites are presented in a graph. Possible explanations for the observed relations are considered, giving attention to several processes which could result in the separation of nebular solids and gases.

  11. 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 significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment-water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

  12. 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.

  13. 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.

  14. 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 ?15N = -20~25 permil during tholin formation, while 13C isotopic fractionation seems almost negligible. This negative ?15N 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 ?15N 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., 2004, 2012). Although the correlation of pressure might be just an apparent one, distinct type of chemistry could be the reason of such isotopic fractionation. The two distinct ?15N could be related to the difference of dominant functional groups, such as -NH2 and -CN. Since N-H functionality is more abundant in the tholins with depleted 15N, the observed isotopic fractionation could be related to the chemical bond change from N2 to -N-H functionality.

  15. 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 conclusions on the impact of depositional setting and diagenetic remobilization and authigenic mineral formation on the REE system in the Marcellus Shale.

  16. 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. Biotechnol. Bioeng. 2016;113: 339-348. © 2015 Wiley Periodicals, Inc. PMID:26332985

  17. 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.

  18. Exponentially accurate spectral and spectral element methods for fractional ODEs

    NASA Astrophysics Data System (ADS)

    Zayernouri, Mohsen; Karniadakis, George Em

    2014-01-01

    Current discretizations of fractional differential equations lead to numerical solutions of low order of accuracy. Here, we present different methods for fractional ODEs that lead to exponentially fast decay of the error. First, we develop a Petrov-Galerkin (PG) spectral method for Fractional Initial-Value Problems (FIVPs) of the form Dt?0u(t)=f(t) and Fractional Final-Value Problems (FFVPs) DT?tu(t)=g(t), where ??(0,1), subject to Dirichlet initial/final conditions. These schemes are developed based on a new spectral theory for fractional Sturm-Liouville problems (FSLPs), which has been recently developed in [1]. Specifically, we obtain solutions to FIVPs and FFVPs in terms of the new fractional (non-polynomial) basis functions, called Jacobi polyfractonomials, which are the eigenfunctions of the FSLP of first kind (FSLP-I). Correspondingly, we employ another space of test functions as the span of polyfractonomial eigenfunctions of the FSLP of second kind (FSLP-II). Subsequently, we develop a Discontinuous Spectral Method (DSM) of Petrov-Galerkin sense for the aforementioned FIVPs and FFVPs, where the basis functions do not satisfy the initial/final conditions. Finally, we extend the DSM scheme to a Discontinuous Spectral Element Method (DSEM) for efficient longer time-integration and adaptive refinement. In these discontinuous schemes, we employ the asymptotic eigensolutions to FSLP-I & -II, which are of Jacobi polynomial forms, as basis and test functions. Our numerical tests confirm the exponential/algebraic convergence, respectively, in p- and h-refinements, for various test cases with integer- and fractional-order solutions.

  19. Modeling rammed earth wall using discrete element method

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    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.

  20. 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.

  1. Uptake and distribution of rare earth elements in rice seeds cultured in fertilizer solution of rare earth elements.

    PubMed

    Yuan, D; Shan, X; Huai, Q; Wen, B; Zhu, X

    2001-04-01

    The uptake behavior of rare earth elements (REEs) under pot conditions using deionized water and a REE fertilizer solution as the culture media as well as the distribution of REEs in rice proteins were studied. The uptake of REEs in rice seeds increased dramatically after a lag period of approximately three days. Roots can accumulate a much higher content of REEs than germs and the resting seeds. The REE content in each water-soluble (albumin) and salt-soluble (globulin) component of the rice seeds accounted for 5-8% and 4-6% of the total REEs, respectively. However, there are less than 1.5% of the total REEs were found in the alcohol-soluble (prolamin) and acetic acid-soluble (glutelin) components. The high performance liquid chromatography (HPLC) in the gel permeation and the reserved-phase were used to monitor changes in the molecular weight distribution changes of the soluble proteins of rice seeds during germination after having been cultured in the same solution for seven days. No changes occurred in the prolamin, while a slight change occurred in the albumin, globulin and glutelin. Fractionation of the albumin of rice seeds cultured in a REE fertilizer solution on the Sephadex G-100 column indicated that REEs, especially Ce, La, Pr and Nd, were associated mainly with biological compounds of a molecular weight between 10,000 and 12,000. PMID:11302578

  2. Rare earth elements as a fingerprint of soil components solubilization

    NASA Astrophysics Data System (ADS)

    Davranche, M.; Grybos, M.; Gruau, G.; Pdrot, M.; Dia, A.

    2009-04-01

    The retention of rare earth element (REE) in the soil profile are mainly controlled by three factors, (i) the stability of the primary REE-carrying minerals, (ii) the presence of secondary phases as clays and Fe- and Mn-oxyhydroxides and (ii) the concentration of colloidal organic matter (OM). Considering that each soil phases (mineral or organic) displays (ii) various surface properties, such as specific area, surface sites density and nature and (ii) their own REE distribution inherited from the rock weathering, their mobilization through various chemical reactions (dissolution, colloidal release.) may involve the development of various shaped REE patterns in the soil solutions. REE fractionation from the different soil phases may therefore be used to identify the response of the soil system to a particular chemical process such as reductive and/or acidic dissolution. To test this purpose, an organic-rich wetland soil sample was incubated under anaerobic condition at both pH 5 and uncontrolled pH. The REE patterns developed in the soil solution were then compared to the REE patterns obtained through either aerobic at pH 3 and 7 incubations or a chemical reduction experiment (using hydroxylamine). REE patterns in anaerobic and aerobic at pH 7 experiments exhibited the same middle rare earth element (MREE) downward concavity significant of the complexation of REE with soil OM. By contrast, under acidic condition, the REE pattern exhibited a positive Eu anomaly due to the dissolution of soil feldspar. Finally, REE pattern obtained from the chemical reducing experiment showed an intermediary flat shape corresponding to a mixing between the soil organic and mineral phases dissolution. The comparison of the various REE pattern shapes allowed to conclude that (i) biological reduction of wetland soil involved amorphous Fe(III) colloids linked to OM and, (ii) that the REE mobility was controlled by the dynamic of OM in wetland soil. They also evidence the potential of REE to be use as a tracer of the soil phases involved in the various chemical processes running in soil solutions.

  3. Rare earth elements in scleractinian cold-water corals

    NASA Astrophysics Data System (ADS)

    Raddatz, J.; Liebetrau, V.; Hathorne, E. C.; Rüggeberg, A.; Dullo, W.; Frank, M.

    2012-12-01

    The Rare Earth Elements (REE) have a great potential to trace continental input, particle scavenging and the oxidation state of seawater. These REE are recorded in the skeleton of the cosmopolitan cold-water corals Lophelia pertusa. Here we use an online preconcentration ICP-MS method (Hathorne et al. 2012) to measure REE concentrations in seawater and associated cold-water coral carbonates in order to investigate their seawater origin. Scleractinian cold-water corals were collected in-situ and alive and with corresponding seawater samples covering from the European Continental Margin. The seawater REE patterns are characterized by the typical negative cerium anomaly of seawater, but are distinct for the northern Norwegian Margin and the Oslo Fjord, probably related to continental input. Initial results for the corresponding coral samples suggest that these distinct REE patterns of ambient seawater are recorded by the coral skeletons although some fractionation during incorporation into the aragonite occurs. This indicates that scleractinian cold-water corals can serve as a valuable archive for seawater derived REE signatures, as well radiogenic Nd isotope compositions. In a second step we analysed fossil coral samples from various locations, which were oxidatively and reductively cleaned prior to analysis. Initial results reveal that sediment-buried fossil (early Pleistocene to Holocene) coral samples from the Norwegian Margin and the Porcupine Seabight (Challenger Mound, IODP Site 1317) do not show the expected seawater REE patterns. In particular, the fossil coral-derived REE patterns lack a negative cerium anomaly suggesting that fossil coral-REE patterns do not represent ambient seawater. Thus, we suggest that the oxidative-reductive cleaning method widely used for cleaning of marine carbonates such as foraminifera prior to measurements of seawater-derived trace metal and isotope compositions are not sufficient for REE and Nd isotopes in sediment-buried coral-water corals and require alternative or additional approaches. Hathorne, E.C., B. Haley, T. Stichel, P. Grasse, M. Zieringer, and M. Frank (2012). Online preconcentration ICP-MS analysis of rare earth elements in seawater, Geochem. Geophys. Geosyst.,13, Q01020, doi:10.1029/2011GC003907. .

  4. 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; Chron, 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 ?REE = 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 ?Nd values that typically range between the ?Nd signatures for terrestrial organic matter (inferred from the analysis of the sedimentary detrital fractions) and marine organic matter (inferred from the analysis of local surface seawater). A notable exception is the case of organic matter (OM) fractions leached from cold seep sediment samples, which sometimes exhibit ?Nd values markedly different from both terrigenous and surface seawater signatures. This suggests that a significant fraction of organic compounds in these sediments may be derived from chemosynthetic processes, recycling pore water REE characterized by a distinct isotopic composition. Overall, our results confirm that organic matter probably plays an important role in the oceanic REE budget, through direct scavenging and remineralization within the water column. Both the high REE abundances and the shape of shale-normalized patterns for leached SOM also suggest that OM degradation in sub-surface marine sediments during early diagenesis could control, to a large extent, the distribution of REE in pore waters. Benthic fluxes of organic-bound REE could hence substantially contribute to the exchange processes between particulates and seawater that take place at ocean margins. Neodymium isotopes could provide useful information for tracing the origin (terrestrial versus marine) and geographical provenance of organic matter, with potential applications in paleoceanography. In particular, future studies should further investigate the potential of Nd isotopes in organic compounds preserved in sedimentary records for reconstructing past variations of surface ocean circulation.

  5. 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.

  6. 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.

  7. 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

  8. Diffusive fractionation of trace elements by chaotic mixing of magmas

    NASA Astrophysics Data System (ADS)

    Perugini, D.; Petrelli, M.; Poli, G.

    2006-03-01

    Recent research on magma mixing systems has shown that the mixing process is governed by chaotic dynamics and that this process is responsible for the generation of fractal structures that propagate within the magmatic mass from the meter to the micrometer length-scale. Laser Ablation ICP-MS trace element analyses have been performed on rock samples with evidence of chaotic mixing phenomena. Results indicate that trace elements with similar values of diffusion coefficient display good correlations in inter-elemental plots, whereas, as the difference between diffusion coefficients increases, the correlation is progressively lost. In addition, a large variability of REE patterns is observed, with the remarkable feature of the presence of positive and negative Eu anomalies occurring at short length scale, of the order of few mm. Given the chaotic nature of magma mixing structures, the mixing process has been simulated by coupling a chaotic advection and a chemical diffusion numerical scheme by considering several trace elements with variable diffusivities. Simulations indicate that such a model explains with good approximation the variable correlations among trace elements observed in natural samples. In addition, the same patterns of REE observed in natural samples, including the occurrence of positive and negative Eu anomalies at short length scale, are observed indicating that a chaotic advection/diffusion dynamic system is a suitable model to explain natural data. Results presented in this contribution indicate that at the micrometric length-scale small volumes of magmas are strongly influenced by the coupled action of chemical diffusion and chaotic flow fields and, hence, they do not represent magmas de facto present in the magmatic system because their compositions may have experienced a 'diffusive fractionation' process. These results may have important petrogenetic implications. For instance, if such melts were trapped as melt inclusions, they would provide misleading information about melt compositions. It is suggested that the approach of studying the degree of correlation among trace elements may be a possible method to test if melt inclusion compositions, commonly used as petrogenetic indicators, display evidence of such a 'diffusive fractionation' process.

  9. Levels of major and trace elements, including rare earth elements, and ²³⁸U in Croatian tap waters.

    PubMed

    Fiket, Željka; Rožmarić, Martina; Krmpotić, Matea; Benedik, Ljudmila

    2015-05-01

    Concentrations of 46 elements, including major, trace, and rare earth elements, and (238)U in Croatian tap waters were investigated. Selected sampling locations include tap waters from various hydrogeological regions, i.e., different types of aquifers, providing insight into the range of concentrations of studied elements and (238)U activity concentrations in Croatian tap waters. Obtained concentrations were compared with the Croatian maximum contaminant levels for trace elements in water intended for human consumption, as well as WHO and EPA drinking water standards. Concentrations in all analyzed tap waters were found in accordance with Croatian regulations, except tap water from Šibenik in which manganese in concentration above maximum permissible concentration (MPC) was measured. Furthermore, in tap water from Osijek, levels of arsenic exceeded the WHO guidelines and EPA regulations. In general, investigated tap waters were found to vary considerably in concentrations of studied elements, including (238)U activity concentrations. Causes of variability were further explored using statistical methods. Composition of studied tap waters was found to be predominately influenced by hydrogeological characteristics of the aquifer, at regional and local level, the existing redox conditions, and the household plumbing system. Rare earth element data, including abundances and fractionation patterns, complemented the characterization and facilitated the interpretation of factors affecting the composition of the analyzed tap waters. PMID:25430011

  10. ?-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.; Sderstrm, 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 ?-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. 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

  12. 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

  13. 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.

  14. Compositional and phase relations among rare earth element minerals

    NASA Technical Reports Server (NTRS)

    Burt, D. M.

    1990-01-01

    This paper discusses the compositional and phase relationships among minerals in which rare earth elements (REE) occur as essential constituents (e.g., bastnaesite, monazite, xenotime, aeschynite, allanite). Particular consideration is given to the vector representation of complex coupled substitutions in selected REE-bearing minerals and to the REE partitioning between minerals as related to the acid-base tendencies and mineral stabilities. It is shown that the treatment of coupled substitutions as vector quantities facilitates graphical representation of mineral composition spaces.

  15. 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, supported by CheMin results (Blake et al, 2013), as well as accurate geometry and environmental conditions are also considered for producing the best bulk chemistry, despite complications inherent to surface dust on unbrushed rock surfaces. The calculation of ALICs by the MSL APXS is a useful tool for producing in-situ values for volatile elements and provides an intermediate connection between the sub millimeter cubed scale of possible hydrogen concentrations found by ChemCam and the meter cubed hydrogen signature detected by DAN. These values also provide useful constraints on the absolute volatile concentrations found by SAM. MSL ALIC results are compared to previous results obtained for the 'dry' soils collected by the APXS on the MER rovers and provide a unique comparison of Martian samples from distinct locations on Mars. Results of MSL APXS data, including comparison with previous rover APXS analyses and complementary data from Curiosity's other instruments, will be presented.

  16. 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

  17. 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 has led to a 40% increase in atmospheric CO2 concentrations, and the atmospheric redistribution of reactive nitrogen and accumulation in remote ecosystems. We note that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements may surpass their corresponding natural fluxes. [1] Klee and Graedel (2004), Annu. Rev. Environ. Resour., 29, p. 69-107 [2] Sen and Peucker-Ehrenbrink (2012), Environ. Sci. Technol., dx.doi.org/10.1021/es301261x

  18. 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.

  19. Rubidium isotopes in primitive chondrites: Constraints on Earth's volatile element depletion and lead isotope evolution

    NASA Astrophysics Data System (ADS)

    Nebel, O.; Mezger, K.; van Westrenen, W.

    2011-05-01

    The bulk silicate Earth (BSE) shows substantial deficits in volatile elements compared to CI-chondrites and solar abundances. These deficits could be caused by pre-accretionary depletion in the solar nebula during condensation of solids, or by later heat-driven evaporation during collision of small bodies that later accreted to form the Earth. The latter is considered to result in isotope fractionation for elements with low condensation temperatures that correlates with the degree of depletion. Here, we report first high-precision isotope ratio measurements of the moderately volatile and lithophile trace element Rb. Data from seventeen chondrite meteorites show that their Rb isotope abundances are nearly indistinguishable from Earth, not deviating more than 1 per mil in their 87Rb/85Rb. The almost uniform solar system Rb isotope pool suggests incomplete condensation or evaporation in a single stage is unlikely to be the cause of the volatile element deficit of the Earth. As Rb and Pb have similar condensation temperatures, we use their different degrees of depletion in the BSE to address the mechanisms and timing of terrestrial volatile depletion. The Rb isotope data are consistent with a scenario in which the volatile budget of the Earth was generated by a mixture of a highly volatile-element depleted early Proto-Earth with undepleted material in the course of terrestrial accretion. Observed Pb and Rb abundances and U-Pb and Rb-Sr isotope systematics suggest that volatile addition occurred at approximately the same time at which last core-mantle equilibration was achieved. In line with previous suggestions, this last equilibration involved a second stage of Pb (but not Rb) depletion from the BSE. The timing of this second Pb loss event can be constrained to ~ 110 Ma after the start of the solar system. This model supports a scenario with core storage of Pb in the aftermath of a putative Moon forming giant impact that also delivered the bulk of the volatile elements to the Earth.

  20. Catalytic properties of monophosphates of rare-earth elements

    SciTech Connect

    Mel'nikov, P.P.; Koldasheva, E.M.; Kubason, A.A.; Lais Pichardo, Kh.

    1986-11-01

    From analysis of literature data it follows that use of structural analogies often leads to new catalytic systems. A characteristic example is zeolites and phosphates of group III elements which have as basic structural unit the PO/sub 4/ tetrahedron. The catalytic properties of zeolites and phosphates are well known in transformations of ethanol. In this work the catalytic properties of the complex rare-earth phosphates H/sub 3/HO (PO/sub 4/)/sub 2/, K/sub 2/CsTm(PO/sub 4/) /sub 2/, and K/sub 2/CsEr(PO/sub 4/) /sub 2/ in the above reaction are investigated, Phosphates containing rare-earth an alkaline cations were obtained by the cryochemical method.

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

    PubMed

    Santoro, A; Thoss, V; Ribeiro Guevara, S; 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 10pgg(-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

  2. 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.

  3. Rare-earth element geochemistry of the Samail Ophiolite near Ibra, Oman

    NASA Astrophysics Data System (ADS)

    Pallister, John S.; Knight, Roy J.

    1981-04-01

    Rare-earth element (REE) analyses of 68 rock and mineral separate samples from the Samail ophiolite clearly differentiate the various units of the ophiolite suite and indicate that the crustal suite is cogenetic, produced by crystal fractionation of basaltic magma in a spreading ridge magma chamber. Mantle peridotites are residual in rare-earth character, but cannot be clearly related to the overlying mafic rocks. Chromian spinel is probably insignificant in its effect on REE distribution during partial melting and crystal fractionation, as indicated by the low REE concentrations in chromitite from the Samail. Layered gabbro REE patterns are dominated by cumulus clinopyroxene and plagioclase. Large positive Eu anomalies demonstrate plagioclase accumulation. Modal mixing (mass balance) calculations reveal that most of these adcumulus gabbros have REE patterns that are the products of the REE concentrations of their constituent cumulus phases in the observed modal proportions; hence no appreciable REE-rich mesostasis is present. Such calculations also allow the prediction of mineral REE concentrations not actually determined by mineral separate analyses. Several high-level (noncumulus?) gabbros yield patterns with positive Eu anomalies suggesting relative plagioclase accumulation, probably due to liquid fractionation (filter pressing). Dike complex REE patterns show light rare-earth element depletions and are similar to, but not necessarily diagnostic of, midocean ridge basalt. They cluster at similar abundance levels; however, the absolute variation in abundance is large, indicative of modification by crystal fractionation. Calculations using partition coefficient data indicate that many dikes represent liquids that could have existed in equilibrium with cumulus minerals of the plutonic suite. Mineral separate REE data from layered cumulus gabbro of the Khafifah stratigraphic section reveal cryptic variation trends that are correlated with major element variation, in support of a long-lived (periodically replenished) magma chamber model (Pallister and Hopson, 1978, 1979, 1981). (Cryptic variation as used herein is defined as the change in mineral composition with respect to stratigraphic position.) The REE cryptic variation shows both direct and inverse correlation to major element variation, indicating that magmatic replenishment was complicated by changes in parent melt REE abundance. A crystal fractionation origin for the small plagiogranite bodies of the Ibra area is favored by REE modeling, although larger bodies (Dasir) may also be related to magmatic inclusion of roofrock with diabase level REE distribution (Gregory and Taylor, 1979).

  4. 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.

  5. 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.

  6. Magnetic property improvement of niobium doped with rare earth elements

    NASA Astrophysics Data System (ADS)

    Jiang, Tao; He, Fei-Si; Jiao, Fei; He, Fa; Lu, Xiang-Yang; Zhao, Kui; Zhao, Hong-Yun; You, Yu-Song; Chen, Lin

    2014-05-01

    A new idea is proposed by the PKU group to improve the magnetic properties of the Type-II superconductor niobium. Rare earth elements like scandium and yttrium are doped into ingot niobium during the smelting processes. A series of experiments have been done since 2010. The preliminary testing results show that the magnetic properties of niobium materials have changed with different doping elements and proportions while the superconductive transition temperature does not change very much. This method may increase the superheating magnetic field of niobium so as to improve the performance of the niobium cavity, which is a key component of SRF accelerators. A Tesla-type single-cell cavity made of scandium-doped niobium is being fabricated.

  7. 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.

  8. Origin of Terrestrial Water: Hydrogen/Deuterium Fractionation into Earth's Core

    NASA Astrophysics Data System (ADS)

    Wu, J.; Buseck, P. R.

    2014-12-01

    Hydrogen isotopic compositions are among the most important constraints on the origin of Earth's water. Earth's bulk water content, which is small but not negligible, is significantly greater than what the thermal gradient of the solar nebula disk would suggest for planetesimal materials condensed at one astronomical unit. The proto-solar nebula is a likely source of early Earth's water, with probable contributions from one or more of the following: water-rich planetesimals, ordinary and carbonaceous meteorites, comets, asteroids, and interplanetary dust particles. However, all of these sources have been questioned, and the proposed proto-solar nebular origin has been disputed in light of the large difference in hydrogen isotopic composition between it and terrestrial water. Current opposition to the solar nebular hypothesis is based on the critical assumption that no processes in the interior of the early Earth changed the isotopic composition of hydrogen. Nevertheless, a hypothesized hydrogenation reaction of liquid iron (2Fe + xH2 ? 2FeHx) during core formation likely provided a fractionation mechanism between hydrogen and deuterium (D). We propose that modern D/H ratios at Earth's surface resulted from this isotopic fractionation and that terrestrial water originated from oxidation of proto-solar hydrogen dissolved in the magma ocean in the early Earth by coexisting oxides (such as FeO). Thus, the isotopic composition of water on Earth can be mainly explained by internal terrestrial processes.

  9. 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

  10. 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

  11. 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.; Thiaudire, Dominique; Charbonnier, Sylvain; Clment, Gal; Bertrand, Loc

    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

  12. 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; Thiaudire, Dominique; Charbonnier, Sylvain; Clment, Gal; Bertrand, Loc

    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

  13. Rare earth element deposition in pelagic sediment at the Cenomanian-Turonian Boundary, Exmouth Plateau

    NASA Astrophysics Data System (ADS)

    Dickens, Gerald R.; Owen, Robert M.

    1995-02-01

    Ocean Drilling Program (ODP) Site 762 (eastern Indian Ocean) includes a section of sediment that spans the Cenomanian-Turonian Boundary (CTB) and was deposited along a continental margin during a period of widespread oceanic O2 deficiency. The rare earth element (REE) content of pre- and post-boundary sediment is similar to that of present-day continental slope material deposited in well-oxygenated seawater, whereas the CTB section is characterized by significantly depleted REE abundances, a bulk Ce anomaly that increases to maximum of 1.0, and a REE pattern that resembles that of present-day fluvial material. We suggest the change in REE patterns reflects release of scavenged REEs upon reductive dissolution of authigenic Fe-Mn oxyhydroxides, such that sediment deposited during the CTB is dominated by the lithogeneous REE fraction. These results are consistent with recent models concerning pervasive fractionation of Mn and Fe and redirection of Mn in pelagic CTB waters.

  14. 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 is probably best explained by preferential alteration of feldspars and/or accessory mineral phases. Importantly, this finding clearly indicates that silicate weathering can lead to decoupling of REE between different grain-size fractions, with implications for sediment provenance studies. Finally, we propose a set of values for a World River Average Clay (WRAC) and Average Silt (WRAS), which provide new estimates for the average composition of the weathered and eroded upper continental crust, respectively, and could be used for future comparison purposes.

  15. 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.

  16. Revisiting the rare earth elements in foraminiferal tests [rapid communication

    NASA Astrophysics Data System (ADS)

    Haley, Brian A.; Klinkhammer, Gary P.; Mix, Alan C.

    2005-10-01

    Are the rare earth elements (REEs) in foraminifera a valuable proxy for use in paleoceanographic and climate change studies? In order to investigate this, we attempted a comprehensive study of REEs in planktonic and benthic foraminifera. Several different cleaning protocols were tested. Although the hydroxylamine used to clean all foraminifera in this study removes an unidentified source of REE contamination, it seems to remobilize metal oxides that are otherwise unaffected in flow-through dissolution. The calculated REE distribution coefficients, KD(REE)s, are between 100 and 500 for both planktonic and benthic foraminifera. These KDs are high compared to other elements in biogenic calcite but can be explained through a general model of element incorporation during foraminiferal calcification. From data taken from eight core tops in the southeast Pacific, we conclude that the REEs in planktonic foraminifera are, indeed, useful as a proxy for upper ocean water mass and mixed layer biogenic productivity. Alternatively, the REEs in benthic foraminifera are useful as a proxy for carbon flux to the sea floor. These proxies should be robust down core unless the sediments have undergone anoxic diagenesis, which stabilizes Fe carbonate thus overprinting the primary REE signature. However, it is clear from REE distributions in foraminiferal tests if anoxic conditions have occurred.

  17. 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 observed in the shergottite pyroxenes is only consistent with degassing of LLE from a Martian melt near its liquidus temperature if the vapor-melt partition coefficient was an order of magnitude larger than observed on Earth. The range in LLE and trace elements observed in shergottite pyroxenes are instead consistent with concurrent mixing and fractionation of heterogeneous melts from the mantle.

  18. Selenium isotopes indicate a chondritic origin of volatile elements on Earth

    NASA Astrophysics Data System (ADS)

    Vollstaedt, H.; Mezger, K.; Leya, I.

    2014-12-01

    For a planet to provide conditions that are conducive for the origin and evolution of life, it is required to host liquid water and other volatile elements and compounds. The details of the planet forming processes starting from the condensation of matter in the solar nebula to the accretion of planets are, however, still elusive. Specifically, how planets like Venus, Earth, and Mars acquired their volatile element content, although they formed so close to the Sun and inside the snowline of the early solar system is a matter of the current scientific debate. To constrain the origin and addition of moderately to highly volatile components to the rocky planets of the inner solar system we studied the variation of the isotopes of the highly volatile, chalcophile, and siderophile element selenium (Se) and its abundance in different early solar system materials, planetesimals, and planets. Selenium is depleted within the Silicate Earth relative to CI , but in chondritic-relative abundance to siderophile elements like S and Te (Wang and Becker, 2013). The latter might reflect the accretion of a chondritic 'late veneer' after core formation which might also be the dominant source of water and carbon. The Se isotope composition (?82/76Se) of ordinary and iron meteorites and a terrestrial sample (Green River Shale, SGR-1, USGS) were found to be identical within the measurement uncertainty. If the depletion of volatile elements on Earth were exclusively caused by removal during core formation and/or evaporation during planet formation, a strongly Se-depleted and isotopically fractionated silicate reservoir would be expected. The relatively uniform ?82/76Se values between different groups of meteorites and the terrestrial value point to a later addition of volatiles to Earth from a source that contained unfractionated Se isotopes and thus originates most likely from a region within the solar system where the volatile elements and compounds condensed quantitatively. Wang, Z., Becker, H., 2013. Ratios of S, Se and Te in the silicate Earth require a volatile-rich late veneer. Nature 499, 328-331.

  19. 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.

  20. Rare earth elements activate endocytosis in plant cells

    PubMed Central

    Wang, Lihong; Li, Jigang; Zhou, Qing; Yang, Guangmei; Ding, Xiao Lan; Li, Xiaodong; Cai, Chen Xin; Zhang, Zhao; Wei, Hai Yan; Lu, Tian Hong; Deng, Xing Wang; Huang, Xiao Hua

    2014-01-01

    It has long been observed that rare earth elements (REEs) regulate multiple facets of plant growth and development. However, the underlying mechanisms remain largely unclear. Here, using electron microscopic autoradiography, we show the life cycle of a light REE (lanthanum) and a heavy REE (terbium) in horseradish leaf cells. Our data indicate that REEs were first anchored on the plasma membrane in the form of nanoscale particles, and then entered the cells by endocytosis. Consistently, REEs activated endocytosis in plant cells, which may be the cellular basis of REE actions in plants. Moreover, we discovered that a portion of REEs was successively released into the cytoplasm, self-assembled to form nanoscale clusters, and finally deposited in horseradish leaf cells. Taken together, our data reveal the life cycle of REEs and their cellular behaviors in plant cells, which shed light on the cellular mechanisms of REE actions in living organisms. PMID:25114214

  1. Rare Earth elements in individual minerals in Shergottites

    NASA Technical Reports Server (NTRS)

    Wadhwa, Meenakshi; Crozaz, Ghislaine

    1993-01-01

    Shergottites (i.e., Shergotty, Zagami, EETA79001, ALHA77005, and LEW88516) are an important set of achondrites because they comprise the majority of the SNC group of meteorites (nine, in total, known to us), which are likely to be samples of the planet Mars. Study of these meteorites may therefore provide valuable information about petrogenetic processes on a large planetary body other than Earth. Rare earth element (REE) distributions between various mineral phases were found to be useful in geochemically modeling the petrogenesis of various rock types (terrestrial and meteoritic). However, with the exception of a few ion microprobe studies and analyses of mineral separates, there has previously not been any comprehensive effort to characterize and directly compare REE in individual minerals in each of the five known shergottites. Ion microprobe analyses were made on thin sections of each of the shergottites. Minerals analyzed were pyroxenes (pigeonite and augite), maskelynite, and whitlockite. The REE concentrations in each mineral type in each shergottite is given.

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

    NASA Astrophysics Data System (ADS)

    Herwartz, Daniel; Ttken, 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.

  3. 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.

  4. Online preconcentration ICP-MS analysis of rare earth elements in seawater

    NASA Astrophysics Data System (ADS)

    Hathorne, Ed C.; Haley, Brian; Stichel, Torben; Grasse, Patricia; Zieringer, Moritz; Frank, Martin

    2012-01-01

    The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available "seaFAST" system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2?) of the technique to be estimated at <23% for all REEs and <15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.

  5. Rare Earth Element Geochemistry of Atacama Desert Soils

    NASA Astrophysics Data System (ADS)

    Sutter, B.; Ewing, S.; Amundson, R.; McKay, C.

    2003-12-01

    The Atacama Desert of northern Chile is one of driest deserts in the world, with a hyper-arid climate that arguably has persisted since the Miocene. Soils in the driest parts of the Atacama record the effects of long-term hyperaridity, retaining atmospherically-derived elements in quantities rarely seen on Earth. Recent work has demonstrated that the hyper-arid environment allows Atacama soils to accumulate large amounts of sulfate (e.g., anhydrite, gypsum), nitrate (NaNO3), and chloride (halite) that result in radical volumetric expansion of the soil. Possible salt sources include eolian redistribution from Atacama playas and/or marine aerosols. The objective of this work is to examine the rare earth element (REE) geochemistry of Atacama soils in order to understand how these trace elements chemically behave as soil water decreases to nearly zero. Two soils developed on fluvial landforms were examined along a south to north transect (Copiapo to Yungay) that coincides with decreasing moisture levels ( 15mm to 2 mm yr-1, south to north). Both soils have likely been undergoing soil formation since the Plio-Pleistocene. REE mass balance determinations were conducted on both soils through a comparison to that of the granitic alluvium from which they formed. An apparent net loss of REE relative to the granitic alluvium (10 to 30% Yungay; 15 to 65% Copiapo) has been calculated for these soils. The apparent loss of REE in both soils suggests that REE have been removed by some process or they have been have been diluted by dust and aerosols that have lower REE levels. Atmospheric deposition of marine and non-marine salts is the likely cause for the net loss of REE in the most arid soil, while weathering and leaching losses are a likely cause in the more humid endmember. Salts of marine origin are known to have low REE levels. Chondrite-normalized REE diagrams of the soils and parent materials are examined to determine if variations in local parent materials are evident. Europium anomalies, La/Yb, Gb/Yb, and Sm/Nd ratios are also presented to assess variations between soil horizons and parent materials.

  6. Rare earth elements in sinters from the geothermal waters (hot springs) on the Tibetan Plateau, China

    NASA Astrophysics Data System (ADS)

    Feng, Jin-Liang; Zhao, Zhen-Hong; Chen, Feng; Hu, Hai-Ping

    2014-10-01

    The mineralogical and geochemical composition of sinters from the geothermal areas on the Tibetan Plateau was determined. They occur as siliceous, salty and calcareous sinters but biogenic siliceous sinters were also found. The analyses indicate that there are no distinct inter -element relationships between individual rare earth elements (REEs) and other elements. Formed from the same geothermal water, the mineralogical and chemical composition of the sinters is influenced by their genesis and formation conditions. The REE distributions depend on the origin of the sinters. Fe-Mn phases in sinters tend to scavenge more REEs from geothermal water. Neither the REE fractionation nor the Ce anomaly seems to be associated with Fe-Mn phases in the sinters. The fourth tetrads of some sinters display weak W-type (concave) effects. In contrast, the third tetrads present large effects in some sinters due to positive Gd anomalies. The origin of the positive Eu anomalies in some sinters seems to be caused by preferential dissolution of feldspars during water-rock interaction. The complexing ligands in geothermal water may contribute significantly to the fractionation of REEs in sinters. The dominant CO32- and HCO3- complexing in geothermal water favors enrichment of heavy REEs in calcareous sinters.

  7. 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

  8. The lherzolitic shergottite Grove Mountains 99027: Rare earth element geochemistry

    NASA Astrophysics Data System (ADS)

    Hsu, Weibiao; Guan, Yunbin; Wang, Henian; Leshin, Laurie A.; Wang, Rucheng; Zhang, Wenlan; Chen, Xiaoming; Zhang, Fusheng; Lin, Chengyi

    2004-05-01

    We report here on an ion probe study of rare earth element (REE) geochemistry in the lherzolitic shergottite Grove Mountains (GRV) 99027. This meteorite shows almost identical mineralogy, petrology, and REE geochemistry to those of the lherzolitic shergottites Allan Hills (ALH) A77005, Lewis Cliff (LEW) 88516, and Yamato (Y-) 793605. REE concentrations in olivine, pyroxenes, maskelynite, merrillite, and melt glass are basically comparable to previous data obtained from ALH A77005, LEW 88516, and Y-793605. Olivine is the dominant phase in this meteorite. It is commonly enclosed by large (up to several mm) pigeonite oikocrysts. Non-poikilitic areas consist of larger olivine grains (~mm), pigeonite, augite, and maskelynite. Minor merrillite (up to 150 mm in size) is widespread in non-poikilitic regions, occurring interstitially between olivine and pyroxene grains. It is the main REE carrier in GRV 99027 and has relatively higher REEs (200-1000 CI) than that of other lherzolitic shergottites. A REE budget calculation for GRV 99027 yields a whole rock REE pattern very similar to that of other lherzolites. It is characterized by the distinctive light REE depletion and a smooth increase from light REEs to heavy REEs. REE microdistributions in GRV 99027 strongly support the idea that all lherzolitic shergottites formed by identical igneous processes, probably from the same magma chamber on Mars. Despite many similarities in mineralogy, petrography, and trace element geochemistry, subtle differences exist between GRV 99027 and other lherzolitic shergottites. GRV 99027 has relatively uniform mineral compositions (both major elements and REEs), implying that it suffered a higher degree of sub-solidus equilibration than the other three lherzolites. It is notable that GRV 99027 has experienced terrestrial weathering in the Antarctic environment, as its olivine and pyroxenes commonly display a light REE enrichment and a negative Ce anomaly. Caution needs to be taken in future chronological studies.

  9. 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.

  10. 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, establishing a company in China can lower the production cost (since the company buys the products used in its production at a lower price). In the fifth session, they study the raw materials trading based on the futures contracts example. A producer, to avoid a rise in prices of raw materials used in his production can use derivative products on the financial market: futures contracts for instance. This product ensures a quantity and quality for a price and a delivery date agreed upon today. Actually, producers can use a method called Fix price hedging in order to fix the price of a specific product. The main idea is to balance out the "physical position" (spot market) and the "paper position" (futures market). Even if the REE are commercialized in form of a non-perishable's oxide, the flow of the stock must be guaranteed and this is why it is important for producers to secure their supply of raw materials. In the last session, students search local companies that use REE in their production process and study their strategy on the market.

  11. Targeting heavy rare earth elements in carbonatite complexes

    NASA Astrophysics Data System (ADS)

    Broom-Fendley, S.; Wall, F.; Gunn, A. G.; Dowman, E.

    2012-04-01

    The world's main sources of the rare earth elements (REE) are concentrated in carbonatite complexes. These have the advantages of high grade and tonnage, combined with low thorium contents, yet they are generally enriched in light rare earths (LREE). The heavy rare earths (HREE, which include Eu-Lu and Y) are more highly sought after because of their role in new and green technologies. HREE are predominantly extracted from ion-adsorption clays in China. These are small, low grade deposits, which are often illegally mined by artisans. Increased government control, environmental legislation and local demand for REE in China have led to high prices and global concerns about the security of supply of the HREE. Alternative sources of the HREE are poorly documented. We present a review of such targets, including: (1) 'abnormal' carbonatites; (2) areas around LREE-rich complexes such as breccia, fenite and latter stage veins; and (3) weathered carbonatites. At Lofdal, Namibia, carbonatite dykes contain xenotime-(Y) together with LREE minerals. The original chemistry of the carbonatite magma, coupled with late-stage magma and fluid evolution, seem to be controlling factors [1, 2]. The Khibina carbonatite, Kola Peninsula, Russia, is an example of where early LREE carbonatites become increasing HREE-enriched as magmas evolve to carbo-hydrothermal fluids [3]. Around carbonatite complexes in Malawi HREE enrichment can be found in breccia and in fenite. Breccia around Songwe shows areas with high Y/La ratios within the matrix caused by narrow zones of xenotime enrichment. Fenite around Kangankunde and Chilwa Island has higher HREE:LREE ratios than the carbonatite [4]. At weathered complexes, such as at Mount Weld in Western Australia, changes in both HREE concentration and LREE:HREE ratios are observed. In currently unworked sections of the deposit, the HREE mineral churchite (YPO4.H2O) has formed concentrations due to groundwater flow [5]. These areas of enrichment are reviewed in terms of their grade, tonnage, rock type and the potential environmental impacts associated with their exploitation. [1] Wall et al. (2008), Can Mineral, 46, 861. [2] Do Cabo et al. (2011), Minmag, 75 (3), 770. [3] Zaitsev et al. (1998), Minmag, 62 (2), 225. [4] Dowman et al. (2011), abstract, Fermor conference, London. [5] Lottermoser (1990), Lithos, 24, 151

  12. 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

  13. Geochemical prospecting for rare earth elements using termite mound materials

    NASA Astrophysics Data System (ADS)

    Horiuchi, Yu; Ohno, Tetsuji; Hoshino, Mihoko; Shin, Ki-Cheol; Murakami, Hiroyasu; Tsunematsu, Maiko; Watanabe, Yasushi

    2014-12-01

    The Blockspruit fluorite prospect, located in North West State of the Republic of South Africa, occurs within an actinolite rock zone that was emplaced into the Kenkelbos-type granite of Proterozoic age. There are a large number of termite mounds in the prospect. For geochemical prospecting for rare earth elements (REEs), in total, 200 samples of termite mound material were collected from actinolite rock and granite zones in the prospect. Geochemical analyses of these termite mound materials were conducted by two methods: portable X-ray fluorescence (XRF) spectrometry and inductively coupled plasma-mass spectrometry (ICP-MS). Comparison of the two methods broadly indicates positive correlations of REEs (La, Ce, Pr, Nd, and Y), in particular Y and La having a strong correlation. As the result of modal abundance analyses, the actinolite rock at surface mainly consists of ferro-actinolite (89.89 wt%) and includes xenotime (0.26 wt%) and monazite (0.21 wt%) grains as REE minerals. Termite mound materials from actinolite rock also contain xenotime (0.27 wt%) and monazite (0.41 wt%) grains. In addition, termite mound materials from the actinolite rock zone have high hematite and Fe silicate contents compared to those from granite zone. These relationships suggest that REE minerals in termite mound materials originate form actinolite rock. Geochemical anomaly maps of Y, La, and Fe concentrations drawn based on the result of the portable XRF analyses show that high concentrations of these elements trend from SW to NE which broadly correspond to occurrences of actinolite body. These results indicate that termite mounds are an effective tool for REE geochemical prospection in the study area for both light REEs and Y, but a more detailed survey is required to establish the distribution of the actinolite rock body.

  14. 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.

  15. 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 provided information about the autochthonous microflora inhabiting skeleton and fine earth as well as information about the fate of soil DNA in terms of presence, persistence and movement of eDNA and the stored genetic information.

  16. 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 elements such as Ca, Mg, Sr or U are relatively high in whitewater rivers, their concentrations are generally lower in clearwater rivers and lowest in blackwater rivers. In contrast, elements including Si, Rb and Cs have their highest concentrations in blackwater rivers, intermediate concentrations in clearwater rivers and their lowest concentrations in whitewater river. [1] Elderfield H., Upstill-Goddard R. and Sholkovitz E.R. (1990): The rare earth elements in rivers, estuaries and coastal seas and their significance to the composition of ocean waters. Geochim.Cosmochim.Acta, 54, 971-991 [2] Gerard M., Seyler P., Benedetti M.F., Alves V.P., Boaventura G.R. and Sondag, F. (2003): Rare earth elements in the Amazon basin. Hydrological Processes, 17, 1379-1392 [3] Molinier M., Guyot J.L., Callede J., Guimaraes V., Oliveira E. and Filizola N. (1997): Hydrologie du bassinamazonien. Evironment et développement en Amazonie brésiliènne, Thery H. (ed.), Berlin Publ., Paris; 24-41

  17. Highly siderophile elements: Constraints on Earth accretion and early differentiation

    NASA Astrophysics Data System (ADS)

    Righter, Kevin

    Highly siderophile elements (HSE: Re, Au, and the PGEs) prefer FeNi metal and sulfide phases over silicate melts and minerals (olivine, pyroxene, feldspar, etc.). In addition, three HSE—Re, Pt, and Os—are involved in radioactive decay schemes: 187Re → 187Os (beta decay) and 192Pt → 188Os (alpha decay). As a result, they have provided constraints on the conditions during establishment of the primitive upper mantle, and the conditions and timing of later mantle differentiation and evolution. Hypotheses proposed to explain HSE elemental and isotopic compositions in the primitive upper mantle include mantle-core equilibrium, outer core metal addition, inefficient core formation, and late accretion (the late veneer). All of these scenarios have problems or unresolved issues. Here a hybrid model is proposed to explain the HSE concentrations in the primitive mantle, whereby Au, Pd, and Pt concentrations are set by high-pressure and temperature metal-silicate equilibrium, and Re, Ru, Rh, Ir, and Os concentrations are set by late accretion of chondritic material that is added via oxidized vapor following a giant impact (post-core formation). Processes affecting the later HSE evolution of the mantle include (1) layering caused by fractionation and/or flotation of mantle phases such as olivine, chromite, and garnet, (2) addition of metal from the outer core, and (3) recycling of oceanic crust. Uncertainties about differences in composition between the upper and lower mantle make evaluation of processes in the first category uncertain, but both the second and third processes can explain some aspects of mantle Os isotope geochemistry. This is a review of the field over the past decade and reports not only progress in the field but also highlights areas where much work remains.

  18. 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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  1. 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

  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. 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.

  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. Viewed globally, the accretional energy is about half the energy required to vaporize the entire Moon. Thus to first approximation, half of the Moon-forming material can be vaporized and lost during accretion. During this process, we would expect preferential loss of relatively volatile elements. Escape will retard the rate of accretion. To test these ideas, we computed detailed models of the thermal state of the Moon during accretion. We pay special attention to the structure of the silicate atmosphere and its loss rate by calculating the chemical species at equilibrium. We used the PHEQ program which includes 12 elements (H,O,C,Mg,Si,Fe,Ca, Al, Na,Ti, and N.) and 272 compounds (including ionic compounds). Because of the large heats of vaporization and ionization, the adiabatic atmosphere is nearly isothermal and massive escape is expected. The pressure of the atmosphere is determined by the balance between vaporization of a accreting material and escape. If the accretion time is one month, a 0.3 bar atmosphere is expected. Elemental fractionation depends strongly on the temperature of the accreting material. The initial temperature of the material can be estimated from the condition of gravitational instability in the protolunar disk. As shown by Ida et al, accretion starts when gravitational instability occurs when more than 99% of the material condenses. At this point, all of Ca, Al, Si, Mg, and Fe, and 95% of Na (probably K also), are in condensed phases. If the moon is formed from the accretion of such material, volatile elements such as Na, and K are retained by the moon only early in accretion. At later times, K and Na are lost and a fraction of the MG, Si and Fe is lost. However, refractory elements such as Ca and Al are retained and so achieve a mild degree (factor 2) of superabundance.

  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. Speciation of adsorbed yttrium and rare earth elements on oxide surfaces

    NASA Astrophysics Data System (ADS)

    Piasecki, Wojciech; Sverjensky, Dimitri A.

    2008-08-01

    The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y 3+ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species 4>SOH+M+2HO=(>SOH)2_M(OH)2++4H was found to account for a significant fraction of the adsorbed Y 3+, La 3+, Nd 3+, Gd 3+, and Yb 3+ on rutile, hematite, alumina and silica over wide ranges of pH and ionic strength. Where adsorption data were available as a function of surface coverage for hematite and silica, an additional reaction involving a mononuclear species could be used to account for the higher surface coverages. However, it is also possible that some of the higher surface coverage data refer to surface precipitation rather than adsorption. The results of the present study provide an internally consistent basis for describing YREE adsorption which could be used to investigate more complex systems in which YREE compete both in aqueous solution and on mineral surfaces with alkaline earths and ligands such as carbonate, sulfate, chloride and organic species, in order to build a predictive adsorption model applicable to natural waters.

  7. Recovery of rare earth elements from the sulfothermophilic red alga Galdieria sulphuraria using aqueous acid.

    PubMed

    Minoda, Ayumi; Sawada, Hitomi; Suzuki, Sonoe; Miyashita, Shin-ichi; Inagaki, Kazumi; Yamamoto, Takaiku; Tsuzuki, Mikio

    2015-02-01

    The demand for rare earth elements has increased dramatically in recent years because of their numerous industrial applications, and considerable research efforts have consequently been directed toward recycling these materials. The accumulation of metals in microorganisms is a low-cost and environmentally friendly method for the recovery of metals present in the environment at low levels. Numerous metals, including rare earth elements, can be readily dissolved in aqueous acid, but the efficiency of metal biosorption is usually decreased under the acidic conditions. In this report, we have investigated the use of the sulfothermophilic red alga Galdieria sulphuraria for the recovery of metals, with particular emphasis on the recovery of rare earth metals. Of the five different growth conditions investigated where G. sulphuraria could undergo an adaptation process, Nd(III), Dy(III), and Cu(II) were efficiently recovered from a solution containing a mixture of different metals under semi-anaerobic heterotrophic condition at a pH of 2.5. G. sulphuraria also recovered Nd(III), Dy(III), La(III), and Cu(II) with greater than 90% efficiency at a concentration of 0.5 ppm. The efficiency remained unchanged at pH values in the range of 1.5-2.5. Furthermore, at pH values in the range of 1.0-1.5, the lanthanoid ions were collected much more efficiently into the cell fractions than Cu(II) and therefore successfully separated from the Cu(II) dissolved in the aqueous acid. Microscope observation of the cells using alizarin red suggested that the metals were accumulating inside of the cells. Experiments using dead cells suggested that this phenomenon was a biological process involving specific activities within the cells. PMID:25283836

  8. 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.

  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 Colomera and Weekeroo Station, formed when a molten Fe ball collided on a differentiated silicate regolith near the surface of an asteroid. Silicate fragments were mixed with molten Fe by the impact. Heat from molten Fe caused localized melting of feldspar + pyroxene + tridymite assemblage. The inclusions remained isolated from one another during subsequent rapid cooling.

  10. 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.

  11. Trace elements in ocean ridge basalt glasses - Implications for fractionations during mantle evolution and petrogenesis

    NASA Technical Reports Server (NTRS)

    Hertogen, J.; Janssens, M.-J.; Palme, H.

    1980-01-01

    Seven documented and fresh glassy selvages from ocean floor basalt pillows were analyzed for trace elements including Ag, Au, Bi, Br, Ni, Pd, and Zn using radiochemical activation analysis. Glasses from DSDP leg 24, site 238 in the Indian Ocean have a trace element pattern which reflects secondary processes at a shallow depth. Chemical fractionations in petrogenesis of tholeiitic basalts indicate that (Ir, Os), Au, Pd, Ni, and Re are strongly fractionated in igneous processes; the unfractionated chondritic mantle pattern thus imposes constraints on mantle evolution models. Finally, the limited Rb/Cs fractionation in oceanic tholeiites reflects the low abundance of volatiles and hydrous silicates in normal ocean ridge basalts.

  12. 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.

  13. ABUNDANCE OF TRACE AND MINOR ELEMENTS IN ORGANIC AND MINERAL FRACTIONS OF COAL

    EPA Science Inventory

    The report gives results of subjecting 27 U.S. coals to float/sink, acid, and ion-exchange treatments. From these treatments, coal fractions were obtained and analyzed to determine the organic and mineral associations of 45 elements. Of the elements studied, B, Be, Br, Ge, and Sb...

  14. Fractionation of trace elements in total atmospheric deposition by filtrating-bulk passive sampling.

    PubMed

    Rueda-Holgado, F; Palomo-Marn, M R; Calvo-Blzquez, L; Cereceda-Balic, F; Pinilla-Gil, E

    2014-07-01

    We have developed and validated a new simple and effective methodology for fractionation of soluble and insoluble forms of trace elements in total atmospheric deposition. The proposed methodology is based on the modification of a standard total deposition passive sampler by integrating a quartz fiber filter that retains the insoluble material, allowing the soluble fraction to pass through and flow to a receiving bottle. The quartz filter containing the insoluble fraction and the liquid containing the soluble fraction are then separately assayed by standardized ICP-MS protocols. The proposed atmospheric elemental fractionation sampler (AEFS) was validated by analyzing a Coal Fly Ash reference material with proper recoveries, and tested for field fractionation of a set of 10 key trace elements in total atmospheric deposition at the industrial area of Puchuncav-Ventanas, Chile. The AEFS was proven useful for pollution assessment and also to identify variability of the soluble and insoluble fractions of the selected elements within the study area, improving the analytical information attainable by standard passive samplers for total deposition without the need of using sophisticated and high cost wet-only/dry only collectors. PMID:24840424

  15. 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)

  16. 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.

  17. Galerkin finite element method for two-dimensional Riesz space fractional diffusion equations

    NASA Astrophysics Data System (ADS)

    Bu, Weiping; Tang, Yifa; Yang, Jiye

    2014-11-01

    In this article, a class of two-dimensional Riesz space fractional diffusion equations is considered. Some fractional spaces are established and some equivalences between fractional derivative spaces and fractional Sobolev space are presented. By the Galerkin finite element method and backward difference method, a fully discrete scheme is obtained. According to Lax-Milgram theorem, the existence and uniqueness of the solution to the fully discrete scheme are investigated. The stability and convergence of the scheme are also derived. Finally, some numerical examples are given for verification of our theoretical analysis.

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

    PubMed

    Olas, M; Cern, J C; Fernndez, 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

  19. 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.

  20. 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 environments leading to preferential removal of MREE and LREE by adsorption and precipitation as Fe-Mn oxy-hydroxides in sediments. PAAS normalised plots also depicted slightly convex sub-parallel shale like patterns with alike enrichment.The same characteristics have been observed for sediments for Kaveri River validating that the sediments brought down during fluvial transport, is the source of REE in Pichavaram. Strong positive Eu anomalies suggested prevalence of reducing conditions as well as it indicated source from the natural weathering of the post Archean charnockitic and gneissic terrain in the course of river Kaveri. Role of different mangroves species in controlling the REE distribution in sediments was also observed . Tidally influenced cores showed complexity of environment these sites were exposed to. Factor analysis delineated three main processes controlling REE distribution in Pichavaram, namely natural weathering, inherent physico-chemical processes and in-situ biogeochemical processes occurring in this hypersaline mangrove environment.

  1. 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-Ni, whereas the corresponding highly siderophile elements remained sequestered by the surviving metal. The highly siderophile elements may have been introduced by a population of ~103 large (~1022 g) planetisimals, similar to those forming the lunar mare basins. ?? 1981.

  2. 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

  3. Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

    USGS Publications Warehouse

    Birdwell, Justin E.

    2012-01-01

    Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

  4. A new convection-fractionation model for the evolution of the principal geochemical reservoirs of the Earth's mantle

    NASA Astrophysics Data System (ADS)

    Walzer, Uwe; Hendel, Roland

    1999-04-01

    There are geochemical reservoirs (CC, DM, PM, EM1, EM2, HIMU) in the Earth's mantle and crust. They are distinguished by their isotopic and chemical abundance ratios and they arise from the combination of partial melting, segregation, ascent of the melt, differentiation of the melt, and lateral transport. The fractionation generates the chemical and isotopic diversity, while the solid-state convection works toward homogenization in particular in mantle areas with high gradient of creeping velocity perpendicular to the velocity vector. The thermal and chemical evolution of the Earth's mantle and crust has been modeled simultaneously by a fractionation mechanism plus 2D-FD Oberbeck-Boussinesq thermal convection. In contrast with the published model K1 [Walzer, U., Hendel, R., 1997a. Time-dependent thermal convection, mantle differentiation and continental-crust growth. Geophys. J. Int. 130, 303-325; geological interpretation: Walzer, U., Hendel, R., 1997b. Tectonic episodicity and convective feedback mechanisms. Phys. Earth Planet. Interiors 100, 167-188], layered convection is not an assumption but the mineral phase changes are introduced for 410 and 660 km depth using customary values of the Clapeyron slope, the density contrast, etc. So we have heat sources and sinks at 410 and 660 km, respectively, in addition to the usual Rayleigh number, Rq, for internal heating by radioactivity and bottom heating at the core-mantle boundary (CMB). The viscosity is a function of the temperature field and the pressure. Segregation takes place if the asthenospheric viscosity falls below a certain threshold. Oceanic plateaus, enriched in incompatible elements, develop leaving behind depleted parts of the mantle (DM). The resulting inhomogeneous heat-source distribution generates a first feedback mechanism. A growing continent is produced by accretion and further fractionation, consuming the older oceanic plateaus. The lateral movability of the growing continent causes a second feedback mechanism. The mentioned mechanisms generate acceptable distributions of the convective vigor and of the growth of juvenile continent material over the time axis. These distributions are stable for a moderate variation of the parameters only. The solutions of the system of differential equations show acceptable values for the distributions of the temperature, viscosity, heat flow, mantle-creep velocity and the continent's velocity. The following new result is insensitive to a strong variation of Rq: After an initially rather complex mixing process of the depleted parts and the pristine parts of the mantle, we arrive at a mainly depleted upper half of the mantle including the uppermost parts of the lower mantle and a predominantly pristine lower half of the mantle in the Phanerozoic at the latest. There is no sharp interface between the halves.

  5. 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...

  6. 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; Bni, 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

  7. 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(?)2) space replacing the complex H(div; ?) space. Some a priori error estimates in L2-norm for the scalar unknown u and in (L2)2-norm for its gradient ?. Moreover, we also discuss a priori error estimates in H1-norm for the scalar unknown u. PMID:24737957

  8. 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, Frdric

    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 (0.26fractionation 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 (0.22fractionation 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 ?66Zn=0.280.05 (2s.d.).

  9. 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 further indicative of an elevated O2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction. ?? 2007 Elsevier Ltd. All rights reserved.

  10. 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...

  11. 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.

  12. 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 (>0.45?m) and dissolved fractions, which included truly dissolved (1 kDa) and colloidal particles (0.45?m-1 kDa)), after filtration through a 0.45 ?m 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.

  13. 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 accomplished by taking the relationship of fractional snow-cover to NDSI from one area (e.g., Alaska) and testing it on the other two areas (e.g. Russia and Quebec). Again the results showed that fractional snow-cover can be estimated to 10 percent. The results have been shown to have advantages over other published fractional snowcover algorithms applied to MODIS data. Most recently the fractional snow-cover algorithm has been applied using 500-meter observations over the state of Colorado for a period spanning 25 days. The results exhibit good behavior in mapping the spatial and temporal variability in snowcover over that 25-day period. Overall these studies indicate that robust estimates of fractional snow-cover can be attained using the NDSI parameter over areas extending in size from watersheds relatively large compared to MODIS pixels to global land cover. Other refinements to this approach as well as different approaches are being examined for mapping fractional snow-cover using MODIS observations.

  14. 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

  15. Volatility Fractionation of REE and Other Trace Elements During Vacuum Evaporation

    NASA Astrophysics Data System (ADS)

    Davis, A. M.; Hashimoto, A.

    1995-09-01

    Volatility-fractionated REE patterns were first recognized in calcium-, aluminum-rich inclusions (CAIs) in meteorites over 20 years ago [1]. Such REE patterns can be modeled quite well by equilibrium thermodynamic calculations [2,3,4], but kinetic effects on fractionation of trace elements between gas and solids or liquids have remained less well-known. We have previously reported on experiments in which melts of initial REE-doped chondritic composition [5] and perovskite composition [6] were evaporated in vacuo. In both series of experiments, residues were formed that had large negative Ce anomalies and small negative Pr and Eu anomalies, but no other significant REE fractionations were observed. In an effort to produce more extensive fractionation of REE and other refractory elements, we made a new, more refractory, starting material (stoichiometric CaTiO3 doped with a number of refractory trace elements in chondritic proportions to a total "trace" element level of 5 wt%) and evaporated it under vacuum at a higher temperature (2150 degrees C) than the earlier experiments (1800-2000 degrees C). The results are shown in Fig. 1. Despite the high temperature, the two most extreme evaporation residues reached the solidus during evaporation; the other residues with lower degrees of evaporation remained liquid until cooled at the end of the experiment. The most extreme residue consists largely of mixed Sc, Y and Zr oxides; most of the Ti and nearly all of the Ca have evaporated. In this residue, there are large depletions in Sr, Nb, Ba, Ce and Eu and smaller depletions of La, Pr, Nd, Sm and Yb compared to Sc, Zr and most heavy REE. There is, however, little fractionation of the heavy REE from one another. The chemical composition and even the physical state of the residues change with degree of evaporation, undoubtedly affecting evaporation rates of trace elements. For example, even though the experiments are all carried out at a single temperature and both Ce and Eu are quite depleted in the most extreme residue, Ce evaporates early and Eu evaporates late (Fig. 1). Ultrarefractory inclusions show substantial fractionations among the heavy REE that have been attributed to volatility fractionation [7]. Kinetically controlled evaporation produces large isotopic mass fractionation effects in Ca and Ti [6], whereas there is minimal isotopic fractionation between gas and condensed phases at high temperatures. The lack of large isotopic fractionation effects in ultrarefractory inclusions [7] suggests that these objects did not form by kinetically controlled evaporation. The residues we have produced have bulk chemical compositions consistent with ultrarefractory inclusions, as they are composed of mixed Sc, Zr and Y oxides, but they do not have as much heavy to light REE fractionation nor do they show the substantial fractionation among the heavy REE that is characteristic of ultrarefractory inclusions. This difference supports the idea that the volatility fractionations of trace elements observed CAIs are thermodynamically rather than kinetically controlled. References: [1] Tanaka T. and Masuda A. (1973) Icarus, 19, 523-530. [2] Boynton W. V. (1975) GCA, 39, 569-584. [3] Davis A. M. and Grossman L. (1979) GCA, 43, 1611-1632. [4] MacPherson G. J. and Davis A. M. (1994) GCA, 58, 5599-5625. [5] Wang J. et al. (1993) Meteoritics, 28, 454-455. [6] Davis A. M. et al. (1995) LPS XXVI, 317-318. [7] Davis A. M. (1991) Meteoritics, 26, 330. Fig. 1. Elemental enrichment factors in residues of initial stoichiometric CaTiO3 composition doped with 5% refractory trace elements in chondritic relative proportions, plotted in order of atomic number.

  16. 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)

  17. 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.

  18. 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.

  19. 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.

  20. RARE EARTH ELEMENT OXIDES FOR TRACING SEDIMENT MOVEMENT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The development of soil conservation plans and evaluation of spatially distributed erosion models require knowledge of rates of soil loss and sedimentation on different landscape elements and slope positions. Characterization of soil erosion rates and patterns within watersheds is important for the ...

  1. INAA application in the assessment of chemical element mass fractions in adult and geriatric prostate glands.

    PubMed

    Zaichick, Vladimir; Zaichick, Sofia

    2014-08-01

    The variation with age of the mass fraction of 37 chemical elements in intact nonhyperplastic prostate of 65 healthy 21-87 year old males was investigated by instrumental neutron activation analysis with high resolution spectrometry of short- and long-lived radionuclides. Mean values (MS??) for mass fractions (mg kg(-1), dry mass basis) of the chemical elements studied were: Ag-0.0550.007, Br-33.23.3, Ca-2150118, Cl-13014703, Co-0.0380.003, Cr-0.470.05, Fe-99.36.1, Hg-0.0440.006, K-11896356, Mg-114968, Mn-1.410.07, Na-10886339, Rb-12.30.6, Sb-0.0490.005, Sc-0.0210.003, Se-0.650.03, and Zn-79571. The mass fraction of other chemical elements measured in this study were lower than the corresponding detection limits (mg kg(-1), dry mass basis): As<0.1, Au<0.01, Ba<100, Cd<2, Ce<0.1, Cs<0.05, Eu<0.001, Gd<0.02, Hf<0.2, La<0.5, Lu<0.003, Nd<0.1, Sm<0.01, Sr<3, Ta<0.01, Tb<0.03, Th<0.05, U<0.07, Yb<0.03, and Zr<0.3. This work revealed that there is a significant trend for increase with age in mass fractions of Co (p<0.0085), Fe (p<0.037), Hg (p<0.035), Sc (p<0.015), and Zn (p<0.0014) and for a decrease in the mass fraction of Mn (p<0.018) in prostates, obtained from young adult up to about 60 years, with age. In the nonhyperplastic prostates of males in the sixth to ninth decades, the magnitude of mass fractions of all chemical element were maintained at near constant levels. Our finding of correlation between the prostatic chemical element mass fractions indicates that there is a great variation of chemical element relationships with age. PMID:24704913

  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 B3?u- ? X3?g- 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) = ) 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 ??(?)/?16(?) - 1 (i = 17, 18) using the above calculated cross sections. Assuming SMOW for the initial oxygen isotopic composition, the isotopic ratios of O atom dissociated from O2 are ?17O = 5.62, ?18O = 3.53, ?17O = 3.8, suggesting large mass-independent isotopic fractionation in photo-dissociation of CiO. Numerical values of isotopic fractionation (e.g. ?17O) can be obtained by solving photochemical reaction equations in the thermosphere conditions (>100 km) with the above estimated dissociation rates, where effective O+ pickup is likely to take place. We are currently working on the latter problem with hopes that this would test the EW hypothesis. References: [1] Ireland et al., 2006, Nature, 440:776. [2] Hashizume & Chaussidon, 2009, GCA, 73:3038. [3] Seki et al., 2001, Science, 291:1939. [4] Ozima et al., 2008, PNAS, 105:17654. [5] Werner & Knowles, http://www.molpro.net. [6] Heller, 1978, J. Chem. Phys., 68:2066. [7] Ackermann et al., 1970, Planet. Space Sci., 18:1639.

  3. Rare earth element abundances in rocks and minerals from the Fiskenaesset Complex, West Greenland. [comparison with lunar anorthosites

    NASA Technical Reports Server (NTRS)

    Henderson, P.; Fishlock, S. J.; Laul, J. C.; Cooper, T. D.; Conard, R. L.; Boynton, W. V.; Schmitt, R. A.

    1976-01-01

    The paper reports activation-analysis determinations of rare-earth-element (REE) and other trace-element concentrations in selected rocks, plagioclase, and mafic separates from the Fiskenaesset Complex. The REE abundances are found to be very low and atypical in comparison with other terrestrial anorthosites. The plagioclases are shown to be characterized by a deficiency in heavy RE elements relative to light ones and a positive Eu anomaly, while the mafic separates are enriched in heavy rare earths and have no Eu anomaly, except in one sample. It is found that the bulk and trace-element abundances of the plagioclases are similar to those observed in some lunar anorthosites, but the degree of Eu anomaly is less in the plagioclases. The data are taken as confirmation of the idea that fractionation processes were involved in the origin of the Complex, and it is concluded that the Complex may have been produced from a magma generated by partial melting of a garnet-bearing source.

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

    NASA Astrophysics Data System (ADS)

    Lonschinski, M.; Merten, D.; Bchel, 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 (Mller, 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 the different aquifers, representing local hydrochemical conditions. Furthermore, also regional prevailing features could be identified, representing processes which occur on a larger scale. On base of these results, continuative investigations on particular processes in the rock-water interaction will be carried out.

  5. Empirical evidence for the fractionation of carbon isotopes between diamond and iron carbide from the Earth's mantle

    NASA Astrophysics Data System (ADS)

    Mikhail, S.; Guillermier, C.; Franchi, I. A.; Beard, A. D.; Crispin, K.; Verchovsky, A. B.; Jones, A. P.; Milledge, H. J.

    2014-04-01

    have studied two samples of mantle diamond containing iron carbide inclusions from Jagersfontein kimberlite, South Africa. Syngenetic crystal growth is inferred using morphological characteristics. These samples provide an opportunity to investigate the isotopic partitioning of 13C in a terrestrial natural high-pressure and high-temperature (HPHT) system. The difference for the ?13C values between the diamond and coexisting iron carbide averaged 7.2 1.3. These data are consistent with available data from the literature showing iron carbide to be 13C-depleted relative to elemental carbon (i.e., diamond). We infer that the minerals formed by crystallization of diamond and iron carbide at HPHT in the mantle beneath the Kaapvaal Craton. It is unclear whether crystallization occurred in subcratonic or sublithospheric mantle; in addition, the source of the iron is also enigmatic. Nonetheless, textural coherence between diamond and iron carbide resulted in isotopic partitioning of 13C between these two phases. These data suggest that significant isotopic fractionation of 13C/12C (?13C up to >7) can occur at HPHT in the terrestrial diamond stability field. We note that under reducing conditions at or below the iron-iron wustite redox buffer in a cratonic or deep mantle environment in Earth, the cogenesis of carbide and diamond may produce reservoirs of 13C-depleted carbon that have conventionally been interpreted as crustal in origin. Finally, the large ?13C for diamond-iron carbide shown here demonstrates ?13C for silicate-metallic melts is a parameter that needs to be constrained to better determine the abundance of carbon within the Earth's metallic core.

  6. Effects of Rare Earth Element Additions on the Impression Creep Behavior of AZ91 Magnesium Alloy

    NASA Astrophysics Data System (ADS)

    Kabirian, F.; Mahmudi, R.

    2009-09-01

    The effects of 1, 2, and 3 wt pct rare earth (RE) element additions on the microstructure and creep behavior of cast AZ91 Mg alloy were investigated by impression tests. The tests were carried out under constant punching stress in the range 200 to 650 MPa at temperatures in the range 425 to 525 K. Analysis of the data showed that for all loads and temperatures, the AZ91-2RE alloy had the lowest creep rates and, thus, the highest creep resistance among all materials tested. This is attributed to the formation of Al11RE3 with a branched morphology, reduction in the volume fraction of the eutectic ?-Mg17Al12 phase, and solid solution hardening effects of Al in the Mg matrix. The stress exponents and activation energies were the same for all alloy systems studied, 5.3 to 6.5 and 90 to 120 kJ mol-1, respectively, with the exception that the activation energy for the AZ91-3RE system was 102 to 126 kJ mol-1. An observed decreasing trend of creep-activation energy with stress suggests that two parallel mechanisms of lattice and pipe diffusion-controlled dislocation climb are competing. Dislocation climb controlled by dislocation pipe diffusion is controlling at high stresses, whereas climb of edge dislocations is the controlling mechanism at low stresses.

  7. 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.

  8. Mobile DNA Elements: The Seeds of Organic Complexity on Earth.

    PubMed

    Habibi, Laleh; Pedram, Mehrdad; AmirPhirozy, Akbar; Bonyadi, Khadijeh

    2015-10-01

    Mobile DNA or transposable elements (TEs) are genomic sequences capable of moving themselves independently into different parts of the genome. Viral invasion of eukaryotic genomes is assumed to be the main source of TEs. Selfish transposition of these elements could be a serious threat to the host cell, as they can insert themselves into the middle of coding genes and/or induce genomic instability. In response, through millions of years of evolution, cells have come up with various mechanisms such as genomic imprinting, DNA methylation, heterochromatin formation, and RNA interference to deactivate them. Interestingly, these processes have also greatly contributed to important cellular functions involved in cell differentiation, development, and differential gene expression. Propagation of TE copies during the course of evolution have resulted in increasing the genome size and providing proper space and flexibility in shaping the genome by creating new genes and establishing essential cellular structures such as heterochromatin, centromere, and telomeres. Yet, these elements are mostly labeled for playing a role in pathogenesis of human diseases. Here, we attempt to introduce TEs as factors necessary for making us human rather than just selfish sequences or obligatory guests invading our DNA. PMID:26222789

  9. The Galerkin finite element method for a multi-term time-fractional diffusion equation

    NASA Astrophysics Data System (ADS)

    Jin, Bangti; Lazarov, Raytcho; Liu, Yikan; Zhou, Zhi

    2015-01-01

    We consider the initial/boundary value problem for a diffusion equation involving multiple time-fractional derivatives on a bounded convex polyhedral domain. We analyze a space semidiscrete scheme based on the standard Galerkin finite element method using continuous piecewise linear functions. Nearly optimal error estimates for both cases of initial data and inhomogeneous term are derived, which cover both smooth and nonsmooth data. Further we develop a fully discrete scheme based on a finite difference discretization of the time-fractional derivatives, and discuss its stability and error estimate. Extensive numerical experiments for one- and two-dimensional problems confirm the theoretical convergence rates.

  10. 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.

  11. Spatiotemporal correlations in Earth's temperature field from fractional stochastic-diffusive energy balance models

    NASA Astrophysics Data System (ADS)

    Rypdal, Kristoffer; Rypdal, Martin; Fredriksen, Hege-Beate

    2015-04-01

    In the Earth temperature field, spatiotemporal long-range dependence is usually explained as a result of nonlinear cross-scale coupling and cascading. In this contribution we challenge that paradigm, demonstrating that the observed correlation structure can arise from simple, linear, conceptual models. A two-dimensional stochastic-diffusive energy balance model (EBM) formulated on a sphere by G. R. North et al., J. Climate, 24:5850-5862, 2011, is explored and generalized. We compute instantaneous and frequency-dependent spatial autocorrelation functions, and local temporal power spectral densities for local sites and for spatially averaged signal up to the global scale. On time scales up to the relaxation time scale given by the effective heat capacities of the ocean mixed layer and land surface, respectively, we obtain scaling features reminiscent of what can be derived from the observed temperature field. On longer time scales, however, the EBM predicts a transition to a white-noise scaling, which is not reflected in the observed records. We propose and explore a fractional generalization (FEBM), which can be considered as a spatiotemporal version of the zero-dimensional, long-memory EBM of M. Rypdal and K. Rypdal, J. Climate, 27:5240-5258, 2014. The fractional equation introduces a power-law (rather than exponential) impulse response representing the delayed action due to the slow heat exchange between the mixed layer and the deep ocean. It is demonstrated that this generalized model describes qualitatively the main spatiotemporal correlation characteristics of the temperature field derived from instrumental data and from a 500 yr control run of the Nor-ESM model. For instance, the FEBM implies temporal power-law spectra where the spectral exponent for globally averaged temperature is twice that of local temperatures, and spatial autocorrelation lengths increases with time scale, in good agreement with the Nor-ESM simulations. It also reproduces the long-time response to a step-function forcing in the Nor-ESM model.

  12. Rare earths and other trace elements in Apollo 14 samples.

    NASA Technical Reports Server (NTRS)

    Helmke, P. A.; Haskin, L. A.; Korotev, R. L.; Ziege, K. E.

    1972-01-01

    REE and other trace elements have been determined in igneous rocks 14053, 14072, and 14310, in breccias 14063 and 14313, and in fines 14163. All materials analyzed have typical depletions of Eu except for feldspar fragments from the breccias and igneous fragments from 14063. Igneous rocks 14072 and 14053 have REE concentrations very similar to Apollo 12 basalts; 14310 has the highest REE concentrations yet observed for a large fragment of lunar basalt. The effects of crystallization of a basaltic liquid as a closed system on the concentrations of Sm and Eu in feldspar are considered. Small anorthositic fragments may have originated by simple crystallization from very highly differentiated basalt (KREEP) or by closed-system crystallization in a less differentiated starting material. Application of independent models of igneous differentiation to Sm and Eu in massive anorthosite 15415 and to Sm and Eu in lunar basalts suggests a common starting material with a ratio of concentrations of Sm and Eu about the same as that in chondrites and with concentrations of those elements about 15 times enriched over chondrites.

  13. 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

    2016-01-01

    Reduction of [Cp*Fe(η(5) -As5 )] with [Cp''2 Sm(thf)] (Cp''=η(5) -1,3-(tBu)2 C5 H3 ) under various conditions led to [(Cp''2 Sm)(μ,η(4) :η(4) -As4 )(Cp*Fe)] and [(Cp''2 Sm)2 As7 (Cp*Fe)]. Both compounds are the first polyarsenides of the rare-earth metals. [(Cp''2 Sm)(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''2 Sm)2 As7 (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''2 Sm)(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

  14. Fractionation of refractory siderophile elements in metal from the Rose City meteorite

    NASA Astrophysics Data System (ADS)

    Rubin, A. E.

    1995-07-01

    An ˜4 x 9 x 12-min concentration of metal (dubbed RCl) situated between silicate melt and a relict chondritic clast in the Rose City H5 impact-melt breccia is compositionally heterogeneous. Approximately 65 wt% of RC1 is enriched in the refractory siderophile elements, Os and Ir, by 30M0% relative to bulk H chondrite metal; ˜20 wt% is depleted in these elements by 31-35%; and 15 wt% is depleted by a considerably greater amount (75%). Common and volatile siderophile elements are essentially unfractionated in all three regions; W is fractionated to only a moderate degree. The compositions of the different regions of RC1 are similar to those of previously analyzed metal nodules and veins in shocked but unmelted ordinary chondrites. Ml of these objects probably formed by a complex process involving vaporization of chondritic material, rapidly followed by oxidation of W to form volatile oxides, fractional condensation of refractory siderophile elements, transport of the residual vapor (containing common and volatile siderophile elements as well as W oxide) and condensation of this vapor in fractures and voids or on metallic liquid substrates. The common occurrence of vugs in shock-heated chondrites and the pervasiveness of vaporization effects recorded in metal masses and veins underscores the important role of superheating in the formation of impact breccias.

  15. Elemental composition of solid aerosols of different size fraction as exemplified by the Baikal region

    NASA Astrophysics Data System (ADS)

    Filippova, U.

    2012-04-01

    It is preferable to analyse fine aerosol fractions (less than 1 micron) to study remote and regional transfers. In our survey, we used a size fraction of 0.39-0.69 micron which can exist in atmosphere air for several days transferred at distance of hundreds of meters from the source of their origin. A six-phase high volume slit cascade impactor TE-236 (Tisch Environmental Inc.) was used for sampling. Among 20 elements analysed by XRFA-SR, the most informative elements (Ti, Mn, Ni, Cu, Zn, Ga, Ge, Sr, Br, and Pb) were chosen having the highest differences among the sources. These sources with chosen elements were divided into two groups: the first was a group of anthropogenic sources of one type and the second was a group of sources differing from the first one. Concentrations of all elements excluding copper were much higher.in the first group than in the second. The curve shape (ratio of elements) for both groups was also significantly different. Differences of elemental ratio in emissions of anthropogenic sources may serve as an indicator of remote effect of these sources on the background territories, in this case, on the southern basin of Lake Baikal. To analyse relative contribution of the sources to the atmosphere pollution of any region, the ratio between concentrations of chosen elements and Cu concentration was used instead of absolute concentrations. Qualitative relative contribution of the sources to aerosols of Southern Baikal (as exemplified by Listvyanka) can be estimated using multiple linear regression analysis. This analysis was used to estimate the effect of two groups of anthropogenic sources on aerosol composition in the settlement Listvyanka. The composition of fine-disperse aerosol fractions was analysed in two samples collected in Listvyanka in 2009. These two samples were obtained during transfer of air masses from Irkutsk. The first sample (20-21 October 2009) was collected at weak north-western (NW) wind and another sample (27-28 October 2009) - at strong NW wind. These results show that at weak north-western transfer the elemental composition of fine-disperse fraction of aerosols in Listvyanka corresponds to the first group of aerosol sources (80-90%), whereas the percentage of more remote sources makes up about 2-3%.

  16. [Study on speciation and fractionation of rare earth eleinents in surface sediments in Gansu, Ningxia and Inner Mongolia sections of Yellow River].

    PubMed

    Liu, Jing-Jun; Lai, Zi-Juan; Liu, Ying

    2013-03-01

    In the present paper, BCR sequential extraction and high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) were performed to analyze the speciation contents of 14 kinds of rare earth elements (REE) in the surface sediments from 12 sampling sites (S1-S12) in Gansu, Ningxia and Inner Mongolia Sections of Yellow River, and REE fractionation were also studied. The results indicated that the contents of REE in 12 sediment samples werethe same order. The average contents of 14 rare earth elements were in this order: Ce(66.4)>La(35.8)>Nd(28.6)>Pr(7.88)>Sm(5.87) >Gd(5.01)>Dy (4.53)>Yb(2.86)>Er(2.51)>Eu(1.31)>Ho(0.856)>Tb(0.760)>Tm(0.428)>Lu(0.404), which were similar to the Chinese soil background. The residual fractions of all elements were present at the highest percentages(71.9%-93.9%), which indicated that the bioavailability or environmental impact was low. The percentage of reducible fraction was the lowest, ranged from 0. 20% to 3. 87% with the mean value of 0.83%, while the oxidizable fraction percentage(7.61%) was close to acid-soluble fraction(7.69%). But in Maqu (S12), oxidizable percentage (16.1%) was significantly higher than the acid-soluble fraction (1.73%). Correlation analysis showed that there was a significant positive correlation between total organic carbon (TOC) content and oxidizable percentage, and the correlation coefficients were between 0.763 and 0.914. REE fractionation results showed that: the contents of REE in surface sediments of Gansu, Ningxia and Inner Mongolia Sections of Yellow River were mainly from soil weathering, with light-REE enrichment and Eu depletion. The chondrite-normalized curve implied that La and Ce in Jinshawan (S8) and Baotou-Dengkou (S1) and heavy REE at all the sampling points might have external REE sources. PMID:23705457

  17. 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.

  18. 2013 Southeast Asian smoke haze: fractionation of particulate-bound elements and associated health risk.

    PubMed

    Betha, Raghu; Behera, Sailesh N; Balasubramanian, Rajasekhar

    2014-04-15

    Recurring biomass burning-induced smoke haze is a serious regional air pollution problem in Southeast Asia (SEA). The June 2013 haze episode was one of the worst air pollution events in SEA. Size segregated particulate samples (2.5-1.0 ?m; 1.0-0.5 ?m; 0.5- 0.2 ?m; and <0.2 ?m) were collected during the June 2013 haze episode. PM2.5 concentrations were elevated (up to 329 ?g/m(3)) during the haze episode, compared to those during the nonhaze period (11-21 ?g/m(3)). Chemical fractionation of particulate-bound trace elements (B, Ca, K, Fe, Al, Ni, Zn, Mg, Se, Cu, Cr, As, Mn, Pb, Co, and Cd) was done using sequential extraction procedures. There was a 10-fold increase in the concentration of K, an inorganic tracer of biomass burning. A major fraction (>60%) of the elements was present in oxidizable and residual fractions while the bioavailable (exchangeable) fraction accounted for up to 20% for most of the elements except K and Mn. Deposition of inhaled potentially toxic trace elements in various regions of the human respiratory system was estimated using a Multiple-Path Particle Dosimetry model. The particle depositions in the respiratory system tend to be more severe during hazy days than those during nonhazy days. A prolonged exposure to finer particles can thus cause adverse health outcomes during hazy days. Health risk estimates revealed that the excessive lifetime carcinogenic risk to individuals exposed to biomass burning-impacted aerosols (18 1 10(-6)) increased significantly (P < 0.05) compared to those who exposed to urban air (12 2 10(-6)). PMID:24646334

  19. 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.

  20. 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.

  1. 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 continued oxidation of Ce(III) to Ce(IV) in the estuary. Fractionation of the light-to-heavy REEs seems to take place, whereas the Y/Ho fractionation is unclear in the estuarine mixing zone.

  2. 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.

  3. 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.

  4. 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, were greater than the reporting limit.

  5. [Leaching of Rare Earth Elements from Coal Ashes Using Acidophilic Chemolithotrophic Microbial Communities].

    PubMed

    Muravyov, M I; Bulaev, A G; Melamud, V S; Kondrat'eva, T F

    2015-01-01

    A method for leaching rare earth elements from coal ash in the presence of elemental sulfur using communities of acidophilic chemolithotrophic microorganisms was proposed. The optimal parameters determined for rare element leaching in reactors were as follows: temperature, 45 degrees C; initial pH, 2.0; pulp density, 10%; and the coal ash to elemental sulfur ratio, 10 : 1. After ten days of leaching, 52.0, 52.6, and 59.5% of scandium, yttrium, and lanthanum, respectively, were recovered. PMID:26263628

  6. A semi-discrete finite element method for a class of time-fractional diffusion equations.

    PubMed

    Sun, HongGuang; Chen, Wen; Sze, K Y

    2013-05-13

    As fractional diffusion equations can describe the early breakthrough and the heavy-tail decay features observed in anomalous transport of contaminants in groundwater and porous soil, they have been commonly used in the related mathematical descriptions. These models usually involve long-time-range computation, which is a critical obstacle for their application; improvement of computational efficiency is of great significance. In this paper, a semi-discrete method is presented for solving a class of time-fractional diffusion equations that overcome the critical long-time-range computation problem. In the procedure, the spatial domain is discretized by the finite element method, which reduces the fractional diffusion equations to approximate fractional relaxation equations. As analytical solutions exist for the latter equations, the burden arising from long-time-range computation can effectively be minimized. To illustrate its efficiency and simplicity, four examples are presented. In addition, the method is used to solve the time-fractional advection-diffusion equation characterizing the bromide transport process in a fractured granite aquifer. The prediction closely agrees with the experimental data, and the heavy-tail decay of the anomalous transport process is well represented. PMID:23547234

  7. Trace-element fractionation in Hadean mantle generated by melt segregation from a magma ocean.

    PubMed

    Caro, Guillaume; Bourdon, Bernard; Wood, Bernard J; Corgne, Alexandre

    2005-07-14

    Calculations of the energetics of terrestrial accretion indicate that the Earth was extensively molten in its early history. Examination of early Archaean rocks from West Greenland (3.6-3.8 Gyr old) using short-lived 146Sm-142Nd chronometry indicates that an episode of mantle differentiation took place close to the end of accretion (4.46 +/- 0.11 Gyr ago). This has produced a chemically depleted mantle with an Sm/Nd ratio higher than the chondritic value. In contrast, application of 176Lu-176Hf systematics to 3.6-3.8-Gyr-old zircons from West Greenland indicates derivation from a mantle source with a chondritic Lu/Hf ratio. Although an early Sm/Nd fractionation could be explained by basaltic crust formation, magma ocean crystallization or formation of continental crust, the absence of coeval Lu/Hf fractionation is in sharp contrast with the well-known covariant behaviour of Sm/Nd and Lu/Hf ratios in crustal formation processes. Here we show using mineral-melt partitioning data for high-pressure mantle minerals that the observed Nd and Hf signatures could have been produced by segregation of melt from a crystallizing magma ocean at upper-mantle pressures early in Earth's history. This residual melt would have risen buoyantly and ultimately formed the earliest terrestrial protocrust. PMID:16015327

  8. [Geochemical characteristics of rare earth elements on sunflower growing area in the west of Jilin Province].

    PubMed

    Li, Shu-Jie; Dou, Sen; Wang, Li-Min; Liu, Zhao-Shun

    2011-07-01

    Soil and plant samples were collected from the sunflower growing area in the west of Jilin province. A variety of ancillary methods were used to determine the soil element content. Then the rare earth elements geochemistry in soil was studied, and the correlation of REEs in this region with other elements and the quality of plant was investigated. The results show that, (1) REE content of the soil in Nong'an is relatively higher to those in Daan and Tongyu. Distribution pattern of rare earth elements in soil for the right tilt of the light rare earth enrichment patterns which is consistent with the national distribution pattern of rare earth elements; (2) REE contents in the three studying areas in the soil are different, and this primarily relates to the soil parent materials; (3) The REEs which positively correlate with soil available potassium are Se, Fe2O3, Ti, P, Mn, Cu, Zn, Cr, Mo, B, F. The protein content of sunflower seeds has a negative correlation with REE. With the exception of Lu, all REEs show a similar correlation. PMID:21922834

  9. 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 during terrestrial weathering.

  10. 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%).

  11. Determination of rare-earth elements in Luna 16 regolith sample by chemical spectral method

    NASA Technical Reports Server (NTRS)

    Stroganova, N. S.; Ryabukhin, V. A.; Laktinova, N. V.; Ageyeva, L. V.; Galkina, I. P.; Gatinskaya, N. G.; Yermakov, A. N.; Karyakin, A. V.

    1974-01-01

    An analysis was made of regolith from layer A of the Luna 16 sample for rare earth elements, by a chemical spectral method. Chemical and ion exchange concentrations were used to determine the content of 12 elements and Y at the level 0.001 to 0.0001 percent with 10 to 15 percent reproducibility of the emission determination. Results within the limits of reproducibility agree with data obtained by mass spectra, activation, and X-ray fluorescent methods.

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

    SciTech Connect

    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.

  13. Geochemistry of ultrahigh-pressure anatexis: fractionation of elements in the Kokchetav gneisses during melting at diamond-facies conditions

    NASA Astrophysics Data System (ADS)

    Stepanov, Aleksandr S.; Hermann, Joerg; Korsakov, Andrey V.; Rubatto, Daniela

    2014-05-01

    The Kokchetav complex in Kazakhstan contains garnet-bearing gneisses that formed by partial melting of metasedimentary rocks at ultrahigh-pressure (UHP) conditions. Partial melting and melt extraction from these rocks is documented by a decrease in K2O and an increase in FeO + MgO in the restites. The most characteristic trace element feature of the Kokchetav UHP restites is a strong depletion in light rare earth elements (LREE), Th and U. This is attributed to complete dissolution of monazite/allanite in the melt and variable degree of melt extraction. In contrast, Zr concentrations remain approximately constant in all gneisses. Using experimentally determined solubilities of LREE and Zr in high-pressure melts, these data constrain the temperature of melting to ~1,000 °C. Large ion lithophile elements (LILE) are only moderately depleted in the samples that have the lowest U, Th and LREE contents, indicating that phengite retains some LILE in the residue. Some restites display an increase in Nb/Ta with respect to the protolith. This further suggests the presence of phengite, which, in contrast to rutile, preferentially incorporates Nb over Ta. The trace element fractionation observed during UHP anatexis in the Kokchetav gneisses is significantly different from depletions reported in low-pressure restites, where generally no LREE and Th depletion occurs. Melting at UHP conditions resulted in an increase in the Sm/Nd ratio and a decoupling of the Sm-Nd and Lu-Hf systems in the restite. Further subduction of such restites and mixing with mantle rocks might thus lead to a distinct isotopic reservoir different from the bulk continental crust.

  14. 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.

  15. 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, 25C/21C, relative humidity of 55 - 65% and photon flux of 150 ?E 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 site. The extraction capacity of the PTE followed the order: EDTA>DTPA>NH4NO3>CaCl2> NaNO3 for both studied locations. Pearson correlation coefficient analysis between the concentrations of PTE accumulated in the bean primary leaves with their extractable concentrations showed a positive significant correlation with dilute CaCl2 and unbuffered nitrate solutions extraction procedures. In contrast, for all studied elements, except for Pb, the complexing and chelating extractants (e.g. EDTA and DTPA) exhibited poor correlation with the dwarf bean leaves concentrations.

  16. 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.

  17. 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.

  18. Environmental biogeochemical behaviors of rare earth elements in soil-plant systems.

    PubMed

    Liang, Tao; Zhang, Shen; Wang, Lijun; Kung, Hsiang-Te; Wang, Yuqi; Hu, Aitang; Ding, Shiming

    2005-12-01

    With the continual increase in the utilization of rare earth elements (REEs) for industrial and agricultural purposes in China, the research into the environmental biogeochemical behavior of REEs has become a pressing issue. The REEs' content in soil and various parts of wheat under different conditions in soil-plant systems were measured by INAA and ICP-MS. The results showed four aspects. (1) The mean value of total REEs in soil of China was 176.8 mg kg(-1). The mean ratio of SigmaLREE/SigmaHREE in soils was 8.0 and cerium accounts for 42% of the total REEs. The content of REEs in wheat seed ranged between 10(-11) and 10(-8) g g(-1), 3-4 orders of magnitude lower than that in soil. (2) The REEs contents in ryegrass, especially in roots, were significantly related to that of soil. The bioavailability of REEs in soil mainly depended on the exchangeable fraction of REEs, which was strongly affected by the physico-chemical properties of the soil. (3) Long-term foliage-dressing with Changle microfertilizer of REEs did not affect the contents and distribution patterns of REEs in soil. At the maturing stage of spring wheat, the REEs content was in the order of root > leaf >stem and crust. Compared with the control, foliage-dressing has a higher accumulation of REEs in root and leaf. However, no significant difference was found in stem and crust between the two treatments. (4) There was no significant accumulation with the soil-dressing method. When comparing controls in both foliage- and soil-dressing methods, no distinct residue of REEs in grains was found. PMID:16027965

  19. 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).

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

    SciTech Connect

    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. Total photon attenuation coefficients in some rare earth elements using selective excitation method

    NASA Astrophysics Data System (ADS)

    SitaMahalakshmi, N. V.; Kareem, M. A.; Premachand, K.

    2015-01-01

    The total mass attenuation coefficients were measured in the elements La, Nd, Sm, Gd and Dy belonging to rare earth region in the energy range 30-55 keV by employing the selective excitation method. This method facilitates selection of excitation energies near the K edge. The present experimental results were compared with the theoretical values due to Chantler and XCOM.

  3. 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...

  4. 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-...

  5. 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.

  6. Rare Earth Element Geochemistry of Angrites Northwest Africa 4590 and Northwest Africa 4801

    NASA Astrophysics Data System (ADS)

    Sanborn, M. E.; Wadhwa, M.

    2009-03-01

    We report ion microprobe analyses of rare earth element abundances in minerals of the plutonic angrites NWA 4590 and NWA 4801. Based on these results, implications are presented for the petrogenetic history of these two angrites and their relationships to other angrites.

  7. 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...

  8. 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...

  9. 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...

  10. Relative sensitivity factors for rare earth elements in different matrices employing spark source mass spectrometry

    SciTech Connect

    Ramakumar, K.L.; Aggarwal, S.K.; Kavimandan, V.D.; Shah, P.M.; Raman, V.A.; Sant, V.L.; Ramasubramanian, P.A.; Jain, H.C.

    1985-07-01

    Relative Sensitivity Factors (RSFs) for the rare earth elements Ce, Nd, Sm, Eu, Gd, Dy, Er, and Lu have been determined in U/sub 3/O/sub 8/-graphite and pure graphite matrices under similar experimental conditions employing Spark Source Mass Spectrometry (SSMS) with electrical detection system in magnetic peak switching mode. The RSF values differ very much when the matrix element (uranium in U/sub 3/O/sub 8/-graphite system or carbon in pure graphite) is the reference, but they show very good agreement when Er, one of the rare earth elements is chosen as internal standard. The literature data on RSF values for the rare earth elements in Y/sub 2/O/sub 3/ as well as Al matrices are compared with those obtained in the present work. An attempt has been made to explain the similar tend in the RSF values in all these matrices in terms of the decomposition pattern of the rare earth oxides. An empirical equation relating the RSFs with the decomposition energies of the lanthanide sesquioxides and monoxides has been shown to be useful in computing the RSFs for the lanthanides in various matrices.

  11. [Spectroscopic Research on Slag Nanocrystal Glass Ceramics Containing Rare Earth Elements].

    PubMed

    Ouyang, Shun-li; Li, Bao-wei; Zhang, Xue-feng; Jia, Xiao-lin; Zhao, Ming; Deng, Lei-bo

    2015-08-01

    The research group prepared the high-performance slag nanocrystal glass ceramics by utilizing the valuable elements of the wastes in the Chinese Bayan Obo which are characterized by their symbiotic or associated existence. In this paper, inductively coupled plasma emission spectroscopy (ICP), X-ray diffraction (XRD), Raman spectroscopy (Raman) and scanning electron microscopy (SEM) are all used in the depth analysis for the composition and structure of the samples. The experiment results of ICP, XRD and SEM showed that the principal crystalline phase of the slag nanocrystal glass ceramics containing rare earth elements is diopside, its grain size ranges from 45 to 100 nm, the elements showed in the SEM scan are basically in consistent with the component analysis of ICP. Raman analysis indicated that its amorphous phase is a three-dimensional network structure composed by the structural unit of silicon-oxy tetrahedron with different non-bridging oxygen bonds. According to the further analysis, we found that the rare earth microelement has significant effect on the network structure. Compared the nanocrystal slag glass ceramic with the glass ceramics of similar ingredients, we found that generally, the Raman band wavenumber for the former is lower than the later. The composition difference between the glass ceramics and the slag nanocrystal with the similar ingredients mainly lies on the rare earth elements and other trace elements. Therefore, we think that the rare earth elements and other trace elements remains in the slag nanocrystal glass ceramics have a significant effect on the network structure of amorphous phase. The research method of this study provides an approach for the relationship among the composition, structure and performance of the glass ceramics. PMID:26672316

  12. Fractionation of elements by particle size of ashes ejected from Copahue Volcano, Argentina.

    PubMed

    Gmez, Dario; Smichowski, Patricia; Polla, Griselda; Ledesma, Ariel; Resnizky, Sara; Rosa, Susana

    2002-12-01

    The volcano Copahue, Neuqun province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view. PMID:12509053

  13. 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.

  14. Oceanic crustal thickness from seismic measurements and rare earth element inversions

    SciTech Connect

    White, R.S.; McKenzie, D.; O'Nions, R.K. )

    1992-12-10

    Seismic refraction results show that the igneous section of oceanic crust averages 7.1 [plus minus] 0.8 km thick away from anomalous regions such as fracture zones and hot-spots, with extremal bounds of 5.0-8.5 km. Rare earth element inversions of the melt distribution in the mantle source region suggest that sufficient melt is generated under normal oceanic spreading centers to produce an 8.3 [plus minus] 1.5 km thick igneous crust. The difference between the thickness estimates from seismics and from rare earth element inversions is not significant given the uncertainties in the mantle source composition. The inferred igneous thickness increases to 10.3 [plus minus] 1.7 km (seismic measurements) and 10.7 [plus minus] 1.6 km (rare earth element inversions) where spreading centers intersect the regions of hotter than normal mantle surrounding mantle plumes. This is consistent with melt generation by decompression of the hotter mantle as it rises beneath spreading centers. Maximum inferred melt volumes are found on aseismic ridges directly above the central rising cores of mantle plumes, and average 20 [plus minus] 1 and 18 [plus minus] 1 km for seismic profiles and rare earth element inversions respectively. Both seismic measurements and rare earth element inversions show evidence for variable local crustal thinning beneath fracture zones, though some basalts recovered from fracture zones are indistinguishable geochemically from those generated on normal ridge segments away from fracture zones. The authors attribute the decreased mantle melting on very slow-spreading ridges to the conductive heat loss that enables the mantle to cool as it rises beneath the rift.

  15. 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

  16. [Determination of ten trace rare earth elements in the sample by atomic emission spectrometry].

    PubMed

    Li, Hui-zhi; Zhai, Dian-tang; Zhang, Jin; Pei, Mei-shan

    2005-09-01

    This paper describes the determination of trace La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Yb and Lu in the sample, using carbon powder, potassium sulfate, barium sulfate, strontium sulfate, and scandium chloride as buffer, by atomic emission spectrometry (AES). Scandium was selected as internal standard line. Sample separation and chemical treatment were not required. The sample was directly loaded into ordinary electrode. The method is simple, rapid and accurate. The determination requirement and influence factors were studied. A new method was developed for the determination of ten rare earth elements, for which the detection limit is smaller than 0.030%, and the range of the recovery is 94%-105%. The results of these elements in standard sample are in agreement with certified values, and the RSD is smaller than 5% (n = 9). The method has been applied to the determination of ten rare earth elements with satisfactory results. PMID:16379301

  17. 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 formation process and subsequent metamorphic history.

  18. 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 suboxic to anoxic conditions of the bottom and pore waters during the formation of Vesiku bone bed. In Ohesaare (Pridoli), the REE compositions were nearly identical across all the morphotypes and histologies of acanthodian microremains showing flat REE patterns with slight depletion in HREE. There were no visible enrichment in MREE, indicating relatively good preservation of original bioapatite and likely absence of any pronounced fractionated REE incorporation during later stages of diagenesis. The shale normalised (La/Yb)SN and (La/Sm)SN REE ratio compilations showed addsorption as dominating REE uptake mechanism across all the studied microfossils. The absence of well-defined Ce anomaly suggest oxic palaeoseawater conditions, which agrees with existing interpretations of Ohesaare sequence as high-energy shoal and regressive open ocean sedimentary environment.

  19. 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

  20. Rare-earth elements in hot brines (165 to 190 degree C) from the Salton Sea geothermal field

    SciTech Connect

    Lepel, E.A.; Laul, J.C.; Smith, M.R.

    1988-01-01

    Rare-earth element (REE) concentrations are important indicators for revealing various chemical fractionation processes (water/rock interactions) and source region geochemistry. Since the REE patterns are characteristic of geologic materials (basalt, granite, shale, sediments, etc.) and minerals (K-feldspar, calcite, illite, epidote, etc.), their study in geothermal fluids may serve as a geothermometer. The REE study may also enable us to address the issue of groundwater mixing. In addition, the behavior of the REE can serve as analogs of the actinides in radioactive waste (e.g., neodymium is an analog of americium and curium). In this paper, the authors port the REE data for a Salton Sea Geothermal Field (SSGF) brine (two aliquots: port 4 at 165{degree}C and port 5 at 190{degree}C) and six associated core samples.

  1. 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.

  2. 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.

  3. Modeling of the lung impedance using a fractional-order ladder network with constant phase elements.

    PubMed

    Ionescu, C M; Machado, J A T; De Keyser, R

    2011-02-01

    The self similar branching arrangement of the airways makes the respiratory system an ideal candidate for the application of fractional calculus theory. The fractal geometry is typically characterized by a recurrent structure. This study investigates the identification of a model for the respiratory tree by means of its electrical equivalent based on intrinsic morphology. Measurements were obtained from seven volunteers, in terms of their respiratory impedance by means of its complex representation for frequencies below 5 Hz. A parametric modeling is then applied to the complex valued data points. Since at low-frequency range the inertance is negligible, each airway branch is modeled by using gamma cell resistance and capacitance, the latter having a fractional-order constant phase element (CPE), which is identified from measurements. In addition, the complex impedance is also approximated by means of a model consisting of a lumped series resistance and a lumped fractional-order capacitance. The results reveal that both models characterize the data well, whereas the averaged CPE values are supraunitary and subunitary for the ladder network and the lumped model, respectively. PMID:23850980

  4. Long-term changes in elemental deposition at the earth's surface.

    PubMed

    Brimblecombe, P

    1994-01-01

    The rate of deposition of elements at a point on the earth's surface can change, quite dramatically, even on relatively short time-scales, as a function of weather patterns. On a global scale volcanoes (and more rarely large meteors) can overwhelm steadier sources of trace elements. In recent centuries human activities have increased emissions to the atmosphere to a point where they are above those of natural sources for some of the rarer elements. On a longer time-scale climate change can also alter the deposition of elements, although such changes are often slower than those brought about through anthropogenic emissions. Changes in climate can also alter the distribution of deposition, but there are few studies estimating such changes. This paper uses estimates of the balance of natural and anthropogenic sources of a range of elements to examine the likely variation in deposition at the earth's surface. It particularly focuses on those elements regarded as toxic, whose concentrations seem likely to go on increasing in industrial areas. PMID:15091753

  5. 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

  6. Study of speciation and size fractionation of trace element between soil solution, bog, river and lake within a boreal watershed (North Karelia, NW Russia) using fractional filtration

    NASA Astrophysics Data System (ADS)

    Ilina, Svetlana M.; Lapitsky, Sergey A.; Alekhin, Yuriy V.; Pokrovsky, Oleg S.; Viers, Jerome

    2010-05-01

    This work is aimed at studying the evolution of migration forms of true dissolved compounds and colloidal entities using an integrated approach of molecular mass distribution and differences in the association of trace elements (TE) with organic matter (OM) or Fe colloids in the system soil water-bog-river-lake. Characterization of TE speciation with colloids during TE migration from the site of colloids origin (bog and soil solutions) towards the transit zone (river) and finally to the deposition, accumulation or transformation zone (lake) is a main fundamental task of this problem. The objects of study include a small stream watershed Vostochniy and the river Palayoki (North Karelia, Russia). The water samplings were performed in July and August 2008 and 2009 and included soil solution, nourishing bog, the middle part of the brook originated from the swamp, the mouth of the brook and the lake Zipringa. We sampled large volumes (50 - 100 liters), and we applied, directly in the in-field-installed "clean laboratory" the sequential frontal filtration and ultrafiltration of samples through the filters of progressively decreasing poresize 100, 20, 10, 5, 0.8, 0.4, 0.2 and 0.1 microns; 100 kDa (0.0065 micron), 10 kDa (0.003 micron) and 1 kDa (0.0014 micron). This allowed separation of organic matter, coarse and fine particulate matter and colloids. All filtrates and selected retentates were analyzed for a wide range of macro-and micronutrients using ICP-MS. In filtrates of the river water, a significant decrease of iron concentration occurred in the range of 5 micron to 0.22 micron and from 100 kDa to 1 kDa. For alkali and alkaline earth elements (Mg, K, Ca), as well as for Cu, Ni, Cr the concentrations changed after passing through the 10 kDa membrane. Na concentration remains constant in all filtrates. The filtrates of the soil solution are characterized by a significant decreases in Na, K, after 0.1 micron, Ca, Cu in the range of 0.22 micron - 100 kDa and Mg, Ni in the range of 0.1 micron - 100 kDa. The changing of REEs concentrations occurred in the fraction smaller than 100 kDa for river water and in the fraction larger than 100 kDa in the soil solution. Concerning the evolution of element concentration in the system "soil solution - nourishing bog - river - lake", the concentration of Ca and Mg increases (with a little decrease in the stage "the nourishing bog - the middle current - the mouth"), and the concentration of Cu, Ni, Cr, Ti, Al decreases (with a slight increase in the interval "the nourishing swamp - the middle current - the mouth). The lanthanides have a maximum of their concentration in the river mouth and the minimum in the lake. Concentration of Fe, Zn in the soil solution is an order of magnitude higher than in the river and lake water. The ratio Fe / Me (where Me = Al, Cu, Zn, Ni, Co, Cr, Mn) naturally decreases in the course of filtration, whereas the ratio of Fe to Ti increases in a series of consecutive filtrates of soil solution. These observations can be interpreted as a result of interplay between the processes of TE leaching from soil and peat, complexation with colloids in the lake water and microbiological transformation of colloids in the course of the river flow and in the lake water. Results of the present study allow straightforward evaluation of the transformation of TE colloidal status between the site of their origin, migration and consumption (deposition) The work is executed at a Russian Federal Property Fund and CNRS support (?? 08-05-00312_a, 07-05-92212-CNRS_a).

  7. 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.

  8. 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 Tulou, if rated by the LEED green building certification program, would earn the highest certification as this rammed earth construction has offered efficient living for hundreds of years. As historic as these rammed earth structures are, they present an environmentally friendly option to structures of the future.

  9. 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.

  10. Stability Constants for Sulfate Complexation of Yttrium and the Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Schijf, J.; Byrne, R. H.

    2002-12-01

    In natural waters, yttrium and the rare earth elements (YREE) are mostly complexed with inorganic anions such as carbonate and chloride. YREE complexation with sulfate is minor (<5%) in seawater and generally negligible in fresh waters, yet it can be quite important in situations where oxidation of pyrite leads to high dissolved sulfate concentrations. The development of a consensus pattern of stability constants for YREE monosulfato-complexes has a quite convoluted history. It is based on a 1974 'compilation' that was derived from a much older, somewhat questionable, dataset, by adding interpolations and omitting a few elements. During subsequent transcriptions, some errors were introduced and the omitted data were interpolated rather than replaced with the original values. All this has resulted in a consensus pattern that is essentially flat, without any structure or fractionation between light and heavy REE. It is widely quoted and has been used to argue that sulfate complexation does not cause YREE fractionation. Conversely, flat YREE patterns in natural waters have been taken as evidence for substantial complexation of the YREE with sulfate. We have taken a new approach to measuring the stability constants of all YREE monosulfato-complexes with the greatest possible precision. Stability constants were determined by comparing the solubility of barium sulfate in YREE chloride solutions and in an ammonium chloride reference solution, all at the ionic strength of seawater. The reference solution and solutions of individual YREE chlorides were equilibrated with a small amount of high purity barium sulfate at t = 25C for at least one week. The equilibrated solutions were then filtered and analyzed for concentrations of YREE and Ba (ICP-MS), chloride and sulfate (ion chromatography), and pH (glass electrode). A simple model was used to determine the stability constants from these measurements. Averaged results from four experiments, two with and two without added sulfate, have standard deviations of 0.03 log units or less. Within this precision, the pattern of stability constants is not flat, as has been assumed, but has a very distinct shape. The pattern is nearly flat from La to Gd, possibly with a slight maximum at Eu. From Gd to Lu it shows a gradual and almost linear decrease, with the stability constant of Lu being more than 0.2 log units below that of La. The stability constant of Y is close to that of Er. Our pattern is in broad agreement with several careful earlier studies that have been largely ignored in the recent literature. Comparison with the substantial body of existing work also indicates that our stability constants are well within the published range for individual YREE. This revised pattern may have significant consequences for the interpretation of YREE patterns in high-sulfate environments such as runoff from mine tailings and certain groundwaters.

  11. 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 ?g/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 and Pd contents can be produced by the exhaustion of sulphide in the source, while the presence of Ru-Os-(Ir) alloys or sulphides (e.g. laurite) associated with Cr-spinel can explain Os, Ir, and Ru retention in the source residue. Such phases have been documented in fluid-fluxed sub-arc mantle from ophiolites. Osmium isotopes co-vary negatively with Os abundance and thus appear to be dominated by shallow level contamination. The most Os-rich samples, however, have 187Os/188Os ratios (0.126-0.132) which are typical of DMM and MORB, suggesting an indistinguishable flux of radiogenic Os from the slab. The significant fractionation of Pt and Re from Os in arc settings will lead, over time, to elevated 186Os and 187Os which may be relevant to the observed enrichments of these isotopes in some mantle regions. In addition, the differing behaviour of Ru and Ir, and the implication of a mantle source containing Ru-rich microphases, may have consequences for the estimation of the HSE composition of primitive upper mantle.

  12. 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

  13. The effect of rare earth elements on the texture and formability of asymmetrically rolled magnesium sheet

    SciTech Connect

    Alderman, Dr. Martyn; Cavin, Odis Burl; Davis, Dr. Bruce; Muralidharan, Govindarajan; Muth, Thomas R; Peter, William H; Randman, David; Watkins, Thomas R

    2011-01-01

    The lack of formability is a serious issue when considering magnesium alloys for various applications. Standard symmetric rolling introduces a strong basal texture that decreases the formability; however, asymmetric rolling has been put forward as a possible route to produce sheet with weaker texture and greater ductility. It has also been shown in recent work that weaker textures can be produced through the addition of rare earth elements to magnesium alloys. Therefore, this study has been carried out to investigate the effect of rare earth additions on the texture changes during asymmetric rolling. Two alloys have been used, AZ31B and ZEK100. The effect that the rare earth additions have on the texture of asymmetrically rolled sheet and the subsequent changes in formability will be discussed.

  14. 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}. Allowing R{sub b} to vary as R{sub p}{sup 1/2}, consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R{sub b} is constant. This model can account for most of the experimental data in the literature on the dependence of {sup 44}Ca/{sup 40}Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for {sup 18}O/{sup 16}O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R{sub b} on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that equire hyper-fast diffusivity in near-surface layers of the solid.

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

    SciTech Connect

    DePaolo, Donald J.

    2011-01-01

    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 (Rp) to the gross forward precipitation rate (Rf), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of Rp has been experimentally measured under varying conditions, but the magnitude of Rf 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, Rf can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (Rb or kb), since at equilibrium Rf = Rb, and Rp = 0. Hence it can be inferred that Rf ? Rp + Rb. 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 Rp (=Rf - Rb) Rb. For precipitation rates high enough that Rp Rb, 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 Rp ? Rb for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate Rf 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 Rp. Allowing Rb to vary as Rp1/2, consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where Rb is constant. This model can account for most of the experimental data in the literature on the dependence of 44Ca/40Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for 18O/16O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of Rb on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.

  16. 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; Bni, 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 essential for the improvement of resource recovery in the Thermo-Re process.

  17. Experimental investigations of trace element fractionation in iron meteorites. II - The influence of sulfur

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

    The partitioning of Ir, Ge, Ga, W, Cr, Au, P, and Ni between solid metal and metallic liquid is investigated as a function of temperature and the S-concentration of the metallic liquid. The partition coefficients for siderophile elements, such as Ir, W, Ga, and Ge, are found to increase by factors of 10-100 as the S-concentration of the metallic liquid increases from 0-30 wt percent. Partition coefficients for other siderophile elements, such as Ni, Au, and P, increase by factors of only 2-3. In contrast, a decrease is seen in the partition coefficients for the more chalcophile element Cr. These experimentally determined coefficients are used in conjunction with a fractional crystallization model to reproduce the geochemical behavior of Ni, P, Au, and Ir during the magmatic evolution of groups IIAB, IIIAB, IVA and IVB iron meteorites. The mean S-concentration for each group increases in the order IVB, IVA, IIIAB, IIAB, which is in accordance with cosmochemical prediction. However, the geochemical behavior of Ge, Ga, W, and Cr cannot be reproduced in an internally consistent way. It is concluded that the magmatic histories of these iron meteorite groups are more complex than has been generally assumed.

  18. Separation of tervalent transplutonium and rare-earth elements using for-tveks

    SciTech Connect

    Zaitsev, B.N.; Korolev, V.A.; Korovin, Y.F.; Kuzovov, Y.I.; Kvasnitskii, I.B.; Popik, V.P.

    1986-03-01

    The authors study the distribution of curium, americium, and certain rare-earth elements (REE) between aqueous nitric acid solutions and FOR-tveks under static and dynamic conditions. It is shown that on introducing diethylenetriaminepentaacetic acid into the aqueous solution separation coefficients for the transplutonium elements and REE can be obtained which are sufficiently high for practical use. A method is proposed for the group separation of REE and transplutonium elements under dynamic conditions. On a column 22 cm high coefficients of approximately 500 are obtained for the purification of curium from cerium, more than 260 from neodymium, 250 from lanthanum, and 14 from europium and gadolinium. The possibility has been studied of separating palladium from transplutonium elements and REE and isolating it as an individual product.

  19. 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.

  20. 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.

  1. Circular dust formations around earth and moon and some structural elements of dust formation around sun

    NASA Astrophysics Data System (ADS)

    Barsukov, V. L.; Nazarova, T. N.

    1989-01-01

    An analysis of meteoroid data from the Elektron 1 and 2, HEOS 2, Luna 10, Zond 3, and Venera 2 probes reveals the existence of circumterrestrial and circumlunar dust envelopes and yields information about the elements of an analogous circumsolar dust envelope. It is shown that meteoritic matter in these envelopes is distributed not uniformly but as individual clusters which move along gravitation centers (the earth, the moon, and the sun) in more or less stable orbits.

  2. 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 medium risk to the environment, and Cd levels in soils adjacent to the GS exhibited higher environment risk. PMID:25940495

  3. 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

  4. 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

  5. Heterogeneous Accretion of the Earth and the Timing of Volatile Element Depletion

    NASA Astrophysics Data System (ADS)

    Schönbächler, M.; Nimmo, F.

    2011-12-01

    The Earth is depleted in moderately volatile elements relative to CI chondrites and thus average solar system material. The timing of this depletion has been a matter of debate. Isotopic constraints from the short-lived Pd-Ag, Mn-Cr and Hf-W decay systems can be used to model the accretion history of the Earth and the timing of moderately volatile element depletion [1]. While the Pd-Ag decay system provides evidence for the accretion of volatile-rich material, other systems like Mn-Cr and Rb-Sr require that the Earth accreted volatile-depleted material [2, 3]. As recently shown [1], the contrasting evidence from these decay systems can be reconciled by heterogeneous accretion, which implies that the composition of the material from which the Earth accreted changed over time. A continuous core formation model was used and the best match was obtained for the Earth mainly accreting volatile-depleted material in the beginning and more volatile-rich material towards the end, while core formation was still ongoing [1]. However, a different study proposed that the bulk of the moderately volatile elements was delivered in a volatile-rich late veneer after core formation ceased [4]. This is not supported by the Pd-Ag data (Ag is a moderately volatile element, while Pd is more refractory). A late veneer of volatile-rich CI material (Pd = 556 ppb and Ag = 197 ppb) after core formation is limited to a maximum of ~0.4 % of the Earth's mass by the Pd concentration of the Earth's mantle today (~3.3 ppb). This amount of CI material does not supply enough Ag to substantially modify the Ag isotope composition of the Earth's mantle. In a scenario where the Earth accretes exceedingly volatile depleted material, its high Pd/Ag ratio would lead to an extreme radiogenic Ag isotope composition of the bulk silicate Earth (BSE), which cannot be counterbalanced by the late veneer to match the observed BSE composition. We also tested the heterogeneous accretion scenario using N-body accretion simulations [5] for the Pd-Ag decay system. Again the best results were obtained when materials with different degrees of volatile depletion (= different Pd/Ag ratios) were accreted. The simulations include early accretion of close-in material and later accretion of material from greater heliocentric distances, which is consistent with a transition from volatile-depleted to volatile-enriched material. Therefore, N-body accretion simulations and the continuous core formation model yield similar results, which demonstrates the robustness of the heterogeneous accretion scenario. [1] Schönbächler et al. (2010), Science 328, 884. [2] Carlson & Lugmair (1988), Earth Planet Sci. Lett. 90, 119. [3] Qin et al. (2009), Geochim. Cosmochim. Acta 74, 1122. [4] Albarède (2009), Nature, 461, 1227.[5] O'Brien et al. (2006), Icarus 184, 36.

  6. Sorption of Yttrium and the Rare Earth Elements on Non-Living Macroalgal Tissue

    NASA Astrophysics Data System (ADS)

    Schijf, J.; Straka, A. M.

    2007-12-01

    We have investigated sorption of yttrium and the rare earth elements (YREEs) on tissue of the green macroalga Ulva lactuca, commonly known as sea lettuce. Due to its nearly worldwide distribution in coastal waters, very simple morphology, and prodigious capacity for trace metal uptake from seawater, members of the Ulva genus serve as a basic but representative model of marine organic substrates in this type of study. In order to exclude active biological uptake effects, allowing us to focus on passive chemical mechanisms, we performed our initial experiments with sea lettuce Certified Reference Material consisting of a dehydrated, powdered tissue homogenate. A small quantity of this powder was suspended in NaCl solutions containing all YREEs, except Pm, at pH 3 and T = 25C. The extent of YREE sorption was determined as a function of pH at constant temperature by titrating the solution with dilute NaOH and measuring the YREE concentrations of 0.2-?m filtered aliquots with an ICP-MS at regular time intervals after each pH adjustment. In NaCl solutions with an ionic strength approaching that of seawater, distribution coefficients, which quantify the proportion of sorbed and dissolved metal concentrations, are a highly linear function of pH in the range 3-8. The slope of the line suggests a sorption mechanism that involves ion exchange with both H+ and Na+ on surface functional groups. The shape of solution YREE patterns indicates that these functional groups are probably carboxylates at low and intermediate pH, but that other groups may contribute at high pH. The identification of carboxylate functional groups appears to be confirmed by preliminary results from EXAFS spectroscopic analyses of individual REE sorbed on the surface of Ulva lactuca tissue under similar conditions, conducted at the ANL Advanced Photon Source. In dilute NaCl solutions the distribution coefficient is largely independent of pH. We believe that prolonged exposure of the tissue to a low ionic strength solution may modify the chemical structure of the cell wall and make it permeable to organic ligands that otherwise sequester the YREEs in the cell interior. Chemical extraction of filtered solutions from the low ionic strength experiment with silica-bonded C18, showing that a substantial fraction of dissolved YREEs is distinctly hydrophobic, seems to support this hypothesis. Additional experiments to clarify these observations, including acid-base titrations of the Ulva lactuca tissue to assess the number of different functional groups and their surface densities, are currently ongoing.

  7. Origin of fluorite mineralizations in the Nuba Mountains, Sudan and their rare earth element geochemistry

    NASA Astrophysics Data System (ADS)

    Ismail, Ibrahim; Baioumy, Hassan; Ouyang, Hegen; Mossa, Hesham; Aly, Hisham Fouad

    2015-12-01

    Among other mineralizations in the basement complex of the Nuba Mountains, fluorite occurs as lenses and veins in a number of localities. The rare earth elements (REE) geochemistry in these fluorites along with their petrography and fluid inclusion was investigated in this study to discuss the origin the fluorites and shed the light on the economic importance of the REE. Fluorites in the Nuba Mountains are classified into four categories based on their petrography. Category I (F1) is characterized by pink color and free of inclusions. Category II (F2) is zoned of alternating pink and colorless zones with euhedral outline or anhedral patchy pink and colorless fluorite enclosing category I fluorite and is usually sieved with submicroscopic silicate minerals. Category III (F3) is colorless, euhedral to anhedral fluorite and associated with quartz and/or orthoclase. Category IV (F4) is colorless, either massive or dispersed, corroded grains associated with calcite and pertain to the late introduced carbonatites in Dumbeir area. Gangue minerals in the studied fluorites include quartz, calcite, orthoclase and muscovite. The ΣREE ranges between 541 and 10,430 ppm with an average of 3234 ppm. Chondrite-normalized REE patterns for fluorite from different localities exhibit LREE enrichment relative to HREE as shown by (La/Yb)N ratios that vary from 16 to 194 and significant positive Eu anomalies that are pronounced with Eu/Eu* from 1.1 to 2.5. The Tb/La and Tb/Ca ratios of fluorites in the present study indicate that they plot mainly in the pegmatitic or high-hydrothermal field with the characteristics of primary crystallization and remobilization trend. The clear heterogeneity of fluorite, abundance of growth zones, irregular shapes of grains, presence of fluorite inclusions in other minerals as well as the relatively high concentration of REE in the studied fluorites are supportive for this interpretation. The relatively high Tb/La (0.002-0.013) and low Tb/Ca (0.0000007-0.0000086) ratios of the studied fluorites suggest that they precipitated from fractionated ore-bearing fluids at a late stage of deposition. The microtherometric measurements of the primary inclusions show that the Nuba Mountains fluorites were formed at temperatures greater than 600 °C. These values along with the low salinity of the fluid inclusions indicates homogenize at moderate temperatures. Thus the studied fluorite probably formed during the late stages of pegmatite consolidation under magmatic-hydrothermal transition conditions supporting the previous conclusions from REE geochemistry.

  8. Highly siderophile elements in Earth's mantle as a clock for the Moon-forming impact

    NASA Astrophysics Data System (ADS)

    Jacobson, Seth A.; Morbidelli, Alessandro; Raymond, Sean N.; O'Brien, David P.; Walsh, Kevin J.; Rubie, David C.

    2014-04-01

    According to the generally accepted scenario, the last giant impact on Earth formed the Moon and initiated the final phase of core formation by melting Earth's mantle. A key goal of geochemistry is to date this event, but different ages have been proposed. Some argue for an early Moon-forming event, approximately 30 million years (Myr) after the condensation of the first solids in the Solar System, whereas others claim a date later than 50 Myr (and possibly as late as around 100 Myr) after condensation. Here we show that a Moon-forming event at 40 Myr after condensation, or earlier, is ruled out at a 99.9 per cent confidence level. We use a large number of N-body simulations to demonstrate a relationship between the time of the last giant impact on an Earth-like planet and the amount of mass subsequently added during the era known as Late Accretion. As the last giant impact is delayed, the late-accreted mass decreases in a predictable fashion. This relationship exists within both the classical scenario and the Grand Tack scenario of terrestrial planet formation, and holds across a wide range of disk conditions. The concentration of highly siderophile elements (HSEs) in Earth's mantle constrains the mass of chondritic material added to Earth during Late Accretion. Using HSE abundance measurements, we determine a Moon-formation age of 95 +/- 32 Myr after condensation. The possibility exists that some late projectiles were differentiated and left an incomplete HSE record in Earth's mantle. Even in this case, various isotopic constraints strongly suggest that the late-accreted mass did not exceed 1 per cent of Earth's mass, and so the HSE clock still robustly limits the timing of the Moon-forming event to significantly later than 40 Myr after condensation.

  9. Highly siderophile elements in Earth's mantle as a clock for the Moon-forming impact.

    PubMed

    Jacobson, Seth A; Morbidelli, Alessandro; Raymond, Sean N; O'Brien, David P; Walsh, Kevin J; Rubie, David C

    2014-04-01

    According to the generally accepted scenario, the last giant impact on Earth formed the Moon and initiated the final phase of core formation by melting Earth's mantle. A key goal of geochemistry is to date this event, but different ages have been proposed. Some argue for an early Moon-forming event, approximately 30 million years (Myr) after the condensation of the first solids in the Solar System, whereas others claim a date later than 50 Myr (and possibly as late as around 100 Myr) after condensation. Here we show that a Moon-forming event at 40 Myr after condensation, or earlier, is ruled out at a 99.9 per cent confidence level. We use a large number of N-body simulations to demonstrate a relationship between the time of the last giant impact on an Earth-like planet and the amount of mass subsequently added during the era known as Late Accretion. As the last giant impact is delayed, the late-accreted mass decreases in a predictable fashion. This relationship exists within both the classical scenario and the Grand Tack scenario of terrestrial planet formation, and holds across a wide range of disk conditions. The concentration of highly siderophile elements (HSEs) in Earth's mantle constrains the mass of chondritic material added to Earth during Late Accretion. Using HSE abundance measurements, we determine a Moon-formation age of 95 ± 32 Myr after condensation. The possibility exists that some late projectiles were differentiated and left an incomplete HSE record in Earth's mantle. Even in this case, various isotopic constraints strongly suggest that the late-accreted mass did not exceed 1 per cent of Earth's mass, and so the HSE clock still robustly limits the timing of the Moon-forming event to significantly later than 40 Myr after condensation. PMID:24695310

  10. A Study on Removal of Rare Earth Elements from U.S. Coal Byproducts by Ion Exchange

    NASA Astrophysics Data System (ADS)

    Rozelle, Peter L.; Khadilkar, Aditi B.; Pulati, Nuerxida; Soundarrajan, Nari; Klima, Mark S.; Mosser, Morgan M.; Miller, Charles E.; Pisupati, Sarma V.

    2016-03-01

    Rare earth elements are known to occur in low concentrations in U.S. coals and coal byproducts. These low concentrations may make rare earth element recovery from these materials unattractive, using only physical separation techniques. However, given the significant production of rare earths through ion exchange extraction in China, two U.S. coal byproducts were examined for ion extraction, using ammonium sulfate, an ionic liquid, and a deep eutectic solvent as lixiviants. Extraction of rare earth elements in each case produced high recoveries of rare earth elements to the solution. This suggests that in at least the cases of the materials examined, U.S. coal byproducts may be technically suitable as REE ores. More work is required to establish economic suitability.

  11. A Study on Removal of Rare Earth Elements from U.S. Coal Byproducts by Ion Exchange

    NASA Astrophysics Data System (ADS)

    Rozelle, Peter L.; Khadilkar, Aditi B.; Pulati, Nuerxida; Soundarrajan, Nari; Klima, Mark S.; Mosser, Morgan M.; Miller, Charles E.; Pisupati, Sarma V.

    2016-01-01

    Rare earth elements are known to occur in low concentrations in U.S. coals and coal byproducts. These low concentrations may make rare earth element recovery from these materials unattractive, using only physical separation techniques. However, given the significant production of rare earths through ion exchange extraction in China, two U.S. coal byproducts were examined for ion extraction, using ammonium sulfate, an ionic liquid, and a deep eutectic solvent as lixiviants. Extraction of rare earth elements in each case produced high recoveries of rare earth elements to the solution. This suggests that in at least the cases of the materials examined, U.S. coal byproducts may be technically suitable as REE ores. More work is required to establish economic suitability.

  12. Complementary rare earth element patterns in unique achondrites, such as ALHA 77005 and shergottites, and in the earth

    NASA Technical Reports Server (NTRS)

    Ma, M.-S.; Schmitt, R. A.; Laul, J. C.

    1982-01-01

    Abundances of major, minor, and trace elements are determined in the Antarctic achondrite Allan Hills (ALHA) 77005 via sequential instrumental and radiochemical neutron activation analysis. The rare earth element (REE) abundances of ALHA 77005 reveal a unique chondritic normalized pattern; that is, the REEs are nearly unfractionated from La to Pr at approximately 1.0X chondrites, monotonically increased from Pr to Gd at approximately 3.4X with no Eu anomaly, nearly unfractionated from Gd and Ho and monotonically decreased from Ho to Lu at approximately 2.2X. It is noted that this unique REE pattern of ALHA 77005 can be modeled by a melting process involving a continuous melting and progressive partial removal of melt from a light REE enriched source material. In a model of this type, ALHA 77005 could represent either a crystallized cumulate from such a melt or the residual source material. Calculations show that the parent liquids for the shergottites could also be derived from a light REE enriched source material similar to that for ALHA 77005.

  13. Environmental impact of toxic elements in red mud studied by fractionation and speciation procedures.

    PubMed

    Mila?i?, Radmila; Zuliani, Tea; ?an?ar, Janez

    2012-06-01

    Aluminum (Al) is mostly produced from bauxite ore, which contains up to 70% of Al(2)O(3) (alumina). Before alumina is refined to aluminum metal, it is purified by hot alkaline extraction. As a waste by-product red mud is formed. Due to its high alkalinity and large quantities, it represents a severe disposal problem. In Kidri?evo (Slovenia), red mud was washed with water before disposal, and after drying, covered with soil. In Ajka (Hungary), the red mud slurry was collected directly in a containment structure, which burst caused a major accident in October 2010. In the present work the environmental impact of toxic elements in red mud from Kidri?evo and Ajka were evaluated by applying a sequential extraction procedure and speciation analysis. The predominant red mud fraction was the insoluble residue; nevertheless, environmental concern was focused on the highly mobile water-soluble fraction of Al and Cr. Al in the water-soluble Ajka mud fraction was present exclusively in form of toxic [Al(OH)(4)](-), while Cr existed in its toxic hexavalent form. Comparative assessment to red mud from Kidri?evo (Slovenia) with a lower alkalinity (pH 9) with that from Ajka demonstrated significantly lower Al solubility and the presence of only trace amounts of Cr(VI), confirming that disposal of neutralized mud is environmentally much more acceptable and carries a smaller risk of ecological accidents. Since during the Ajka accident huge amounts of biologically available Al and moderate Cr(VI) concentrations were released into the terrestrial and aquatic environments, monitoring of Al and Cr(VI) set free during remedial actions at the contaminated site is essential. Particular care should be taken to minimize the risk of release of soluble Al species and Cr(VI) into water supplies and surface waters. PMID:22542238

  14. Numerical Analysis of an H1-Galerkin Mixed Finite Element Method for Time Fractional Telegraph Equation

    PubMed Central

    Wang, Jinfeng; Zhao, Meng; Zhang, Min; Liu, Yang; Li, Hong

    2014-01-01

    We discuss and analyze an H1-Galerkin mixed finite element (H1-GMFE) method to look for the numerical solution of time fractional telegraph equation. We introduce an auxiliary variable to reduce the original equation into lower-order coupled equations and then formulate an H1-GMFE scheme with two important variables. We discretize the Caputo time fractional derivatives using the finite difference methods and approximate the spatial direction by applying the H1-GMFE method. Based on the discussion on the theoretical error analysis in L2-norm for the scalar unknown and its gradient in one dimensional case, we obtain the optimal order of convergence in space-time direction. Further, we also derive the optimal error results for the scalar unknown in H1-norm. Moreover, we derive and analyze the stability of H1-GMFE scheme and give the results of a priori error estimates in two- or three-dimensional cases. In order to verify our theoretical analysis, we give some results of numerical calculation by using the Matlab procedure. PMID:25184148

  15. Numerical analysis of an H1-Galerkin mixed finite element method for time fractional telegraph equation.

    PubMed

    Wang, Jinfeng; Zhao, Meng; Zhang, Min; Liu, Yang; Li, Hong

    2014-01-01

    We discuss and analyze an H(1)-Galerkin mixed finite element (H(1)-GMFE) method to look for the numerical solution of time fractional telegraph equation. We introduce an auxiliary variable to reduce the original equation into lower-order coupled equations and then formulate an H(1)-GMFE scheme with two important variables. We discretize the Caputo time fractional derivatives using the finite difference methods and approximate the spatial direction by applying the H(1)-GMFE method. Based on the discussion on the theoretical error analysis in L(2)-norm for the scalar unknown and its gradient in one dimensional case, we obtain the optimal order of convergence in space-time direction. Further, we also derive the optimal error results for the scalar unknown in H(1)-norm. Moreover, we derive and analyze the stability of H(1)-GMFE scheme and give the results of a priori error estimates in two- or three-dimensional cases. In order to verify our theoretical analysis, we give some results of numerical calculation by using the Matlab procedure. PMID:25184148

  16. Siku: A Sea Ice Discrete Element Method Model on a Spherical Earth

    NASA Astrophysics Data System (ADS)

    Kulchitsky, A. V.; Hutchings, J. K.; Johnson, J.

    2014-12-01

    Offshore oil and gas exploration and production activities in the Beaufort and Chukchi Seas can be significantly and adversely affected by sea ice. In the event of an oil spill, sea ice complicates the tracking of ice/oil trajectories and can hinder cleanup operations. There is a need for a sea ice dynamics model that can accurately simulate ice pack deformation and failure to improve the ability to track ice/oil trajectories and support oil response operations. A discrete element method (DEM) model, where each ice floe is represented by discrete elements that are initially bonded (frozen) together will be used to address the difficulty continuum modeling approaches have with representing discrete phenomena in sea ice, such as the formation of leads and ridges. Each discrete element in the DEM is a rigid body driven by environmental forcing (wind, current and Coriolis forces) and interaction forces with other discrete elements (compression, shear, tension, bond rupture and regrowth). We introduce a new DEM model ``Siku'', currently under development, to simulate ice drift of an ice floe on a spherical Earth. We will present initial free-drift results. Siku is focused on improving sea ice interaction mechanics and providing an accurate geometrical representation needed for basin scale and regional simulations. Upon completion, Siku will be an open source GNU GPL licensed user friendly program with embedded python capability for setting up simulations "scenarios" and coupling with other models to provide forcing fields. We use a unique quaternion representation for position and orientation of polygon sea-ice elements that use a second order integration scheme of sea-ice element motion on the Earth's sphere that does not depend on the location of the element and, hence, avoids numerical problems near the pole.

  17. Theoretical insights on the mobility and diffusive fractionation of incompatible elements in mantle rocks (Invited)

    NASA Astrophysics Data System (ADS)

    Dohmen, R.

    2010-12-01

    Solid-state diffusion is commonly regarded as a sluggish and inefficient process; even for long geological time scales it appears to affect the chemistry only on a very small scale (e.g. micrometer scale). However, grain and interface boundaries provide fast and interconnected pathways for diffusion that can significantly enhance the net mobility of elements (e.g., Hayden and Watson 2007). Whether diffusion along these transport paths dominate the bulk diffusivity in a rock depends not only on the relative diffusivity between the mineral volumes and grain boundaries, Dgb/Dl}, but also on the partitioning between the various diffusion media. It has been recently recognized that incompatible elements are located preferentially along grain and interface boundaries (e.g. Hiraga and Kohlstedt 2007), which can be characterized by the segregation coefficient, s. The mathematical model of Mishin and Herzig (1995) extends the commonly used classification scheme of Harrison (1961) for diffusion in mono-phase polycrystalline systems and considers explicitly the grain boundary segregation. For the time scales that allow the diffusive equilibration of an individual grain, three different situations can be distinguished, formally classified as A-regime, A’-regime, and A°-regime. If the grain size d is much greater than sδ /2 Dgb/Dl, the bulk diffusivity is effectively equal to Dl, which corresponds to the classical A regime. For the opposite case, when d << sδ /2 Dgb/Dl, grain boundary diffusion dominates the bulk diffusivity, which is roughly given by sδ /d Dgb and this case corresponds to the A’-regime. A rather extreme case occurs when sδ >> d, which requires extremely small grain size, large segregation, or both. In this situation the bulk diffusivity can be approximated at all times by Dgb. An important consequence for the A’-regime is that the bulk diffusivity of an element becomes sensitive to its segregation coefficient, which provides a mechanism for kinetic fractionation of elements, even if their grain boundary diffusion coefficients are identical. As shown by Hiraga and Kohlstedt (2007), segregation of incompatible elements can be well approximated using mineral-melt partition coefficients, since segregation is dominated by crystal chemistry effects. Based on this approximation, simple model calculations for diffusive transport of REE in an olivine aggregate indicate that at typical mantle temperatures, volumes of up to several km3 of mantle rock can be affected by diffusive transport (see also Hayden and Watson 2007 for experimental data). Since the segregation is analogous to mineral-melt partitioning this process produces different and characteristic trace element patterns at various places within this mantle region that overlap with those modelled by partial melting and extraction. Therefore, in various cases diffusive fractionation might be also considered as the origin or have an additional influence for observed trace element patterns. Harrison LG (1961) Trans Faraday Soc 57:1191 Hayden LA, Watson EB (2007) Nature 450:709 Hiraga T, Kohlstedt DL (2007) Geochim Cosmochim Acta 71:1281 Mishin Y, Herzig C (1995) Nanostruct Material 6:859

  18. What Can Neutrinos Tell Us about Light Elements in Earth's Core?

    NASA Astrophysics Data System (ADS)

    Li, J.; Dye, S.; Enomoto, S.

    2014-12-01

    The light element composition of the Earth's core remains mysterious despite decades' of research. Without any direct samples, our knowledge of the core composition has relied on a diversity of constraints including the density and velocity profiles derived from seismic and geophysical observations, the composition models proposed on the basis of geochemical and cosmochemical measurements, the material properties determined by mineral physics investigations, and the thermal and dynamo requirements coming out of dynamic modeling. The leading candidates for the principal light element include hydrogen, carbon, oxygen, sulfur and silicon, in the order of increasing atomic number. While each candidate stands out in some aspects and raises questions in others, none has been universally accepted as the dominant light element in the core. The controversy arises partly because the properties and behavior of various iron-alloys at extreme pressure and temperature conditions have not been fully constrained. It is also conceivable that existing approaches will not produce unique solution, and therefore requires new strategies. Neutrino oscillation tomography has recently emerged as a promising technique to probe the composition of Earth's interior. Neutrinos are produced in the atmosphere by cosmic ray interactions. Atmospheric neutrinos pass through the Earth's mantle and core, with flavor oscillations being affected by the electron density of the medium along the trajectories. The unique sensitivity of the atmospheric neutrinos to electron density introduces a contrast between hydrogen, which has a higher electron density, and carbon, oxygen, sulfur, and silicon, which have lower and similar electron densities. With sufficient exposure to an appropriate energy range, atmospheric neutrino measurements may allow us to detect the presence of the core and measure its radius. Here we compare electron densities of candidate model compositions of Earth's core and estimate the exposure requirements for identifying the dominant light element thorough neutrino oscillation tomography for both neutrino mass hierarchies. In particular, we will evaluate if any of the on-going and next-generation projects IceCube, PINGU, MICA, and HyperK can tell us about the light elements in Earth's core.

  19. Investigation of biological activity of fine fraction of lunar surface material returned to earth by the Luna 16 automatic station

    NASA Technical Reports Server (NTRS)

    Kustov, V. V.; Ostapenko, O. F.; Petrukhin, V. G.

    1974-01-01

    The biological action of a sample of lunar surface material returned to earth by the Luna 16 automatic station from a new region of the mare surface on male white mice was studied. The condition and behavior of the animals were observed; the intensity of their oxygen consumption was recorded, and motor activity of the muscles, leucocyte and erythrocytes counts in the peripheral blood, and the activity of whole blood chloinesterase were determined. Experimental results showed that the tested doses of the fine fraction of the lunar surface material from the Sea of Fertility were virtually innocuous for white mice.

  20. Experimental partitioning of rare earth elements and scandium among armalcolite, ilmenite, olivine and mare basalt liquid

    NASA Technical Reports Server (NTRS)

    Irving, A. J.; Merrill, R. B.; Singleton, D. E.

    1978-01-01

    An experimental study was carried out to measure partition coefficients for two rare-earth elements (Sm and Tm) and Sc among armalcolite, ilmenite, olivine and liquid coexisting in a system modeled on high-Ti mare basalt 74275. This 'primitive' sample was chosen for study because its major and trace element chemistry as well as its equilibrium phase relations at atmospheric pressure are known from previous studies. Beta-track analytical techniques were used so that partition coefficients could be measured in an environment whose bulk trace element composition is similar to that of the natural basalt. Partition coefficients for Cr and Mn were determined in the same experiments by microprobe analysis. The only equilibrium partial melting model appears to be one in which ilmenite is initially present in the source region but is consumed by melting before segregation of the high-Ti mare basalt liquid from the residue.

  1. Bioleaching of rare earth and radioactive elements from red mud using Penicillium tricolor RM-10.

    PubMed

    Qu, Yang; Lian, Bin

    2013-05-01

    The aim of this work is to investigate biological leaching of rare earth elements (REEs) and radioactive elements from red mud, and to evaluate the radioactivity of the bioleached red mud used for construction materials. A filamentous, acid-producing fungi named RM-10, identified as Penicillium tricolor, is isolated from red mud. In our bioleaching experiments by using RM-10, a total concentration of 2% (w/v) red mud under one-step bioleaching process was generally found to give the maximum leaching ratios of the REEs and radioactive elements. However, the highest extraction yields are achieved under two-step bioleaching process at 10% (w/v) pulp density. At pulp densities of 2% and 5% (w/v), red mud processed under both one- and two-step bioleaching can meet the radioactivity regulations in China. PMID:23548400

  2. Separation method and yields of small quantities of rare earth elements

    NASA Astrophysics Data System (ADS)

    Boulin, Y.; Juery, A.

    1992-08-01

    The EMIS PARSIFAL was designed to purify very small quantities of radioactive isotopes. Yields are therefore an important component of the separations. The ionization is done in a thermoionization source or a plasma source, according to the physical properties of the concerned elements. For rare earth elements (REE), hydroxides are electrodeposited on a tantalum wire; for thermoionization, the wire is introduced in a tungsten crucible whose depth is linked to the boiling point of the element. Samples weigh between 0.2 and 0.9 mg. The crucible, heated at 3050C by electron bombardment, gives REE yields from 20 to 40% and usually 50% for europium. The total beam intensity is about 5 10 -6 A and separations last from 2 to 20 hours until the whole sample is consumed.

  3. Bacterial Disproportionation of Elemental Sulfur Inferred from a Field Study of Stable-Isotope Fractionations between Elemental Sulfur and Pyrite

    NASA Astrophysics Data System (ADS)

    Hardisty, D.; Pratt, L. M.; Olyphant, G. A.; Bell, J.; Johnson, A.

    2011-12-01

    Elemental sulfur (ES) is a common product of pyrite oxidation during acid mine drainage (AMD), but bacterial disproportionation of ES has not previously been inferred in acidic environments. Pore water profiles were collected seasonally within a coal-mine waste deposit, Minnehaha, in Southwest Indiana that has been abandoned for over 30 years. Geochemical characterization and modeling were used to assess how the interactions between the sulfur and iron cycle are affected by seasonally dynamic hydrologic conditions. Pore waters were collected seasonally and concentrations of Fe-species and sulfur isotopic compositions of sulfate were determined. Additionally, a sediment core was collected and used for sequential extraction and isotopic characterization of solid-phase sulfur species including elemental sulfur (?34Ses), pyrite (?34Spy), acid-volatile sulfides, water-soluble sulfates, and acid-soluble sulfates. The dominant disulfide phase was found to be pyrite through x-ray diffraction of an additional sediment core. Sulfur isotope fractionations between ?34Spy and ?34Ses (?34Ses-py) of up to -33% are inferred to indicate bacterial disproportionation of ES in the presence of a non-limiting sulfide 'scrub' Fe(III). The initial isotopic composition, following formation from pyrite oxidation, is inferred from ?34Spy, found to be ? 8.75% at the study site. Although ES has previously been found to accumulate in acidic Fe(III)-rich pore waters, ES is typically assumed to account for less than 1% of the oxidized sulfur pool and measurements of the ES isotopic composition are often neglected during field studies of acid AMD. The pore waters at Minnehaha were seasonally suboxic with sharp transitions from Fe(III)- to Fe(II)- dominated conditions near the phreatic surface. It is hypothesized that the sulfide product of ES disproportionation, fractionated by up to -8.6%, is immediately re-oxidized to ES near the redox gradient via reaction with Fe(III). Sulfide re-oxidation allows for the accumulation of isotopically light ES that can then become subject to further sulfur disproportionation. A mass-balance model for ES, incorporating seasonally varying rates for pyrite oxidation, ES disproportionation, and ES oxidation, was developed in order to determine the potential and conditions necessary for extensive recycling of ES by disproportionating bacteria to produce ES enriched in 32S compared to the pyrite source. Simulations run for 32 seasonal cycles resulted in a ?34Ses-py of -16.4.% and an ES concentration of 170 ppm, which is consistent with average values obtained from the sediment core. The findings suggest that ES disproportionation is likely an important microbial process in AMD that should be considered at similar mining waste deposits experiencing seasonally varying hydrologic conditions and that ?34Ses-py can be used to estimate multiple cycles of ES disproportionation in oxic settings where the original source of ES is pyrite oxidation.

  4. Toward understanding early Earth evolution: prescription for approach from terrestrial noble gas and light element records in lunar soils.

    PubMed

    Ozima, Minoru; Yin, Qing-Zhu; Podosek, Frank A; Miura, Yayoi N

    2008-11-18

    Because of the almost total lack of geological record on the Earth's surface before 4 billion years ago, the history of the Earth during this period is still enigmatic. Here we describe a practical approach to tackle the formidable problems caused by this lack. We propose that examinations of lunar soils for light elements such as He, N, O, Ne, and Ar would shed a new light on this dark age in the Earth's history and resolve three of the most fundamental questions in earth science: the onset time of the geomagnetic field, the appearance of an oxygen atmosphere, and the secular variation of an Earth-Moon dynamical system. PMID:19001263

  5. Improved provenance tracing of Asian dust sources using rare earth elements and selected trace elements for palaeomonsoon studies on the eastern Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Ferrat, Marion; Weiss, Dominik J.; Strekopytov, Stanislav; Dong, Shuofei; Chen, Hongyun; Najorka, Jens; Sun, Youbin; Gupta, Sanjeev; Tada, Ryuji; Sinha, Rajiv

    2011-11-01

    The Asian Monsoon forms an important part of the earth's climate system, yet our understanding of the past interactions between its different sub-systems, the East Asian and Indian monsoons, and between monsoonal winds and other prevailing wind currents such as the Westerly jet, is limited, particularly in central Asia. This in turn affects our ability to develop climate models capable of accurately predicting future changes in atmospheric circulation patterns and monsoon intensities in Asia. Provenance studies of mineral dust deposited in terrestrial settings such as peat bogs can address this problem directly, by offering the possibility to examine past deposition rates and wind direction, and hence reconstruct past atmospheric circulation patterns. However, such studies are challenged by several issues, most importantly the identification of proxies that unambiguously distinguish between the different potential dust sources and that are independent of particle size. In addition, a single analytical method that is suitable for sample preparation of both dust source (i.e. desert sand, soil) and receptor (i.e. dust archive such as peat or soil profiles) material is desirable in order to minimize error propagation derived from the experimental and analytical work. Here, an improved geochemical framework of provenance tracers to study atmospheric circulation patterns and palaeomonsoon variability in central Asia is provided, by combining for the first time mineralogical as well as major and trace elemental (Sc, Y, Th and the rare earth elements) information on Chinese (central Chinese loess plateau, northern Qaidam basin and Taklamakan, Badain Juran and Tengger deserts), Indian (Thar desert) and Tibetan (eastern Qinghai-Tibetan Plateau) dust sources. Quartz, feldspars and clay minerals are the major constituents of all studied sources, with highly variable calcite contents reflected in the CaO concentrations. Chinese and Tibetan dust sources are enriched in middle REE relative to the upper continental crust and average shale but the Thar desert has a REE signature distinctly different from all other dust sources. There are significant differences in major, trace and REE compositions between the coarse and fine fractions of the surface sands, with the finest <4 μm fraction enriched in Al 2O 3, Fe 2O 3, MnO, MgO and K 2O and the <32 μm fractions in Sc, Y, Th and the REE relative to the coarse fractions. The <4 μm fraction best represents the bulk REE geochemistry of the samples. The provenance tracers Y/∑REE, La/Er, La/Gd, Gd/Er, La/Yb, Y/Tb, Y/La, Y/Nd and to a certain extent the europium anomaly Eu/Eu ∗ (all REE normalized to post-Archean Australian shale, PAAS) are particle size-independent tracers, of which combinations of Y/∑REE, La/Yb, Y/Tb, Y/La and Eu/Eu ∗ can be used to distinguish the Thar desert, the Chinese deserts, the Chinese loess plateau and the Tibetan soils. Their independence upon grain size means that these tracers can be applied to the long-range provenance tracing of Asian dust even when only bulk samples are available in the source region. Combinations of La/Th, Y/Tb, Y/∑REE, Sc/La and Y/Er distinguish the Tibetan soils from the Chinese loess plateau and the Chinese deserts. La/Th and notably Th/∑REE isolate the signature of the Badain Juran desert and the combination of Sc/La and Y/Er that of the Taklamakan desert. The similarity in all trace and REE-based provenance tracers between the northern Qaidam basin and Tengger desert suggests that these two deposits may have a common aeolian source.

  6. Behavior and Distribution of Heavy Metals Including Rare Earth Elements, Thorium, and Uranium in Sludge from Industry Water Treatment Plant and Recovery Method of Metals by Biosurfactants Application

    PubMed Central

    Gao, Lidi; Kano, Naoki; Sato, Yuichi; Li, Chong; Zhang, Shuang; Imaizumi, Hiroshi

    2012-01-01

    In order to investigate the behavior, distribution, and characteristics of heavy metals including rare earth elements (REEs), thorium (Th), and uranium (U) in sludge, the total and fractional concentrations of these elements in sludge collected from an industry water treatment plant were determined and compared with those in natural soil. In addition, the removal/recovery process of heavy metals (Pb, Cr, and Ni) from the polluted sludge was studied with biosurfactant (saponin and sophorolipid) elution by batch and column experiments to evaluate the efficiency of biosurfactant for the removal of heavy metals. Consequently, the following matters have been largely clarified. (1) Heavy metallic elements in sludge have generally larger concentrations and exist as more unstable fraction than those in natural soil. (2) Nonionic saponin including carboxyl group is more efficient than sophorolipid for the removal of heavy metals in polluted sludge. Saponin has selectivity for the mobilization of heavy metals and mainly reacts with heavy metals in F3 (the fraction bound to carbonates) and F5 (the fraction bound to Fe-Mn oxides). (3) The recovery efficiency of heavy metals (Pb, Ni, and Cr) reached about 90100% using a precipitation method with alkaline solution. PMID:22693485

  7. Quantification of rare earth elements using laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Martin, Madhavi; Martin, Rodger C.; Allman, Steve; Brice, Deanne; Wymore, Ann; Andre, Nicolas

    2015-12-01

    A study of the optical emission as a function of concentration of laser-ablated yttrium (Y) and of six rare earth elements, europium (Eu), gadolinium (Gd), lanthanum (La), praseodymium (Pr), neodymium (Nd), and samarium (Sm), has been evaluated using the laser-induced breakdown spectroscopy (LIBS) technique. Statistical methodology using multivariate analysis has been used to obtain the sampling errors, coefficient of regression, calibration, and cross-validation of measurements as they relate to the LIBS analysis in graphite-matrix pellets that were doped with elements at several concentrations. Each element (in oxide form) was mixed in the graphite matrix in percentages ranging from 1% to 50% by weight and the LIBS spectra obtained for each composition as well as for pure oxide samples. Finally, a single pellet was mixed with all the elements in equal oxide masses to determine if we can identify the elemental peaks in a mixed pellet. This dataset is relevant for future application to studies of fission product content and distribution in irradiated nuclear fuels. These results demonstrate that LIBS technique is inherently well suited for the future challenge of in situ analysis of nuclear materials. These studies also show that LIBS spectral analysis using statistical methodology can provide quantitative results and suggest an approach in future to the far more challenging multielemental analysis of ~ 20 primary elements in high-burnup nuclear reactor fuel.

  8. Spectral Analysis of Rare Earth Elements using Laser-Induced Breakdown Spectroscopy

    SciTech Connect

    Madhavi Z. Martin; Robert V. Fox; Andrzej W. Miziolek; Frank C. DeLucia, Jr.; Nicolas Andre

    2001-05-01

    There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to be able to quantify the concentrations of various REEs in realworld complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.

  9. Spectral analysis of rare earth elements using laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Martin, Madhavi Z.; Fox, Robert V.; Miziolek, Andrzej W.; DeLucia, Frank C.; André, Nicolas

    2015-06-01

    There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to be able to quantify the concentrations of various REEs in realworld complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.

  10. Rare earth elements recycling from waste phosphor by dual hydrochloric acid dissolution.

    PubMed

    Liu, Hu; Zhang, Shengen; Pan, Dean; Tian, Jianjun; Yang, Min; Wu, Maolin; Volinsky, Alex A

    2014-05-15

    This paper is a comparative study of recycling rare earth elements from waste phosphor, which focuses on the leaching rate and the technical principle. The traditional and dual dissolution by hydrochloric acid (DHA) methods were compared. The method of dual dissolution by hydrochloric acid has been developed. The Red rare earth phosphor (Y0.95Eu0.05)2O3 in waste phosphor is dissolved during the first step of acid leaching, while the Green phosphor (Ce0.67Tb0.33MgAl11O19) and the Blue phosphor (Ba0.9Eu0.1MgAl10O17) mixed with caustic soda are obtained by alkali sintering. The excess caustic soda and NaAlO2 are removed by washing. The insoluble matter is leached by the hydrochloric acid, followed by solvent extraction and precipitation (the DHA method). In comparison, the total leaching rate of the rare earth elements was 94.6% by DHA, which is much higher than 42.08% achieved by the traditional method. The leaching rate of Y, Eu, Ce and Tb reached 94.6%, 99.05%, 71.45%, and 76.22%, respectively. DHA can decrease the consumption of chemicals and energy. The suggested DHA method is feasible for industrial applications. PMID:24681591

  11. Earth

    NASA Technical Reports Server (NTRS)

    Carr, M. H.

    1984-01-01

    The following aspects of the planet Earth are discussed: plate tectonics, the interior of the planet, the formation of the Earth, and the evolution of the atmosphere and hydrosphere. The Earth's crust, mantle, and core are examined along with the bulk composition of the planet.

  12. Geochemical behaviour of trace elements during fractional crystallization and crustal assimilation of the felsic alkaline magmas of the state of Rio de Janeiro, Brazil.

    PubMed

    Motoki, Akihisa; Sichel, Susanna E; Vargas, Thais; Melo, Dean P; Motoki, Kenji F

    2015-12-01

    This paper presents geochemical behaviour of trace elements of the felsic alkaline rocks of the state of Rio de Janeiro, Brazil, with special attention of fractional crystallization and continental crust assimilation. Fractionation of leucite and K-feldspar increases Rb/K and decreases K2O/(K2O+Na2O). Primitive nepheline syenite magmas have low Zr/TiO2, Sr, and Ba. On the Nb/Y vs. Zr/TiO2 diagram, these rocks are projected on the field of alkaline basalt, basanite, and nephelinite, instead of phonolite. Well-fractionated peralkaline nepheline syenite has high Zr/TiO2 but there are no zircon. The diagrams of silica saturation index (SSI) distinguish the trends originated form fractional crystallization and crustal assimilation. In the field of SSI<-200, Zr/TiO2 and Ba/Sr have negative correlations to SSI in consequence of fractional crystallization. In the field of SSI>-200, they show positive correlations due to continental crust assimilation. Total REEs (Rare Earth Elements) is nearly 10 times that of granitic rocks, but LaN/SmN and LaN/YbN are similar. REE trend is linear and Eu anomaly is irrelevant. The pegmatitic liquid generated by country rock partial melting is SiO2-oversaturated and peraluminous with high Ba, Sr, Ba/Sr, Zr/TiO2, and SSI, with high content of fluids. This model justifies the peraluminous and SiO2-oversaturated composition of the rocks with relevant effects of continental crust assimilation. PMID:26628026

  13. The chemistry of the light rare-earth elements as determined by electron energy loss spectroscopy

    SciTech Connect

    Fortner, J.A.; Buck, E.C.

    1996-06-01

    The energy loss spectra of the rare earths are characterized by sharp {ital M}{sub 4,5} edges, the relative intensities of which are characteristic of the 4{ital f}-shell occupancy of the excited ion. For the light rare earths, the dependence of these relative peak heights on 4{ital f}-shell occupancy is quite pronounced. Thus they may be used to determine the oxidation state of the multivalent elements Ce and Pr. The second derivative of the spectrum is shown to be extremely sensitive to the chemical environment. Modern instrumentation and detection techniques allow the oxidation state of Ce and Pr to be determined even when they are present as only minor constituents. {copyright} {ital 1996 American Institute of Physics.}

  14. Origin of Volatiles in Earth: Indigenous Versus Exogenous Sources Based on Highly Siderophile, Volatile Siderophile, and Light Volatile Elements

    NASA Technical Reports Server (NTRS)

    Righter, K.; Danielson, L.; Pando, K. M.; Marin, N.; Nickodem, K.

    2015-01-01

    Origin of Earth's volatiles has traditionally been ascribed to late accretion of material after major differentiation events - chondrites, comets, ice or other exogenous sources. A competing theory is that the Earth accreted its volatiles as it was built, thus water and other building blocks were present early and during differentiation and core formation (indigenous). Here we discuss geochemical evidence from three groups of elements that suggests Earth's volatiles were acquired during accretion and did not require additional sources after differentiation.

  15. Systematics of metal-silicate partitioning for many siderophile elements applied to Earths core formation

    NASA Astrophysics Data System (ADS)

    Siebert, Julien; Corgne, Alexandre; Ryerson, Frederick J.

    2011-03-01

    Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 C, relative oxygen fugacities of IW-1.5 to IW-3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P- T- X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P- T- fO 2 conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P- T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P- T conditions constrained by the peridotite liquidus and fixed fO 2 yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO 2 conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth's mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.

  16. NEW RARE EARTH ELEMENT ABUNDANCE DISTRIBUTIONS FOR THE SUN AND FIVE r-PROCESS-RICH VERY METAL-POOR STARS

    SciTech Connect

    Sneden, Christopher; Lawler, James E.; Den Hartog, Elizabeth A.; Cowan, John J.; Ivans, Inese I. E-mail: jelawler@wisc.edu E-mail: cowan@nhn.ou.edu

    2009-05-15

    We have derived new abundances of the rare earth elements Pr, Dy, Tm, Yb, and Lu for the solar photosphere and for five very metal-poor, neutron-capture r-process-rich giant stars. The photospheric values for all five elements are in good agreement with meteoritic abundances. For the low-metallicity sample, these abundances have been combined with new Ce abundances from a companion paper, and reconsideration of a few other elements in individual stars, to produce internally consistent Ba, rare earth, and Hf (56 {<=} Z {<=} 72) element distributions. These have been used in a critical comparison between stellar and solar r-process abundance mixes.

  17. Peculiarities of the distribution of rare-earth elements and yttrium in mineral phases of the ferromanganese crusts from the Detroit guyot (Pacific Ocean)

    NASA Astrophysics Data System (ADS)

    Khanchuk, A. I.; Mikhailik, P. E.; Mikhailik, E. V.; Zarubina, N. V.; Blokhin, M. G.

    2015-12-01

    The concentrations of rare-earth elements and yttrium (REY) were first determined in four major mineral fractions of cobalt-rich ferromanganese crusts (CMC) from the Detroit guyot at the northern latitudes of the Pacific Ocean. It was shown that REY in the CMC from these latitudes are mainly adsorbed by the manganese phase unlike the crusts of the equatorial part of the ocean where iron hydroxides are the key REY sorbents from seawater. This is caused by the variations in the hydrochemical characteristics of seawater with the latitude of the CMC formation.

  18. Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques.

    PubMed

    Spalla, S; Baffi, C; Barbante, C; Turetta, C; Turretta, C; Cozzi, G; Beone, G M; Bettinelli, M

    2009-10-30

    In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries. PMID:19757452

  19. Rare earth elements geochemistry in springs from Taftan geothermal area SE Iran

    NASA Astrophysics Data System (ADS)

    Shakeri, Ata; Ghoreyshinia, Sayedkazem; Mehrabi, Behzad; Delavari, Morteza

    2015-10-01

    Concentrations of rare earth elements (REEs) were determined in springs and andesitic-dacitic rocks of Taftan geothermal field. Hydrochemical results of major ions indicate that thermal springs are Na-SO4-Cl and Ca-SO4-Cl types. Concentrations of REEs are in ranges of 10- 4 to 1.2 and 49 to ~ 62 times of chondrite for springwater and rock samples, respectively. The thermal (STS and TTS) and the cold (APS) springs with low pH values exhibit a very high REE contents (0.64 to 3.15 mg/l). Saturation index indicates that Fe and Al phases can control dissolved REE concentration in FTS and PF cold springs. The speciation of REE complexes indicates dominant presence of LnSO4+ and free ion in the Taftan thermal springs. In APS cold spring with pH ~ 4, fluoride complexes are dominate over the free ion and sulfate species, while in PF and FTS cold springs with pH 6.4 and 7, respectively, carbonate complexes (LnCO3+) are predominant species. Chondrite-normalized pattern for the low-pH waters show very distinctive gull-wing patterns, characteristic feature of acid-sulfate geothermal systems, and are similar to those of the host rocks. Chemical characteristics of rare earth elements in spring and volcanic rock samples indicate that REEs are originated from the andesitic-dacitic host rocks. Whole-rock-normalized REE patterns and petrographic evidences show that rare earth elements leached mainly from marginal alteration of minerals and matrix decomposition in volcanic rocks. In chondrite-normalized REE patterns, significant negative Eu anomaly in the cold springs compare to the thermal and acidic springs indicates that alteration of plagioclase is more intense in the later, corresponding to increasing in temperature and acidic state of reactant water.

  20. Study on the activated laser welding of ferritic stainless steel with rare earth elements yttrium

    NASA Astrophysics Data System (ADS)

    Wang, Yonghui; Hu, Shengsun; Shen, Junqi

    2015-10-01

    The ferritic stainless steel SUS430 was used in this work. Based on a multi-component activating flux, composed of 50% ZrO2, 12.09 % CaCO3, 10.43 % CaO, and 27.49 % MgO, a series of modified activating fluxes with 0.5%, 1%, 2%, 5%, 10%, 15%, and 20% of rare earth (RE) element yttrium (Y) respectively were produced, and their effects on the weld penetration (WP) and corrosion resistant (CR) property were studied. Results showed that RE element Y hardly had any effects on increasing the WP. In the FeCl3 spot corrosion experiment, the corrosion rates of almost all the samples cut from welded joints turned out to be greater than the parent metal (23.51 g/m2 h). However, there was an exception that the corrosion rate of the sample with 5% Y was only 21.96 g/m2 h, which was even better than parent metal. The further Energy Dispersive Spectrometer (EDS) test showed the existence of elements Zr, Ca, O, and Y in the molten slag near the weld seam while none of them were found in the weld metal, indicating the direct transition of element from activating fluxes to the welding seam did not exist. It was known that certain composition of activating fluxes effectively restrain the loss of Cr element in the process of laser welding, and as a result, the CR of welded joints was improved.

  1. Black Body Temperature in Terms of Earth's Orbital Elements and the Milankovitch Precession Index

    NASA Astrophysics Data System (ADS)

    Rubincam, D. P.

    2002-12-01

    The temperature T of a black or gray body orbiting the Sun can be expressed in terms of spherical harmonics in latitude and longitude, its Keplerian orbital elements, and a variable describing rotation about its axis. Assuming that the Earth is a gray body, the resulting equation for T exhibits previously unrecognized odd-degree zonal terms dubbed "Seversmith psychroterms." They cause a hemispheric temperature gradient which depends upon e sin w, where e is the orbital eccentricity and w is the Sun's argument of perihelion measured in an Earth-centered frame. The hemisphere containing perihelion is the cooler. For a gray body with the Earth's average albedo of 0.3, an emissivity of unity, and an obliquity of 23.5 degrees, the pole-to-pole temperature difference for the combined first and third degree spherical harmonic psychroterms can reach 3.4 K for the present eccentricity of 0.016, and 12.9 K for the maximum eccentricity of 0.06. While a black body with its boiling hot subsolar point and nights at absolute zero is a poor model for the Earth, the Seversmith psychroterms survive in more realistic models (although with smaller amplitudes) because the Earth radiates nonlinearly in T. The psychroterms acts in the direction opposite to the Milankovitch precession index, which also depends on e sin w: by warming the cool northern summers, the psychroterms make it harder for the traditional Milankovitch mechanism to operate. It may in fact be the Seversmith psychroterms which are actually responsible for the ice sheets which cycle with e sin w, instead of the Milankovitch mechanism. By cooling the southern hemisphere when perihelion is in the south, the psychroterms may somehow cause the southern hemisphere to control the northern ice sheets associated with the 19 kyr and 23 kyr periods (kyr = kiloyear), possibly through ice-albedo feedback in the sea-ice surrounding Antarctica.

  2. Influence of rare earth elements (Nd, Sm, Gd) on the physicochemical properties of ges crystal

    NASA Astrophysics Data System (ADS)

    Madatov, R. S.; Alekperov, A. S.; Magerramova, Dzh. A.

    2015-11-01

    Layered semiconductors (including GeS), which are widely used in modern electronics, are of great interest for researchers. New GeS-based devices have been developed for holographic recording, optical processing, and storage of information. In the last few years, American scientists have developed a unique GeS-based device that makes it possible to accumulate an immense amount of solar energy. The introduction of rare earth elements (REEs) facilitates the healing of metal and chalcogenide vacancies, removes polytypism, and enhances interlayer interaction.

  3. Studies of rare earth element distribution and action in human erythrocyte and animal hepatocyte by PIXE

    NASA Astrophysics Data System (ADS)

    Wu, Y. P.; Mi, Y.; Shen, H.; Yao, H. Y.; Cheng, Y.; Wang, X.; Zhang, J. X.

    2002-04-01

    PIXE analysis is applied to investigate a long-term disputed issue whether the rare earth element (REE) can enter the cell across the cell membrane or not. It has been illustrated that REE could travel across the biomembrane into the cells by cell studies in vitro as well as in studies of animals fed with REEs diet. The binding of REE by membrane changes its permeability and makes intracellular ion transportable. Entrance of REEs may influence the cellular function. In addition, the REE distribution and behavior in cell are discussed.

  4. Just How Earth-like are Extrasolar Super-Earths? Constraints on H+He Envelope Fractions from Kepler's Planet Candidates

    NASA Astrophysics Data System (ADS)

    Wolfgang, Angie; Lopez, E.; Kepler Team; SAMSI Bayesian Characterization of Exoplanet Populations Working Group

    2013-10-01

    With 3500 planetary candidates discovered in its first 3 years of data, the Kepler Mission promises to answer one of the most fundamental questions posed in exoplanetary research: what kinds of planets occur most often in our Galaxy? As Kepler primarily yields planetary radii and orbital periods, it has enabled numerous studies of the occurrence rate of planets as a function of these variables. Unfortunately, the full mass distribution, and thus a direct measure of these planets' possible compositions, remains elusive due to the unsuitability of these faint targets for radial velocity follow-up and the relative rareness of transit timing variations. We show, however, that relatively straightforward models of planetary evolution in an irradiated environment can make some progress without this full mass distribution towards understanding bulk compositions of the abundant Super-Earth/Sub-Neptunes that Kepler has discovered. In particular, we constrain the distribution of envelope fractions, i.e. the fraction of a planet's mass that is in a gaseous hydrogen and helium envelope around its rocky core, for this exoplanet population that has no analogs in our Solar System.

  5. Just How Earth-like are Extrasolar Super-Earths? Constraints on H+He Envelope Fractions from Kepler's Planet Candidates

    NASA Astrophysics Data System (ADS)

    Wolfgang, Angie; Lopez, E.; Kepler Team; SAMSI Bayesian Characterization of Exoplanet Populations Working Group

    2014-01-01

    With 3500 planetary candidates discovered in its first 3 years of data, the Kepler Mission promises to answer one of the most fundamental questions posed in exoplanetary research: what kinds of planets occur most often in our Galaxy? As Kepler primarily yields planetary radii and orbital periods, it has enabled numerous studies of the occurrence rate of planets as a function of these variables. Unfortunately, the full mass distribution, and thus a direct measure of these planets' possible compositions, remains elusive due to the unsuitability of these faint targets for radial velocity follow-up and the relative rareness of transit timing variations. We show, however, that relatively straightforward models of planetary evolution in an irradiated environment can make some progress without this full mass distribution towards understanding bulk compositions of the abundant Super-Earth/Sub-Neptunes that Kepler has discovered. In particular, we constrain the distribution of envelope fractions, i.e. the fraction of a planet's mass that is in a gaseous hydrogen and helium envelope around its rocky core, for this exoplanet population that has no analogs in our Solar System. This research builds on collaborations between astronomers and statisticians forged during a three week workshop on "Modern Statistical and Computational Methods for Analysis of Kepler Data" at SAMSI in June 2013.

  6. Schwann cells stimulated by axolemma-enriched fractions express cyclic AMP responsive element binding protein.

    PubMed

    Lee, M M; Sato-Bigbee, C; De Vries, G H

    1996-10-15

    Both axolemma-enriched fractions (AEF) and cyclic AMP have been shown to regulate the proliferation and differentiation of cultured primary Schwann cells (SC). We have evaluated the role of CREB, a transcription factor that binds to the cAMP-responsive element, in mediating the AEF-stimulated SC proliferation and differentiation. We detected CREB in nuclear extracts derived from SC stimulated with 40 micrograms/ml of AEF for 16, 24, 48, 72, and 96 hr, using a DNA-electrophoretic mobility shift assay. Unstimulated quiescent SC contained low levels of CREB which increased to a maximal level after 48 hr of AEF treatment. Using anti-CREB antibodies and Western blot analysis, after 24 hr of AEF treatment we first detected CREB as a 45 kDa protein which reached a maximal level of expression after 72 hr. Double labeled immunocytochemistry using anti-CREB and anti-5-bromo-2'-deoxy-uridine antibodies demonstrated maximal CREB expression after 72 hr of AEF treatment, closely coinciding with the temporal expression of SC proliferation. At all times examined, all AEF-treated SC labeled by anti-CREB antibodies were also labeled with anti-BrdU antibodies. These observations are consistent with the view that CREB could play an important role in the induction of SC proliferation by AEF. PMID:8915897

  7. An EDTA-?-cyclodextrin material for the adsorption of rare earth elements and its application in preconcentration of rare earth elements in seawater.

    PubMed

    Zhao, Feiping; Repo, Eveliina; Meng, Yong; Wang, Xueting; Yin, Dulin; Sillanp, Mika

    2016-03-01

    The separation and recovery of Rare earth elements (REEs) from diluted aqueous streams has attracted great attention in recent years because of ever-increasing REEs demand. In this study, a green synthesized EDTA-cross-linked ?-cyclodextrin (EDTA-?-CD) biopolymer was prepared and employed in adsorption of aqueous REEs, such as La(III), Ce(III), and Eu(III). EDTA acts not only as cross-linker but also as coordination site for binding of REEs. The adsorption properties for the adsorption of REEs by varying experimental conditions were carried out by batch tests. The kinetics results revealed that the surface chemical sorption and the external film diffusion were the rate-determining steps of the adsorption process. The obtained maximum adsorption capacities of EDTA-?-CD were 0.343, 0.353, and 0.365mmolg(-1) for La(III), Ce(III) and Eu(III), respectively. Importantly, the isotherms fitted better to Langmuir than Freundlich and Sips models, suggesting a homogenous adsorption surface for REEs on the adsorbent. Moreover, the multi-component adsorption, which was modeled by extended Sips isotherms, revealed adsorbent's selectivity to Eu(III). More significantly, the successful recoveries of the studied ions from tap water and seawater samples makes EDTA-?-CD a promising sorbent for the preconcentration of REEs from diluted aqueous streams. PMID:26674238

  8. Three dimensional analysis of unconfined seepage in earth dams by the weak form quadrature element method

    NASA Astrophysics Data System (ADS)

    Yuan, Shuai; Zhong, Hongzhi

    2016-02-01

    It remains challenging to determine the unknown free surface in three dimensional unconfined seepage in earth dams. A number of iterations are frequently required which make the problem computationally expensive. In the present research, a weak form quadrature element formulation is presented for three dimensional analysis of unconfined seepage which is an extension of the recently established method for two dimensional seepage problems. "Free points" are introduced by the interpolation of which the free surfaces are smoothly approximated. Grid lines are constructed in the element and the "free points" are confined to the lines when updated. An interpolatory scheme for locating the exit points is proposed. Formulations and procedures of the method are given in detail. Results of numerical examples are compared with available analytical solutions and numerical solutions in the literature and agreement is reached demonstrating the efficiency and reliability of the present formulation.

  9. Application of rare-earth element Y in refining impure copper

    NASA Astrophysics Data System (ADS)

    Li, Hai-hong; Sun, Xue-qin; Zhang, Shang-zhou; Zhao, Qin-yi; Wang, Guang-zhen

    2015-05-01

    The effects of rare-earth element Y in refining impure copper were investigated in this paper. The composition, microstructures, and corrosion resistance properties of impure copper before and after refinement with Y were investigated using direct-reading spectrometry, inductively coupled plasma atomic emission spectrometry, optical microscopy, scanning electron microscopy, and potentiodynamic polarization measurements. The results show that the concentrations of impurities S, As, Sb, Bi, Al, Cd, and Se are remarkably decreased. Adding an appropriate amount of Y refines the microstructure and enhances the corrosion resistance properties of impure copper in HCl solution via a purification effect. The formation enthalpies of compounds formed between Y and various impurity elements were calculated on the basis of Miedema's theory. The thermodynamic mechanisms of the refinement of impure copper by Y were also discussed

  10. Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China

    USGS Publications Warehouse

    Zheng, Lingyun; Liu, Gaisheng; Chou, C.-L.; Qi, C.; Zhang, Y.

    2007-01-01

    The rare earth elements (REEs) in coals are important because of: (a) REE patterns can be an indicator of the nature of source rocks of the mineral matter as well as sedimentary environments; (b) REEs abundance in coal may have industrial-significance. In this study, a total of thirty-four samples of Permian coal, partings, roof, and floor were collected from the Huaibei Coalfield, Anhui Province, China. Abundances of rare earth elements (REEs) and other elements in the samples were determined by inductively coupled-plasma mass spectrometry (ICP-MS) and inductively coupled-plasma atomic emission spectrometry (ICP-AES). The results show that the REEs are enriched in coals in the Huaibei Coalfield as compared with Chinese and U.S. coals and the world coal average. Coals in the Lower Shihezi Formation (No. 7, 5, and 4 Coals) and Upper Shihezi Formation (No. 3) have higher REE abundances than the coals in Shanxi Formation (No. 10). Magmatic intrusion resulted in high enrichment of REEs concentrations in No. 5 and 7 Coals. The REE abundances are positively correlated with the ash content. The mineral matter in these coals is mainly made up of clay minerals and carbonates. The REEs are positively correlated with lithophile elements including Si, Al, Ti, Fe, and Na, which are mainly distributed in clay minerals, indicating that REEs are contained mainly in clay minerals. The REE abundances in coals normalized by the ash are higher than that in partings. REEs abundances of coals cannot be accounted for by the REE content in the mineral matter, and some REEs associated with organic matter in coals. ?? 2007 Elsevier Ltd. All rights reserved.

  11. Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China

    NASA Astrophysics Data System (ADS)

    Zheng, Liugen; Liu, Guijian; Chou, Chen-Lin; Qi, Cuicui; Zhang, Ying

    2007-10-01

    The rare earth elements (REEs) in coals are important because of: (a) REE patterns can be an indicator of the nature of source rocks of the mineral matter as well as sedimentary environments; (b) REEs abundance in coal may have industrial-significance. In this study, a total of thirty-four samples of Permian coal, partings, roof, and floor were collected from the Huaibei Coalfield, Anhui Province, China. Abundances of rare earth elements (REEs) and other elements in the samples were determined by inductively coupled-plasma mass spectrometry (ICP-MS) and inductively coupled-plasma atomic emission spectrometry (ICP-AES). The results show that the REEs are enriched in coals in the Huaibei Coalfield as compared with Chinese and U.S. coals and the world coal average. Coals in the Lower Shihezi Formation (No. 7, 5, and 4 Coals) and Upper Shihezi Formation (No. 3) have higher REE abundances than the coals in Shanxi Formation (No. 10). Magmatic intrusion resulted in high enrichment of REEs concentrations in No. 5 and 7 Coals. The REE abundances are positively correlated with the ash content. The mineral matter in these coals is mainly made up of clay minerals and carbonates. The REEs are positively correlated with lithophile elements including Si, Al, Ti, Fe, and Na, which are mainly distributed in clay minerals, indicating that REEs are contained mainly in clay minerals. The REE abundances in coals normalized by the ash are higher than that in partings. REEs abundances of coals cannot be accounted for by the REE content in the mineral matter, and some REEs associated with organic matter in coals.

  12. Elemental composition and functional groups in soil labile organic matter fractions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Labile organic matter fractions are major components involved in nutrient cycle in soil. In this chapter, we examine three labile organic matter fraction: light fraction (LF), humic acid (HA) and fulvic acid (HA) in Alabama cotton soils (ultisol) amended with chemical fertilizer (NH4NO3) and poult...

  13. Mineralogy and geochemistry of trace and Rare Earth Element from the Manaila massive sulphide deposit (Eastern Carpathians, Romania)

    NASA Astrophysics Data System (ADS)

    Moldoveanu, S.; Iancu, O. G.; Kasper, H. U.

    2012-04-01

    Keywords: Eastern Carpathians, M?n?ila deposit, REE, trace elements, pyrite The present paper deal with the mineralogy and trace elements geochemistry of sulphide deposits from M?n?ila mine field located in NE area of Eastern Carpathians Mountains (Romania). The mineralization occurs within metamorphic rocks of Tulghe? terrane, part of Crystalline-Mezozoic zone of the Eastern Carpathians. The metamorphic rocks in M?n?ila area consist of felsic metavolcanics rocks with quartzites and quartz-feldspathic rocks as prevailing types. The P-T metamorphic conditions are typical of greenschis facies with biotite and garnet (Mn-Grt) in mineral assemblage. The mineralogical study was performed using reflected light microscope and Scanning Electron Microscopy (SEM) methods. Thus, the both methods show that the main sulphides minerals are represented by pyrite and chalcopyrite, being followed by sphalerite, galena and little amount of Cu sulphosalts (tetrahedrite and bournonite) and also by gangue minerals (quartz and carbonates). Pyrite occurs as large euhedral to subhedral grains in quartz and small rounded inclusion in chalcopyrite. The trace elements analysis was achieved on whole-rock samples and involved the determination of REE, LIL (Rb, Ba, Sr) and HFS (Y, Zr, Hf, U, Th, Nb, Ta) by ICP-MS method. The concentration of LIL and HFS trace elements in mineralized rocks decrease as follows: Ba > Bi > As > Sb > Co > Ga > Ni > Cd. Even if the barium contents in M?n?ila ore is high, baritina (BaSO4) was not identified throught the mineralogical analyses carried out so far. The total rare earth element content (REE) of the samples from M?n?ila range from 26.84 to 246.46 ppm. Chondrite - normalized REE patterns of the mineralized rocks show that the LREE are enriched in relation to the HREE. Also a positive Ce anomalies and negative Eu anomalies are present. Y/Ho and Zr/Hf ratios are close to the chondritic ratios indicating Charge-and-Radius-Controlled (CHARAC) behavior of these elements in pure silicate melts. The REE patterns of the ores are highly variable and do not appear to be related to the mineral compositions. This feature may reflect contributions from several factors involved in fluid formation, ore mineral deposition and post-depositional processes. The lack of a relation between major mineral composition and REE patterns suggests complex REE fractionation processes during the ore formation. This work was supported by the European Social Fund in Romania, under the responsibility of the Managing Authority for the Sectoral Operational Programme for Human Resources Development 2007-2013 (grant POSDRU/88/1.5/S/47646).

  14. Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

    USGS Publications Warehouse

    James, O.B.; Floss, C.; McGee, J.J.

    2002-01-01

    We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = CREE in low-Ca pyroxene/CREE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals. Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. "Equilibrium" liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates. Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occured significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ??Nd will be in error. Copyright ?? 2002 Elsevier Science Ltd.

  15. Toward understanding early Earth evolution: Prescription for approach from terrestrial noble gas and light element records in lunar soils

    PubMed Central

    Ozima, Minoru; Yin, Qing-Zhu; Podosek, Frank A.; Miura, Yayoi N.

    2008-01-01

    Because of the almost total lack of geological record on the Earth's surface before 4 billion years ago, the history of the Earth during this period is still enigmatic. Here we describe a practical approach to tackle the formidable problems caused by this lack. We propose that examinations of lunar soils for light elements such as He, N, O, Ne, and Ar would shed a new light on this dark age in the Earth's history and resolve three of the most fundamental questions in earth science: the onset time of the geomagnetic field, the appearance of an oxygen atmosphere, and the secular variation of an Earth–Moon dynamical system. PMID:19001263

  16. Spectral-finite element approach to three-dimensional viscoelastic relaxation in a spherical earth

    NASA Astrophysics Data System (ADS)

    Martinec, Zden?k.

    2000-07-01

    We present a spectral-finite element approach to the forward modelling of the visco-elastic response of a spherical earth with a 3-D viscosity structure to a surface mass load. It represents an alternative to a variety of numerical methods for 2-D and 3-D postglacial rebound modelling used recently (the finite element method, the perturbation method, the semi-analytical approach and the spectral-finite difference method). For a fixed time, the problem is reformulated in a weak sense and parametrized by tensor surface spherical harmonics in the angular direction, whereas piecewise linear finite elements span the radial direction. The solution is obtained with the Galerkin method, which leads to solving a system of linear algebraic equations. The time dependence of the problem is treated directly in the time domain (not in the Laplace domain) as a time evolution problem. The time derivative in the constitutive equation for a Maxwell viscoelastic body is approximated by the explicit Euler time-differencing scheme, which leads to time splitting of the stress tensor. The spectral-finite element method and the associated numerical code have been tested for 2-D (azimuthally symmetric) eccentrically nested spheres models, and good agreement has been obtained.

  17. Spectral-finite element approach to three-dimensional electromagnetic induction in a spherical earth

    NASA Astrophysics Data System (ADS)

    Martinec, Zden?k

    1999-01-01

    We present a spectral-finite element approach to the forward problem of 3-Dglobal-scale electromagnetic induction in a heterogeneous conducting sphere excited by an external source current. It represents an alternative to a variety of numerical methods for 3-D global-scale electromagnetic induction modelling developed recently (the perturbation expansion approach and the finite element and finite difference schemes). Two possible formulations of electromagnetic induction boundary-value problem are introduced. The boundary data used in the Dirichlet boundary-value problem consist of the horizontal components of the total magnetic induction measured on the Earth's surface, whereas the mixed boundary-value problem makes use of the scalar spherical harmonic expansion coefficients of the normal component of total magnetic induction in a near-space atmosphere. The latter problem is then reformulated in a weak sense and parametrized by vector spherical harmonics in the angular direction, whereas piecewise linear finite elements span the radial direction. The solution is searched for using the Galerkin method, which leads to solving a system of linear algebraic equations. We employ the biconjugate gradient method with preconditioning to solve the Galerkin system numerically. Particular care is devoted to the construction of a preconditioner that stabilizes the solution and speeds up the convergence of iterations. The spectral-finite element method and associated numerical code have been tested for 2-D (azimuthally symmetric) and 3-D (off-axis) eccentrically nested spheres models, and good agreement has been obtained.

  18. While China's dominance in rare earths dips, concerns remain about these and other elements

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2012-05-01

    China's dominance in the production of rare earth elements (REEs) peaked with that nation producing 97% of them in 2010; this number already has dipped to 90% in 2012 as mines in other nations are coming online, according to REE expert Karl Gschneidner Jr., a professor at Iowa State University's Ames Laboratory. Chinese production could drop to 60% by 2014, with production increasing at mines in the United States and other countries, he said. However, this reduction in China's share of REE production does not signal an end to the production crisis in REEs and other critical minerals, Gschneidner and others noted during a 1 May panel discussion on critical materials shortages at the AGU Science Policy Conference in Washington, D. C. REEs are a group of 17 chemically similar metallic elements used in a variety of electronic, optical, magnetic, and catalytic applications, and despite their name, they are relatively plentiful in the Earth's crust. China's control of known REE reserves has dropped from 75% in 1975 to 30.9% in 2012, with other regions also having large reserves, including the Commonwealth of Independent States (some former Soviet Republic states), the United States, and Australia, according to Gschneidner. Critical minerals are mineral commodities that are particularly important for a nation's economy or national defense that could potentially face supply disruptions.

  19. Rare earth elements in soils from selected areas on the Island of Hawaii

    SciTech Connect

    Barnard, W.M.; Halbig, J.B.

    1985-07-01

    Fifty soil samples for the wet, windward (east) side and dry, leeward (west) side of the Island of Hawaii were analyzed for La, Ce, Sm, Eu, Yb, and Lu by neutron activation/gamma-ray spectroscopic analysis. Data on concentrations in each sample are listed and analyzed statistically for soil samples collected from the western slope of Kohala Mountain, the western coastal plain of Mauna Kea, and the Northeastern coastal plain of Maunal Loa. Rare earth element (REE) concentrations are two to six times greater in soils from the western, dry side of the island, and good statistical correlation is exhibited among the samples for pairs of individual REEs. In the organic-rich soils of the east side, correlations are poor but are markedly improved when sample weights are adjusted for weight due to organic matter and water in soil colloids. If the mean compositions of selected rock samples from the Hawaii Reference Suite are representative of the compositions of the parent materials, REEs in the soils are moderately enriched (up to two times, based on oven-dry weights). Rare earth element concentrations in the island's western soils are as much as two times greater than the mean REE values of common sedimentary rocks worldwide; however, they are well within the concentration ranges of soils of continental origin. The eastern soils tend to have less La and Ce, but similar amounts of the middle and heavy REEs.

  20. Seawater rare-earth element patterns preserved in apatite of Pennsylvanian conodonts?

    NASA Astrophysics Data System (ADS)

    Bright, Camomilia A.; Cruse, Anna M.; Lyons, Timothy W.; MacLeod, Kenneth G.; Glascock, Michael D.; Ethington, Raymond L.

    2009-03-01

    Past workers have used rare-earth element patterns recorded in biogenic apatite as proxies for original seawater chemistry. To explore the potency of this approach, we analyzed Pennsylvanian conodonts from limestones, gray shales, and black shales of the Fort Scott and Pawnee formations (Desmoinesian) and Swope and Dennis formations (Missourian) in Kansas, Missouri, and Iowa, U.S.A. Analysis of individual platform conodonts from seven taxa using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) revealed a consistent enrichment in the middle rare-earth elements (MREE). Analogous MREE enrichment has been observed in authigenic apatite and bulk samples of phosphate-rich black shales from the same formations. Importantly, however, phosphate-depleted shales intimately associated with the P-rich intervals are relatively depleted in MREE. These antithetic patterns argue convincingly for secondary migration from the bulk sediment into the phosphate, and the extent of MREE enrichment in the conodonts is correlated positively with the total REE content. MREE enrichment in conodonts does not vary systematically as a function of lithology, stratigraphic level, conodont genus, geographic location, or with independent estimates of paleoredox conditions in the bottom waters. Collectively, these results argue for postmortem (diagenetic) REE uptake resulting in a pronounced (and progressive) MREE enrichment. Any cerium anomalies, if initially present, were masked by diagenetic uptake of REE. Paleoenvironmental interpretations of conodont REE, particularly for samples exhibiting MREE enrichment, should therefore be viewed with caution.

  1. The History and Use of Our Earth's Chemical Elements: A Reference Guide (by Robert E. Krebs)

    NASA Astrophysics Data System (ADS)

    Bracken, Reviewed By Jeffrey D.

    1999-04-01

    Greenwood Press: Westport, CT, 1998. 282 pp + 25 pp glossary + 37 pp index. 15.9 x 24.1 cm. ISBN 0-313-30123-9. $39.95. This book is an excellent resource for chemical educators at the high school and college levels. The format of the text is consistent and the writing style is clear and concise, making it ideally suited for student use also. The first three chapters serve to introduce the reader to a brief history of chemistry, early models of the atom, and the development of the periodic table. Names of the contributing scientists are mentioned whenever necessary, but the overall purpose of these introductory chapters is simply to lay a foundation for the subsequent seven chapters. A complete glossary of important scientific terms mentioned in the text should allow beginning students to use this book without feeling overwhelmed. Each entry for the 112 elements contains the following information: elemental symbol, atomic number, period, common valence, atomic weight, natural state, common isotopes, properties, characteristics, abundance, natural sources, history, common uses and compounds, and safety hazards. This information is well organized, with clear headings and separate sections making the book extremely user-friendly. Readers can easily obtain the information they desire without having to skim the full entry for a chosen element. One very nice feature of this book is that the elements entries are arranged by their locations in the periodic table. For example, chapter 4 contains the alkali metals and alkaline earth metals. This organizational scheme allows one to quickly see the patterns and trends within groups of elements. This format is significantly better than arranging the elements in alphabetical order, which places the entry for sodium far removed from the entries for lithium and potassium. I would highly recommend this book to high school teachers and college chemistry professors. It is well written and is an excellent source of information for both students and educators.

  2. Constraining Major Element Fractionation in an Alkali Gabbroic Sill using Mass Balance Modelling.

    NASA Astrophysics Data System (ADS)

    Ek, M.; Hogmalm, K. J.; Larson, S.-.

    2012-04-01

    The Ringkallen hill gabbro (RHG) is an ~225m thick layered alkali gabbroic sill in central Sweden. It is a part of the much larger ~1.26 Ga Ulv Gabbro complex, a series of 200-300m thick saucer-shaped alkali gabbroic intrusions with diameters of 30-80km. The anorthite (An.) content of plagioclase decrease gradually from ~70% at the margins to ~45% at the Sandwich Horizon, and the bulk composition of the RHG calculated from whole-rock analyses closely resembles the chilled margin composition, suggesting that the intrusion crystallised from a single pulse of magma in a closed system. Mass balance calculations were used to calculate the evolution of the supernatant liquid to the point where 90% of the intrusion had crystallised. The results show a successive decrease in the concentration of Al2O3 and MgO, an increase in MnO, TiO2, Na2O and K2O, while the concentrations of SiO2 and CaO remain stable. The major element variations of the calculated supernatant liquid were used to constrain the proportion between cumulus phases and crystallising liquid fraction (CLF). By iteratively changing the bulk partition coefficient by varying the proportion between the cumulus phases and the CLF for a given interval, the best estimate was found using root mean square method. The results indicate that the intrusion crystallised with a CLF of ~0.8 for the first 50% of crystallisation, and the next 30% had an estimated CLF of ~0.6 and the final 10% had ~0.8 CLF. At the point where 90% of the intrusion had crystallised, the stratigraphy contained only ~25% cumulus minerals. In strong contrast, simulation of the stratigraphic decrease in An. content of plagioclase by thermodynamic modelling suggests more than 70% fractional crystallisation. The strong stratigraphic decrease of plagioclase An. content is inconsistent with the modest change of the An. content of the calculated liquid. This suggests that the linear partitioning in the binary plagioclase system for these alkali gabbroic intrusions may be different from experimental results.

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

    SciTech Connect

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

    1981-10-10

    A wide range of rock types (abyssal tholeiite, Fe-Ti-rich basalt, andesite, and rhyodacite) were dredged from near 95/sup 0/ W and 85/sup 0/ W 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 P/sub 2/O/sub 5//K/sub 2/O ratio averages 0.83 at 95/sup 0/W and 1.66 at 85/sup 0/W and implies distinct mantle source compositions for the two areas. These source regions also have different rare earth element (REE) abundance patterns, with (La/Sm)/sub EF/ = 0.67 at 95/sup 0/W and 0.46 at 85/sup 0/W. The sequence of fractional lavas differs for the two areas and indicates earlier fractionation of apatite and titanomagnetite in the lavas from 95/sup 0/W. Incompatible trace element abundances in 26 samples are used to infer that the range of Fe-Ti-rich basalt from 85/sup 0/W represents 19 to 35% residual liquid following crystal fractionation of a mineral assemblage of plagioclase, clinopyroxene, and lesser olivine. Most samples from 85/sup 0/W can be related to a common parental magma that contained approximately 9 wt %FeO*, 1 wt % TiO/sub 2/, and had an Mg number (Mg/sup 3/ = 100 Mg/(Mg+Fe/sup 2 +/)) of about 65. Although the samples from 95/sup 0/W cannot all be derived from a common parental magma, the inferred parental magmas may have been derived by varying degrees of partial melting of a common source. The fractionation sequence consists of two parts: an initial iron enrichment trend followed by a silica enrichment trend. The most iron rich lavas represent about 32% residual liquid derived by crystal fractionation of plagioclase, clinopyroxene, and lesser olivine from a parental magma with an Mg number of about 66. The silicic enrichment trend results from crystallization of titanomagnetite and some apatite.

  4. The Koshak section: Evidence for element fractionation and an oxidation event at the K/T boundary

    NASA Technical Reports Server (NTRS)

    Nazarov, M. A.; Badjukov, D. D.; Barsukova, L. D.; Kolesov, G. M.; Naidin, D. P.

    1993-01-01

    The Koshak site is a new K/T section located about 125 km EEN of the Fort Shevchenko city, Mangyshlak, Kazakhstan. In this paper, we report results of geochemical and mineralogical studies of this section which indicate a deep element fractionation and an oxidation event at the K/T boundary.

  5. Earth Observatory Satellite system definition study. Report no. 5: System design and specifications. Part 1: Observatory system element specifications

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The performance, design, and quality assurance requirements for the Earth Observatory Satellite (EOS) Observatory and Ground System program elements required to perform the Land Resources Management (LRM) A-type mission are presented. The requirements for the Observatory element with the exception of the instruments specifications are contained in the first part.

  6. Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

    USGS Publications Warehouse

    Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

    1996-01-01

    In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive YSN and GdSN anomalies in seawater.

  7. Effect of the addition of low rare earth elements (lanthanum, neodymium, cerium) on the biodegradation and biocompatibility of magnesium.

    PubMed

    Willbold, Elmar; Gu, Xuenan; Albert, Devon; Kalla, Katharina; Bobe, Katharina; Brauneis, Maria; Janning, Carla; Nellesen, Jens; Czayka, Wolfgang; Tillmann, Wolfgang; Zheng, Yufeng; Witte, Frank

    2015-01-01

    Rare earth elements are promising alloying element candidates for magnesium alloys used as biodegradable devices in biomedical applications. Rare earth elements have significant effects on the high temperature strength as well as the creep resistance of alloys and they improve magnesium corrosion resistance. We focused on lanthanum, neodymium and cerium to produce magnesium alloys with commonly used rare earth element concentrations. We showed that low concentrations of rare earth elements do not promote bone growth inside a 750 μm broad area around the implant. However, increased bone growth was observed at a greater distance from the degrading alloys. Clinically and histologically, the alloys and their corrosion products caused no systematic or local cytotoxicological effects. Using microtomography and in vitro experiments, we could show that the magnesium-rare earth element alloys showed low corrosion rates, both in in vitro and in vivo. The lanthanum- and cerium-containing alloys degraded at comparable rates, whereas the neodymium-containing alloy showed the lowest corrosion rates. PMID:25278442

  8. Fractionation of highly siderophile elements in refertilized mantle: Implications for the Os isotope composition of basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, Claudio; Dale, Christopher W.; Garrido, Carlos J.; Pearson, D. Graham; Bosch, Delphine; Bodinier, Jean-Louis; Gervilla, Fernando; Hidas, Károly

    2014-08-01

    Highly fertile lherzolite and spinel websterite in the Ronda peridotite massif are enriched in Pt and Pd compared to Os, Ir, Ru and Re. The fractionation of the highly siderophile elements (HSE) in these rocks was produced by reaction of melt with their peridotite and pyroxenite precursors. Modeling indicates that upon reaction primary HSE hosts were dissolved and magmatic sulphides precipitated, largely erasing the original HSE signature of reacting protoliths. The budget of HSE in the melt was controlled by sulphide-silicate partitioning or entrainment of molten sulphide in silicate melt. Rhenium was likely removed from precursor peridotite and pyroxenite by previous melt extraction. Refertilization of peridotite by melts increased Al2O3, CaO, Pt, Pd contents and 187Os/188Os beyond typical values for mantle peridotite and the primitive upper mantle. The interaction of melts with residual peridotite and pyroxenite, as illustrated in the Ronda massif, can generate radiogenic-Os-enriched domains in the mantle with high melt productivity, higher Pt/Os and Pt/Re than common peridotite, and lower Re/Os than typical pyroxenite. As also previously proposed for pyroxenites, these “hybrid” domains can account for the difference in Os isotope compositions between many basalts (e.g., MORB and OIB) and common depleted mantle peridotites. Moreover, the presence of these enriched hybrid components in the mantle, evolved over sufficient timescales and in geologically reasonable proportions, may account for the 186Os-187Os enrichment of plume lavas without requiring a chemical contribution from the core.

  9. Fractionation of Highly Siderophile Elements in Refertilized Mantle: Implications for the Os Isotope Composition of Basalts

    NASA Astrophysics Data System (ADS)

    Marchesi, C.; Dale, C. W.; Garrido, C. J.; Pearson, D. G.; Bosch, D.; Bodinier, J. L.; Gervilla, F.; Hidas, K.

    2014-12-01

    Highly fertile lherzolite and spinel websterite in the Ronda peridotite massif are enriched in Pt and Pd compared to Os, Ir, Ru and Re. The fractionation of the highly siderophile elements (HSE) in these rocks was produced by reaction of melt with their peridotite and pyroxenite precursors. Modelling indicates that upon reaction primary HSE hosts were dissolved and magmatic sulphides precipitated, largely erasing the original HSE signature of reacting protoliths. The budget of HSE in the melt was controlled by sulphide-silicate partitioning or entrainment of molten sulphide in silicate melt. Rhenium was likely removed from precursor peridotite and pyroxenite by previous melt extraction. Refertilization of peridotite by melts increased Al2O3, CaO, Pt, Pd contents and 187Os/188Os beyond typical values for mantle peridotite and the primitive upper mantle. The interaction of melts with residual peridotite and pyroxenite, as illustrated in the Ronda massif, can generate radiogenic-Os-enriched domains in the mantle with high melt productivity, higher Pt/Os and Pt/Re than common peridotite, and lower Re/Os than typical pyroxenite. As also previously proposed for pyroxenites, these "hybrid" domains can account for the difference in Os isotope compositions between many basalts (e.g., MORB and OIB) and common depleted mantle peridotites. Moreover, the presence of these enriched hybrid components in the mantle, evolved over sufficient timescales and in geologically reasonable proportions, may account for the 186Os-187Os enrichment of plume lavas without requiring a chemical contribution from the core.

  10. Decrease of concentration and colloidal fraction of organic carbon and trace elements in response to the anomalously hot summer 2010 in a humic boreal lake.

    PubMed

    Shirokova, L S; Pokrovsky, O S; Moreva, O Yu; Chupakov, A V; Zabelina, S A; Klimov, S I; Shorina, N V; Vorobieva, T Ya

    2013-10-01

    The colloidal distribution and size fractionation of organic carbon (OC), major elements and trace elements (TE) were studied in a seasonally stratified, organic-rich boreal lake, Lake Svyatoe, located in the European subarctic zone (NW Russia, Arkhangelsk region). This study took place over the course of 4 years in both winter and summer periods using an in situ dialysis technique (1 kDa, 10 kDa and 50 kDa) and traditional frontal filtration and ultrafiltration (5, 0.22 and 0.025 μm). We observed a systematic difference in dissolved elements and colloidal fractions between summer and winter periods with the highest proportion of organic and organo-ferric colloids (1 kDa-0.22 μm) observed during winter periods. The anomalously hot summer of 2010 in European Russia produced surface water temperatures of approximately 30°C, which were 10° above the usual summer temperatures and brought about crucial changes in element speciation and size fractionation. In August 2010, the concentration of dissolved organic carbon (DOC) decreased by more than 30% compared to normal period, while the relative proportion of organic colloids decreased from 70-80% to only 20-30% over the full depth of the water column. Similarly, the proportion of colloidal Fe decreased from 90-98% in most summers and winters to approximately 60-70% in August 2010. During this hot summer, measurable and significant (>30% compared to other periods) decreases in the colloidal fractions of Ca, Mg, Sr, Ba, Al, Ti, Ni, As, V, Co, Y, all rare earth elements (REEs), Zr, Hf, Th and U were also observed. In addition, dissolved (<0.22 μm) TE concentrations decreased by a factor of 2 to 6 compared to previously investigated periods. The three processes most likely responsible for such a crucial change in element biogeochemistry with elevated water temperature are 1) massive phytoplankton bloom, 2) enhanced mineralization (respiration) of allochthonous dissolved organic matter by heterotrophic aerobic bacterioplankton and 3) photo-degradation of DOM and photo-chemical liberation of organic-bound TE. While the first process may have caused significant decreases in the total dissolved concentration of micronutrients (a factor of 2 to 5 for Cr, Mn, Fe, Ni, Cu, Zn and Cd and a factor of >100 for Co), the second and third factors could have brought about the decrease of allochthonous DOC concentration as well as the concentration and proportion of organic and organo-mineral colloidal forms of non-essential low-soluble trace elements present in the form of organic colloids (Al, Y, Ti, Zr, Hf, Th, Pb, all REEs). It can be hypothesized that climate warming in high latitudes capable of significantly raising surface water temperatures will produce a decrease in the colloidal fraction of most trace elements and, as a result, an increase in the most labile low molecular weight LMW(<1 kDa) fraction. PMID:23792250

  11. Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: a new perspective.

    PubMed

    Delgado, Joaqun; Prez-Lpez, Rafael; Galvn, Laura; Nieto, Jos Miguel; Boski, Tomasz

    2012-09-01

    Rare earth elements (REE) were analyzed in surface sediments from the Guadiana Estuary (SW Iberian Pyrite Belt). NASC (North American Shale Composite) normalized REE patterns show clearly convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE, indicating acid-mixing processes between fluvial waters affected by acid mine drainage (AMD) and seawater. However, REE distributions in the mouth (closer to the coastal area) show slightly LREE-enriched and flat patterns, indicating saline-mixing processes typical of the coastal zone. NASC-normalized ratios (La/Gd and La/Yb) do not discriminate between both mixing processes in the estuary. Instead, a new parameter (E(MREE)) has been applied to measure the curvature in the MREE segment. The values of E(MREE)>0 are indicative of acid signatures and their spatial distribution reveal the existence of two decantation zones from flocculation processes related to drought periods and flood events. Studying REE fractionation through the E(MREE) may serve as a good proxy for AMD-pollution in estuarine environments in relation to the traditional methods. PMID:22748838

  12. Dissolved indium and rare earth elements in three Japanese rivers and Tokyo Bay: Evidence for anthropogenic Gd and In

    NASA Astrophysics Data System (ADS)

    Nozaki, Yoshiyuki; Lerche, Dorte; Alibo, Dia Sotto; Tsutsumi, Makoto

    2000-12-01

    New data on the dissolved (<0.04 ?m) rare earth elements (REEs) and In in the Japanese Ara, Tama, and Tone river-estuaries and Tokyo Bay are presented. Unique shale-normalized REE patterns with a distinct positive Gd anomalies and a strong heavy-REE enrichment were seen throughout the data. The dissolved Gd anomaly is caused by local anthropogenic input mainly due to recent use of Gado-pentetic acid as a medical agent for magnetic resonance imaging (MRI) in hospitals. The heavy-REE enrichment may be attributed to fractionation during weathering and transport in the upstream of the rivers, and only partially to removal of light- and middle-REE enriched river colloids by the use of a new ultrafiltration technique. Dissolved In concentrations in the Japanese rivers are extraordinarily high as compared to those in the pristine Chao Phraya river of Thailand reported elsewhere (Nozaki et al., in press). Like Gd, the high dissolved In in the study area can also be ascribed to recent use of In-containing organic compound, In(DTPA) 2- in medical diagnosis. Thus, in the highly populated and industrialized area, dissolved heavy metal concentrations in rivers and estuaries may be significantly perturbed by human activities and the fate of those anthropogenic soluble substances in the marine environment needs to be investigated further.

  13. Rare earth element compositions of core sediments from the shelf of the South Sea, Korea: Their controls and origins

    NASA Astrophysics Data System (ADS)

    Jung, Hoi-Soo; Lim, Dhongil; Choi, Jin-Yong; Yoo, Hae-Soo; Rho, Kyung-Chan; Lee, Hyun-Bok

    2012-10-01

    Rare earth elements (REEs) of bulk sediments and heavy mineral samples of core sediments from the South Sea shelf, Korea, were analyzed to determine the constraints on REE concentrations and distribution patterns as well as to investigate their potential applicability for discriminating sediment provenance. Bulk sediment REEs showed large variation in concentrations and distribution patterns primarily due to grain size and carbonate dilution effects, as well as due to an abundance of heavy minerals. In the fine sandy sediments (cores EZ02-15 and 19), in particular, heavy minerals (primarily monazite and titanite/sphene) largely influenced REE compositions. Upper continental crust-normalized REE patterns of these sand-dominated sediments are characterized by enriched light REEs (LREEs), because of inclusion of heavy minerals with very high concentrations in LREEs. Notably, such a strong LREE enrichment is also observed in Korean river sediments. So, a great care must be taken when using the REE concentrations and distribution patterns of sandy and coarse silty shelf sediments as a proxy for discriminating sediment provenance. In the fine-grained muddy sediments with low heavy mineral abundance, in contrast, REE fractionation ratios and their UCC-normalized patterns seem to be reliable proxies for assessing sediment provenance. The resultant sediment origin suggested a long lateral transportation of some fine-grained Chinese river sediments (probably the Changjiang River) to the South Sea of Korea across the shelf of the northern East China Sea.

  14. Investigating the Partitioning of Inorganic Elements Consumed by Humans between the Various Fractions of Human Wastes: An Alternative Approach

    NASA Technical Reports Server (NTRS)

    Wignarajah, Kanapathipillai; Pisharody, Suresh; Fisher, John W.

    2003-01-01

    The elemental composition of food consumed by astronauts is well defined. The major elements carbon, hydrogen, oxygen, nitrogen and sulfur are taken up in large amounts and these are often associated with the organic fraction (carbohydrates, proteins, fats etc) of human tissue. On the other hand, a number of the elements are located in the extracellular fluids and can be accounted for in the liquid and solid waste fraction of humans. These elements fall into three major categories - cationic macroelements (e.g. Ca, K, Na, Mg and Si), anionic macroelements (e.g. P, S and Cl and 17 essential microelements, (e.g. Fe, Mn, Cr, Co, Cu, Zn, Se and Sr). When provided in the recommended concentrations to an adult healthy human, these elements should not normally accumulate in humans and will eventually be excreted in the different human wastes. Knowledge of the partitioning of these elements between the different human waste fractions is important in understanding (a) developing waste separation technologies, (b) decision-making on how these elements can be recovered for reuse in space habitats, and (c) to developing the processors for waste management. Though considerable literature exists on these elements, there is a lack of understanding and often conflicting data. Two major reasons for these problems include the lack of controlled experimental protocols and the inherently large variations between human subjects (Parker and Gallagher, 1988). We have used the existing knowledge of human nutrition and waste from the available literature and NASA documentation to build towards a consensus to typify and chemically characterize the various human wastes. It is our belief, that this could be a building block towards integrating a human life support and waste processing in a closed system.

  15. Cracking the Code of Soil Genesis. The Early Role of Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Zaharescu, D. G.; Dontsova, K.; Burghelea, C. I.; Maier, R. M.; Huxman, T. E.; Chorover, J.

    2014-12-01

    Soil is terrestrial life support system. Its genesis involves tight interactions between biota and mineral surfaces that mobilize structural elements into biogeochemical cycles. Of all chemical elements rare earth elements (REE) are a group of 16 non-nutrient elements of unusual geochemical similarity and present in all components of the surface environment. While much is known about the role of major nutrients in soil development we lack vital understanding of how early biotic colonization affects more conservative elements such as REE. A highly controlled experiment was set up at University of Arizona's Biosphere-2 that tested the effect of 4 biological treatments, incorporating a combination of microbe, grass, mycorrhiza and uninoculated control on REE leaching and uptake in 4 bedrock substrates: basalt, rhyolite, granite and schist. Generally the response of REE to biota presence was synergistic. Variation in total bedrock chemistry could explain major trends in pore water REE. There was a fast transition from chemistry-dominated to a biota dominated environment in the first 3-4 months of inoculation/seeding which translated into increase in REE signal over time. Relative REE abundances in water were generally reflected in plant concentrations, particularly in root, implying that below ground biomass is the main sync of REE in the ecosystem. Mycorrhiza effect on REE uptake in plant organs was significant and increased with infection rates. Presence of different biota translated into subtle differences in REE release, reveling potential biosignatures of biolota-rock colonization. The results thus bring fundamental insight into early stages non-nutrient cycle and soil genesis.

  16. Levels of platinum group elements and rare-earth elements in wild mushroom species growing in Poland.

    PubMed

    Mleczek, Mirosław; Niedzielski, Przemysław; Kalač, Pavel; Siwulski, Marek; Rzymski, Piotr; Gąsecka, Monika

    2016-01-01

    Due to limited data-describing abilities of mushrooms to accumulate platinum group elements (PGEs) and rare-earth elements (REEs), the aim of this study was to determine, by inductively coupled plasma optical emission spectrometry followed by microwave-assisted sample digestion by nitric acid, the content of these elements in 20 mushroom species (10 above ground and 10 growing on wood), mostly edible, collected near a busy trunk road. The highest content of PGEs in above-ground mushroom species was observed in Lepista gilva and Suillus bovinus fruit bodies (0.38 ± 0.05 and 0.37 ± 0.03 mg kg(-1) DW, respectively), while in mushrooms growing on wood, the highest content was observed in Pleurotus ostreatus (0.35 ± 0.04 mg kg(-1) DW). The mean content of PGEs for both these groups was 0.23 ± 0.08 and 0.26 ± 0.07 mg kg(-1) DW, respectively. The highest content of REEs in Suillus luteus and Tricholoma equestra was 5.03 ± 0.50 and 2.18 ± 0.56 mg kg(-1) DW, respectively, but within mushrooms growing on wood in Ganoderma applanatum fruiting bodies it was 4.19 ± 0.78 mg kg(-1) DW. Mean contents of REEs were 1.39 ± 1.21 and 1.61 ± 0.97 mg kg(-1) DW in above-ground species and species growing on wood, respectively. Generally, the group of mushroom species growing on wood was capable of slightly higher accumulation of both REEs and PGEs. No limits have been established for both the groups until now. PMID:26515437

  17. Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina.

    PubMed

    Fujiwara, Fabin; Dos Santos, Marina; Marrero, Julieta; Polla, Griselda; Gmez, Daro; Dawidowski, Laura; Smichowski, Patricia

    2006-09-01

    A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources. PMID:16951751

  18. Siderophile and chalcophile element abundances in oceanic basalts, Pb isotope evolution and growth of the earth's core

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.; White, W. M.; Jochum, K. P.; Hofmann, A. W.

    1986-01-01

    The hypothesis that the mantle Pb isotope ratios reflect continued extraction of Pb into the earth's core over geologic time is evaluated by studying the depeletion of chalcophile and siderophile elements in the mantle. Oceanic basalt samples are analyzed in order to determine the Pb, Sr, and Nd isotropic compositions and the abundances of siderophile and chalcophile elements and incompatible lithophile elements. The data reveal that there is no systematic variation of siderophile or chalcophile element abundances relative to abundances of lithophile elements and the Pb/Ce ratio of the mantle is constant. It is suggested that the crust formation involves nonmagmatic and magmatic processes.

  19. Grain Boundary Segregation of Rare-Earth Elements in Magnesium Alloys

    NASA Astrophysics Data System (ADS)

    Robson, Joseph D.; Haigh, Sarah J.; Davis, Bruce; Griffiths, David

    2016-01-01

    Small additions of rare-earth (RE) elements have been shown to have a powerful effect in modifying the texture of wrought magnesium alloys, giving a highly beneficial effect in improving their formability. Recent work has shown that segregation of RE atoms to grain boundaries is important in producing this texture change. In this work, two Mg-RE systems have been studied Mg-Y and Mg-Nd using high-resolution scanning transmission electron microscopy that permits both imaging and elemental analysis with a spatial resolution of better than 0.1 nm. The Mg-Y alloy, where the solubility and level of addition are relatively high, showed the RE texture change effect. This was accompanied by clustering of Y on the grain boundaries, consistent with previous studies of the Mg-Gd system. The Mg-Nd alloy, where the solubility and level of addition are relatively low, showed no texture change and no segregation. In this case, impurity elements binding the RE into insoluble particles, rendering it ineffective. The results are analyzed by modifying a previous model for the solute drag effect on boundaries expected due to the RE additions. This predicts that both Gd and Y will strongly inhibit boundary motion, with Gd being approximately twice as effective as Y.

  20. 'Nano' Morphology and Element Signatures of Early Life on Earth: A New Tool for Assessing Biogenicity

    NASA Technical Reports Server (NTRS)

    Oehler, D. Z.; Mostefaoui, S.; Meibom, A.; Selo, M.; McKay, D. S.; Robert, F.

    2006-01-01

    The relatively young technology of NanoSIMS is unlocking an exciting new level of information from organic matter in ancient sediments. We are using this technique to characterize Proterozoic organic material that is clearly biogenic as a guide for interpreting controversial organic structures in either terrestrial or extraterrestrial samples. NanoSIMS is secondary ion mass spectrometry for trace element and isotope analysis at sub-micron resolution. In 2005, Robert et al. [1] combined NanoSIMS element maps with optical microscopic imagery in an effort to develop a new method for assessing biogenicity of Precambrian structures. The ability of NanoSIMS to map simultaneously the distribution of organic elements with a 50 nm spatial resolution provides new biologic markers that could help define the timing of life s development on Earth. The current study corroborates the work of Robert et al. and builds on their study by using NanoSIMS to map C, N (as CN), S, Si and O of both excellently preserved microfossils and less well preserved, non-descript organics in Proterozoic chert from the ca. 0.8 Ga Bitter Springs Formation of Australia.

  1. Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

    USGS Publications Warehouse

    Bullen, T.D.; Bailey, S.W.

    2005-01-01

    Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87Sr/86Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87Sr/86Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87Sr/86Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms. ?? Springer 2005.

  2. Rare-earth element geochemistry and the origin of andesites and basalts of the Taupo Volcanic Zone, New Zealand

    USGS Publications Warehouse

    Cole, J.W.; Cashman, K.V.; Rankin, P.C.

    1983-01-01

    Two types of basalt (a high-Al basalt associated with the rhyolitic centres north of Taupo and a "low-Al" basalt erupted from Red Crater, Tongariro Volcanic Centre) and five types of andesite (labradorite andesite, labradorite-pyroxene andesite, hornblende andesite, pyroxene low-Si andesite and olivine andesite/low-Si andesite) occur in the Taupo Volcanic Zone (TVZ), North Island, New Zealand. Rare-earth abundances for both basalts and andesites are particularly enriched in light rare-earth elements. High-Al basalts are more enriched than the "low-Al" basalt and have values comparable to the andesites. Labradorite and labradorite-pyroxene andesites all have negative Eu anomalies and hornblende andesites all have negative Ce anomalies. The former is probably due to changing plagioclase composition during fractionation and the latter to late-stage hydration of the magma. Least-squares mixing models indicate that neither high-Al nor "low-Al" basalts are likely sources for labradorite/labradorite-pyroxene andesites. High-Al basalts are considered to result from fractionation of olivine and clinopyroxene from a garnet-free peridotite at the top of the mantle wedge. Labradorite/labradorite-pyroxene andesites are mainly associated with an older NW-trending arc. The source is likely to be garnet-free but it is not certain whether the andesites result from partial melting of the top of the subducting plate or a hydrated lower portion of the mantle wedge. Pyroxene low-Si andesites probably result from cumulation of pyroxene and calcic plagioclase within labradorite-pyroxene andesites, and hornblende andesites by late-stage hydration of labradorite-pyroxene andesite magma. Olivine andesites, low-Si andesites and "low-Al" basalts are related to the NNE-trending Taupo-Hikurangi arc structure. Although the initial source material is different for these lavas they have probably undergone a similar history to the labradorite/labradorite-pyroxene andesites. All lavas show evidence of crustal contamination. ?? 1983.

  3. Comparison of single and sequential extraction procedures for the study of rare earth elements remobilisation in different types of soils.

    PubMed

    Rao, Chebrolu Rama Mohan; Sahuquillo, Angels; Lopez-Sanchez, Jose Fermin

    2010-03-10

    With the continual increase in the utilisation of rare earth elements (REE) for industrial and agricultural purposes, research into the environmental and biogeochemical behaviour of REE had attracted much interest in recent times. This study principally describes the distribution of REE in four different types of soils like lateritic soil (S-1), in situ natural soil (S-2), soil contaminated by mining activity (S-3) and accidentally polluted soil (S-4) utilizing the optimised BCR sequential extraction procedure and partial extractions with various types of single extractants such as unbuffered salt solutions 0.1 M NaNO(3), 0.01 M CaCl(2), 1 M NH(4)NO(3); complexing agents 0.005 M DTPA and 0.05 M EDTA; acid solutions 0.43 M CH(3)COOH and 1 M HCl. Comparison of the sum of the four BCR fractions, which included an aqua regia attack on the residue, with the pseudo-total aqua regia digest values to assess the accuracy of the BCR partioning approach has been undertaken. Partial extraction results with several single extractants have also been reported for all the REE elements including yttrium which have been analysed by the optimised BCR procedure. Results obtained after 24 h extraction with each of the single extractant have also been discussed. The extraction with 1 M HCl during 24 h yielded similar quantities of REE as those released under the combined steps of 1, 2 and 3 of the BCR sequential extraction for all the four different type of soil samples indicating that this reagent can be used successfully to estimate the total extractable contents of REE in various types of soil samples. PMID:20171311

  4. Road-deposited sediments in an urban environment: A first look at sequentially extracted element loads in grain size fractions.

    PubMed

    Sutherland, Ross A; Tack, Filip M G; Ziegler, Alan D

    2012-07-30

    Sediments stored in urban drainage basins are important environmental archives for assessing contamination. Few studies have examined the geochemical fractionation of metals in individual grain size classes of solid environmental media. This is the first study of road sediments to quantify the mass loading of Al, Cu, Pb, and Zn in individual grain size classes (<63?m to 1000-2000?m) and partition contributions amongst four sequentially extracted fractions (acid extractable, reducible, oxidizable, and residual). The optimized BCR sequential extraction procedure was applied to road sediments from Palolo Valley, Oahu, Hawaii. Road sediments from this non-industrialized drainage basin exhibited significant enrichment in Cu, Pb, and Zn. Metal mass loading results indicate that the <63?m grain size class dominated almost all fraction loads for a given element. The residual fraction dominated the Al loading for this geogenic element. The reducible fraction, associated with Fe and Mn oxides, was the most important component for Cu, Pb, and Zn loading. These results have direct implications for environmental planners charged with reducing sediment-associated contaminant transport in urbanized drainage basins. PMID:22609391

  5. The distribution of Sr and REE between diopside and silicate liquid. [Rare Earth Elements

    NASA Technical Reports Server (NTRS)

    Grutzeck, M.; Kridelbaugh, S.; Weill, D.

    1974-01-01

    Experimental determination of the distribution coefficients in diopside-liquid pairs for strontium and nine rare-earth elements in the system CaMgSi2O6-NaAlSi3O8-CaAl2Si2O8. In experiments in air at 1265 C it is found that most of the Sr(2+), Eu(2+), and RE(3+) ions substitute for Ca(2+) and, in addition, a coupled substitution of Al(3+) for Si(4+) occurs. All of the trace ions considered are found to be excluded from the diopside lattice relative to the liquid. In the case of the trivalent ions the exclusion is much more pronounced for La and Ce, which have ionic radii larger than that of Ca(2+) in 8-fold oxygen coordination. Divalent Sr and Eu with even larger radii are also strongly excluded.

  6. Anthropogenic rare earth element fluxes into floodplains: Coupling between geochemical monitoring and hydrodynamic sediment transport modelling

    NASA Astrophysics Data System (ADS)

    Hissler, Christophe; Hostache, Renaud; Iffly, Jean François; Pfister, Laurent; Stille, Peter

    2015-09-01

    As all rare earth elements (REEs) have an increasingly important role in high tech industries, they are now recognized as emergent pollutants in river systems impacted by anthropogenic activity. Over the past 20 years, significant anthropogenic contributions were reported for Gd, La and Sm, and we may expect that REE contamination in rivers is to further increase in a near future. Despite the work done to assess the environmental impact of REE pollutions in larger river systems, we are still lacking information on the dynamics of these anthropogenic compounds in relation to hydrological changes. Here, we observed for the first time particulate Ce originating from local industrial activities in Luxembourg and we quantified the anthropogenic contribution to the REE fluxes at the river basin scale during a single flood event.

  7. Rare earths, other trace elements and iron in Luna 20 samples.

    NASA Technical Reports Server (NTRS)

    Helmke, P. A.; Blanchard, D. P.; Jacobs, J. W.; Haskin, L.; Haskin, A.

    1973-01-01

    The results of the analysis by neutron activation of six samples from the Luna 20 mission and one sample of less than 1 mm fines from Apollo 16 are reported. The concentrations of the rare-earth elements (REE) in the samples of fines from Luna 20 and Apollo 16 are less than those found for corresponding materials from the mare areas but a negative Eu anomaly is still present. The concentrations of the REE in fines from Luna 20 are only about two-thirds as great as in the sample of Apollo 16 fines, but the concentration of Co, Sc and Cr are greater by factors ranging from 1.5 to 2.3.

  8. Naturally occurring radionuclides and rare earth elements in weathered Japanese soil samples

    NASA Astrophysics Data System (ADS)

    Sahoo, Sarata; Hosoda, Masahiro; Prasad, Ganesh; Takahashi, Hiroyuki; Sorimachi, Atsuyuki; Ishikawa, Tetsuo; Tokonami, Shinji; Uchida, Shigeo

    2013-08-01

    The activity concentrations of 226Ra and 228Ac in weathered Japanese soils from two selected prefectures have been measured using a ?-ray spectroscopy system with high purity germanium detector. The uranium, thorium, and rare earth elements (REEs) concentrations were determined from the same soil samples using inductively coupled plasma mass spectrometry (ICP-MS). For example, granitic rocks contain higher amounts of U, Th, and light REEs compared to other igneous rocks such as basalt and andesites. Therefore, it is necessary to understand the interaction between REEs and nature of soils since soils are complex heterogeneous mixture of organic and inorganic solids, water, and gases. In this paper, we will discuss about distribution pattern of 238U and 232Th along with REEs in soil samples of weathered acid rock (granite) collected from two prefectures of Japan: Hiroshima and Miyagi.

  9. Rare earth and trace element geochemistry of a fragment of Jurassic seafloor, Point Sal, California

    NASA Technical Reports Server (NTRS)

    Menzies, M.; Blanchard, D.; Brannon, J.; Korotev, R.

    1977-01-01

    Rocks from an ophiolite suite once on the seafloor were analyzed for rare earth elements (REE), Sc, Co, Na2O, Cr, Zn and FeO. Strontium isotope exchange noted in some of the lavas is attributed to basalt-seawater interaction; the Ce abundance in smectite- and zeolite-bearing lavas may also be due to prolonged exposure to seawater. The higher grades of metamorphic rock, however, show no variation from the usual flat or slightly light REE depleted profiles. Plutonic igneous rock, all light REE depleted, have total REE abundances varying by a factor of 100 between the dunites and diorites. In order of decreasing REE abundance are hornblende, clinopyroxene, plagioclase, orthopyroxene and olivine. Calculations of REE contents of liquids in equilibrium with early cumulative clinopyroxenes suggest that the parent to the stratiform sequence was more depleted in light REE than the parent to the lava pile.

  10. Origin of middle rare earth element enrichment in acid mine drainage-impacted areas.

    PubMed

    Grawunder, Anja; Merten, Dirk; Bchel, Georg

    2014-01-01

    The commonly observed enrichment of middle rare earth elements (MREE) in water sampled in acid mine drainage (AMD)-impacted areas was found to be the result of preferential release from the widespread mineral pyrite (FeS2). Three different mining-impacted sites in Europe were sampled for water, and various pyrite samples were used in batch experiments with diluted sulphuric acid simulating AMD-impacted water with high sulphate concentration and high acidity. All water samples independent on their origin from groundwater, creek water or lake water as well as on the surrounding rock types showed MREE enrichment. Also the pyrite samples showed MREE enrichment in the respective acidic leachate but not always in their total contents indicating a process-controlled release. It is discussed that most probably complexation to sulphite (SO3 (2-)) or another intermediate S-species during pyrite oxidation is the reason for the MREE enrichment in the normalized REE patterns. PMID:24385183

  11. Behavior of Rare Earth Element In Geothermal Systems; A New Exploration/Exploitation Tool

    SciTech Connect

    Scott A. Wood

    2002-01-28

    The goal of this four-year project was to provide a database by which to judge the utility of the rare earth elements (REE) in the exploration for and exploitation of geothermal fields in the United States. Geothermal fluids from hot springs and wells have been sampled from a number of locations, including: (1) the North Island of New Zealand (1 set of samples); (2) the Cascades of Oregon; (3) the Harney, Alvord Desert and Owyhee geothermal areas of Oregon; (4) the Dixie Valley and Beowawe fields in Nevada; (5) Palinpion, the Philippines: (6) the Salton Sea and Heber geothermal fields of southern California; and (7) the Dieng field in Central Java, Indonesia. We have analyzed the samples from all fields for REE except the last two.

  12. Light shifts and magic wavelengths for heavy alkaline earth elements: Ba and Ra

    NASA Astrophysics Data System (ADS)

    Dammalapati, U.; Santra, B.; Willmann, L.

    2012-01-01

    In this paper, we investigate light shifts of heavy alkaline earth elements barium (Ba) and radium (Ra), which are interesting for optical lattice clocks and for permanent electric dipole moment searches. Detailed knowledge is required in the design of efficient loading of atoms from a magneto-optical trap into an optical dipole trap, to facilitate Doppler cooling while trapping and to achieve longer lifetimes of the trapped atoms with reduced heating rates. The wavelength dependence of light shifts of the ns2 1S0 ground state, the nsnp 3P1 and ns(n - 1)d 1D2 excited states in barium (n = 6) and the n s2 1S0 ground state, the nsnp 3P1 and ns(n - 1)d 3D2 excited states in radium (n = 7) are calculated. Several magic wavelengths in the visible and infrared regions accessible with commercial lasers for optical dipole trapping of Ba and Ra are identified.

  13. Study on the electrochemical extraction of rare earth elements from FLINAK

    SciTech Connect

    Long, Dewu; Huang, Wei; Jiang, Feng; Tian, Lifang; Li, Qingnuan

    2013-07-01

    Electrochemical behaviors of rare earth elements, such as NdF{sub 3}, GdF{sub 3}, SmF{sub 3}, YF{sub 3}, and EuF{sub 3}, were investigated in a LiF-NaF-KF (46.5-11.5-42.0 mol %, FLINAK, m. p. 454 Celsius degrees) solvent. The results indicated that it is possible to extract Nd, Gd and Y directly by electrochemical deposition since the reductions of those cations to metal are located in the electrochemical window of the FLINAK eutectic, while the reductions of Sm and Eu metal are out of the range of the medium. Subsequently electro-deposition of Nd was carried out with two kinds of cathodic materials, namely, an inert cathode, Pt, and a reactive electrode, Cu. The collected products were characterized by various techniques revealing that a Nd-rich product was obtained. (authors)

  14. Predictive model for ionic liquid extraction solvents for rare earth elements

    NASA Astrophysics Data System (ADS)

    Grabda, Mariusz; Oleszek, Sylwia; Panigrahi, Mrutyunjay; Kozak, Dmytro; Eckert, Franck; Shibata, Etsuro; Nakamura, Takashi

    2015-12-01

    The purpose of our study was to select the most effective ionic liquid extraction solvents for dysprosium (III) fluoride using a theoretical approach. Conductor-like Screening Model for Real Solvents (COSMO-RS), based on quantum chemistry and the statistical thermodynamics of predefined DyF3-ionic liquid systems, was applied to reach the target. Chemical potentials of the salt were predicted in 4,400 different ionic liquids. On the base of these predictions set of ionic liquids' ions, manifesting significant decrease of the chemical potentials, were selected. Considering the calculated physicochemical properties (hydrophobicity, viscosity) of the ionic liquids containing these specific ions, the most effective extraction solvents for liquid-liquid extraction of DyF3 were proposed. The obtained results indicate that the COSMO-RS approach can be applied to quickly screen the affinity of any rare earth element for a large number of ionic liquid systems, before extensive experimental tests.

  15. Bioadsorption of Rare Earth Elements through Cell Surface Display of Lanthanide Binding Tags.

    PubMed

    Park, Dan M; Reed, David W; Yung, Mimi C; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Fujita, Yoshiko; Riman, Richard E; Navrotsky, Alexandra; Jiao, Yongqin

    2016-03-01

    With the increasing demand for rare earth elements (REEs) in many emerging clean energy technologies, there is an urgent need for the development of new approaches for efficient REE extraction and recovery. As a step toward this goal, we genetically engineered the aerobic bacterium Caulobacter crescentus for REE adsorption through high-density cell surface display of lanthanide binding tags (LBTs) on its S-layer. The LBT-displayed strains exhibited enhanced adsorption of REEs compared to cells lacking LBT, high specificity for REEs, and an adsorption preference for REEs with small atomic radii. Adsorbed Tb(3+) could be effectively recovered using citrate, consistent with thermodynamic speciation calculations that predicted strong complexation of Tb(3+) by citrate. No reduction in Tb(3+) adsorption capacity was observed following citrate elution, enabling consecutive adsorption/desorption cycles. The LBT-displayed strain was effective for extracting REEs from the acid leachate of core samples collected at a prospective rare earth mine. Our collective results demonstrate a rapid, efficient, and reversible process for REE adsorption with potential industrial application for REE enrichment and separation. PMID:26836847

  16. Planktonic foraminiferal rare earth elements as a potential new aeolian dust proxy

    NASA Astrophysics Data System (ADS)

    Chou, C.; Liu, Y.; Lo, L.; Wei, K.; Shen, C.

    2012-12-01

    Characteristics of rare earth elements (REEs) have widely been used as important tracers in many fields of earth sciences, including lithosphere research, environmental change, ocean circulation and other natural carbonate materials. Foraminiferal test REE signatures have been suggested to reflect ambient seawater conditions and serve as valuable proxies in the fields of paleoceanography and paleoclimate. Here we present a 60-kyr planktonic foraminifera Globigerinoides ruber (white, 250-300 ?m) REE record of a sediment core MD05-2925 (920.61'S, 15127.61'E, water depth 1660 m) from the Solomon Sea. The REE diagram shows two dominant sources of local seawater and nearby terrestrial input. The variability of foraminiferal REE/Ca time series is different from Mg/Ca-inferred sea surface temperature and ?18O records during the past 60-kyr. This inconsistency suggests that planktonic foraminiferal REE content cannot result only from changes in ice volume and temperature. Synchroneity between high planktonic foraminiferal REE content and Antarctic ice core dust amount record implies the same dust sources, probably from Australia or mainland China. Our results suggest that foraminiferal REE can potentially be as a new dust proxy and record dry/humid conditions at the source area.

  17. Finite difference/finite element method for two-dimensional space and time fractional Bloch-Torrey equations

    NASA Astrophysics Data System (ADS)

    Bu, Weiping; Tang, Yifa; Wu, Yingchuan; Yang, Jiye

    2015-07-01

    In this paper, a class of two-dimensional space and time fractional Bloch-Torrey equations (2D-STFBTEs) are considered. Some definitions and properties of fractional derivative spaces are presented. By finite difference method and Galerkin finite element method, a semi-discrete variational formulation for 2D-STFBTEs is obtained. The stability and convergence of the semi-discrete form are discussed. Then, a fully discrete scheme of 2D-STFBTEs is derived and the convergence is investigated. Finally, some numerical examples based on linear piecewise polynomials and quadratic piecewise polynomials are given to prove the correctness of our theoretical analysis.

  18. X-ray fluorescence analysis of rare earth elements in rocks using low dilution glass beads.

    PubMed

    Nakayama, Kenichi; Nakamura, Toshihiro

    2005-07-01

    Major and trace elements (Na, Mg, Al, Si, P, K, Ca, Ti, Mn, Fe, Rb, Sr, Y, Zr, La, Ce, Pr, Nd, Sm, Gd, Dy, Th and U) in igneous rocks were assayed with fused lithium borate glass beads using X-ray fluorescence spectrometry. Low dilution glass beads, which had a 1:1 sample-to-flux ratio, were prepared for determination of rare earth elements. Complete vitrification of 1:1 mixture required heating twice at 1200 degrees C with agitation. Extra pure reagents containing determinants were used for calibrating standards instead of the rock standard. The calibration curves of the 23 elements showed good linearity. Furthermore, the lower limits of detection corresponding to three times the standard deviation for blank measurements were 26 mass ppm for Na2O, 6.7 for MgO, 4.5 for Al2O3, 4.5 for SiO2, 18 for P2O5, 1.1 for K2O, 4.0 for CaO, 3.9 for TiO2, 1.6 for MnO, 0.8 for Fe2O3, 0.5 for Rb, 0.2 for Sr, 0.4 for Y, 0.5 for Zr, 3.3 for La, 6.5 for Ce, 2.7 for Pr, 2.1 for Nd, 1.7 for Sm, 0.7 for Gd, 2.7 for Dy, 0.5 for Th, and 0.6 for U. Using the present method, we determined the contents of these 23 elements in four rhyolitic and granitic rocks from Japan. PMID:16038502

  19. Geology and market-dependent significance of rare earth element resources

    NASA Astrophysics Data System (ADS)

    Simandl, G. J.

    2014-09-01

    China started to produce rare earth elements (REEs) in the 1980s, and since the mid-1990s, it has become the dominant producer. Rare earth element export quotas first introduced by the Chinese government in the early 2000s were severely reduced in 2010 and 2011. This led to strong government-created disparity between prices within China and the rest of the world. Industrialized countries identified several REEs as strategic metals. Because of rapid price increases of REE outside of China, we have witnessed a world-scale REE exploration rush. The REE resources are concentrated in carbonatite-related deposits, peralkaline igneous rocks, pegmatites, monazite ± apatite veins, ion adsorption clays, placers, and some deep ocean sediments. REE could also be derived as a by-product of phosphate fertilizer production, U processing, mining of Ti-Zr-bearing placers, and exploitation of Olympic Dam subtype iron oxide copper gold (IOCG) deposits. Currently, REEs are produced mostly from carbonatite-related deposits, but ion adsorption clay deposits are an important source of heavy REE (HREE). Small quantities of REE are derived from placer deposits and one peralkaline intrusion-related deposit. The ideal REE development targets would be located in a politically stable jurisdiction with a pro-mining disposition such as Canada and Australia. REE grade, HREE/light REE (LREE) ratio of the mineralization, tonnage, mineralogy, and permissive metallurgy are some of the key technical factors that could be used to screen potential development projects. As REEs are considered strategic metals from economic, national security, and environmental points of view, technical and economic parameters alone are unlikely to be used in REE project development decision-making. Recycling of REE is in its infancy and unless legislated, in the short term, it is not expected to contribute significantly to the supply of REE.

  20. Geology and market-dependent significance of rare earth element resources

    NASA Astrophysics Data System (ADS)

    Simandl, G. J.

    2014-12-01

    China started to produce rare earth elements (REEs) in the 1980s, and since the mid-1990s, it has become the dominant producer. Rare earth element export quotas first introduced by the Chinese government in the early 2000s were severely reduced in 2010 and 2011. This led to strong government-created disparity between prices within China and the rest of the world. Industrialized countries identified several REEs as strategic metals. Because of rapid price increases of REE outside of China, we have witnessed a world-scale REE exploration rush. The REE resources are concentrated in carbonatite-related deposits, peralkaline igneous rocks, pegmatites, monazite ± apatite veins, ion adsorption clays, placers, and some deep ocean sediments. REE could also be derived as a by-product of phosphate fertilizer production, U processing, mining of Ti-Zr-bearing placers, and exploitation of Olympic Dam subtype iron oxide copper gold (IOCG) deposits. Currently, REEs are produced mostly from carbonatite-related deposits, but ion adsorption clay deposits are an important source of heavy REE (HREE). Small quantities of REE are derived from placer deposits and one peralkaline intrusion-related deposit. The ideal REE development targets would be located in a politically stable jurisdiction with a pro-mining disposition such as Canada and Australia. REE grade, HREE/light REE (LREE) ratio of the mineralization, tonnage, mineralogy, and permissive metallurgy are some of the key technical factors that could be used to screen potential development projects. As REEs are considered strategic metals from economic, national security, and environmental points of view, technical and economic parameters alone are unlikely to be used in REE project development decision-making. Recycling of REE is in its infancy and unless legislated, in the short term, it is not expected to contribute significantly to the supply of REE.

  1. A major light rare-earth element (LREE) resource in the Khanneshin carbonatite complex, southern Afghanistan

    USGS Publications Warehouse

    Tucker, Robert D.; Belkin, Harvey E.; Schulz, Klaus J.; Peters, Stephen G.; Horton, Forrest; Buttleman, Kim; Scott, Emily R.

    2012-01-01

    The rapid rise in world demand for the rare-earth elements (REEs) has expanded the search for new REE resources. We document two types of light rare-earth element (LREE)-enriched rocks in the Khanneshin carbonatite complex of southern Afghanistan: type 1 concordant seams of khanneshite-(Ce), synchysite-(Ce), and parisite-(Ce) within banded barite-strontianite alvikite, and type 2 igneous dikes of coarse-grained carbonatite, enriched in fluorine or phosphorus, containing idiomorphic crystals of khanneshite-(Ce) or carbocernaite. Type 1 mineralized barite-strontianite alvikite averages 22.25 wt % BaO, 4.27 wt % SrO, and 3.25 wt % ∑ LREE2O3 (sum of La, Ce, Pr, and Nd oxides). Type 2 igneous dikes average 14.51 wt % BaO, 5.96 wt % SrO, and 3.77 wt % ∑ LREE2O3. A magmatic origin is clearly indicated for the type 2 LREE-enriched dikes, and type 1 LREE mineralization probably formed in the presence of LREE-rich hydrothermal fluid. Both types of LREE mineralization may be penecontemporaneous, having formed in a carbonate-rich magma in the marginal zone of the central vent, highly charged with volatile constituents (i.e., CO2, F, P2O5), and strongly enriched in Ba, Sr, and the LREE. Based on several assumptions, and employing simple geometry for the zone of LREE enrichment, we estimate that at least 1.29 Mt (million metric tonnes) of LREE2O3 is present in this part of the Khanneshin carbonatite complex.

  2. Natural radioactivity and rare earth elements in feldspar samples, Central Eastern desert, Egypt.

    PubMed

    Walley El-Dine, Nadia; El-Shershaby, Amal; Afifi, Sofia; Sroor, Amany; Samir, Eman

    2011-05-01

    The pegmatite bodies of the Eastern Desert of Egypt are widely distributed especially along the Marsa-Alam-Idfu road. The Abu Dob area covers about 150km(2) of the Arabian Nubian shield at the central part of the Eastern Desert of Egypt. Most of the pegmatite is zoned; the zonation starts with milky quartz at the core followed by alkali feldspar at the margins. The feldspars vary in color from rose to milky and in composition from K-feldspar to Na-feldspar, sometimes interactions of both types are encountered. Thirteen feldspar samples were collected from different locations in the Abu Dob area for measuring the natural radioactivity of (238)U, (232)Th and (40)K using an HPGe detector. The variation in concentration of radionuclides for the area under investigation can be classified into regions of high, medium and low natural radioactivity. The average concentration in BqKg(-1) has been observed to be from 9.5 to 183675.7BqKg(-1) for (238)U, between 6.1 and 94,314.2BqKg(-1) for (232)Th and from 0 to 7894.6BqKg(-1) for (40)K. Radium equivalent activities (Ra(eq)), dose rate (D(R)) and external hazard (H(ex)) have also been determined. In the present work, the concentration of rare earth elements are measured for two feldspar samples using two techniques, Environmental Scanning Electron microscope XIL 30 ESEM, Philips, and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). The existence of rare earth elements in this area are very high and can be used in different important industries. PMID:21324705

  3. Performance evaluation of Laser Induced Breakdown Spectroscopy (LIBS) for quantitative analysis of rare earth elements in phosphate glasses

    NASA Astrophysics Data System (ADS)

    Devangad, Praveen; Unnikrishnan, V. K.; Nayak, Rajesh; Tamboli, M. M.; Muhammed Shameem, K. M.; Santhosh, C.; Kumar, G. A.; Sardar, D. K.

    2016-02-01

    In the current study, we have determined the elemental compositions of synthesized rare earth doped phosphate glasses using a laboratory Laser-Induced Breakdown Spectroscopy (LIBS) system. LIBS spectra of this rare earth (samarium (Sm), thulium (Tm) and ytterbium (Yb)) doped glass samples with known composition are recorded using a highly sensitive detector. Major atomic emission lines of Sm, Tm and Yb found in LIBS spectra are reported. By considering the atomic emission line of phosphorous as an internal standard, calibration curves were constructed for all the rare earth concentrations. Very good linear regression coefficient (R2) values were obtained using this technique. Analytical predictive skill of LIBS was studied further using leave-one-out method. Low values of the reported correlation uncertainty between measured LIBS concentration ratio and certified concentration ratio confirms that LIBS technique has great potential for quantitative analysis of rare earth elements in glass matrix.

  4. Dissolved Rare Earth Element Concentrations in the Upwelling area off Peru

    NASA Astrophysics Data System (ADS)

    Grasse, P.; Plass, A.; Hathorne, E. C.; Frank, M.

    2012-12-01

    Rare earth elements (REEs) are powerful tracers of continental input, particle exchange and scavenging processes, as well as for water mass transport in the ocean. We present a first data set of dissolved REE distributions in filtered seawater covering the major gradients of bio-productivity and oxygen concentrations in the upwelling area off Peru. A total of 22 stations were analyzed along a shelf, a nearshore and an offshore transect to investigate the influence of local inputs versus water mass mixing. The Peruvian coastal upwelling area is a highly dynamic system characterized by intense upwelling of nutrient-rich subsurface water and therefore high productivity that leads to one of the globally largest Oxygen Minimum Zones (OMZ). The upwelling area off Peru is of particular interest for understanding the biogeochemical cycling of REEs and other redox-sensitive metals because anoxic conditions are expected to release of REEs from the shelf, whereas high particle densities and fluxes efficiently remove the REEs from the water column. Despite their high potential as tracers few systematic investigations of seawater REEs have been carried out so far because the low concentrations of REEs (pM) are difficult to measure. In this study an online preconcentration (OP) system (seaFast, Elemental Scientific Inc.) was used with a technique slightly modified from Hathorne et al. (2012). The OP system efficiently separates seawater matrix elements from the REEs and elutes the preconcentrated sample directly into the spray chamber of the ICP-MS instrument. Repeated measurements of a seawater reference sample (n= 20) during this study gave a reproducibility of between 5% and 15% (2?), with the worst reproducibility for Sm, Eu, and Gd (12% to 15%). In general, the REEs, except Ce, show a nutrient-like behavior in seawater increasing in concentration with water depth. However, such distributions were not observed for some stations on the shelf where the highest concentrations, especially of the light REEs, were found in surface waters. Shelf locations show an enrichment in light REEs with higher (La/Yb)PAAS ratios (~0.7) in comparison to offshore stations (~0.3), likely reflecting continental input from the shelf sediments. Compared to North Pacific Deep Water (Alibo and Nozaki, 1999) the shelf samples are depleted in REEs, except for La and Ce, revealing that in addition to shelf inputs and dissolution of lithogenic particles, particle scavenging processes in the highly productive shelf area exert a major control on the REE concentrations. Interestingly there is no clear correlation between oxygen concentration and the Ce anomaly (Ce*) as in waters with oxygen concentrations below 5 ?mol/kg the Ce* ranged between 0.2 and 1.0. References: Hathorne, E. C., Haley, B., Stichel, T., Grasse, P., Zieringer, M., & Frank, M. (2012). Online preconcentration ICP-MS analysis of rare earth elements in seawater. Geochemistry Geophysics Geosystems, 13(1), 1-12. doi:10.1029/2011GC003907 Alibo, D. S., & Nozaki, Y. (1999). Rare earth elements in seawater: Particle association, shale-normalization, and Ce oxidation. Geochimica et Cosmochimica Acta, 63(3/4), 363-372.

  5. Structural Elements in a Persistent Identifier Infrastructure and Resulting Benefits for the Earth Science Community

    NASA Astrophysics Data System (ADS)

    Weigel, T.; Toussaiant, F.; Stockhause, M.; Höck, H.; Kindermann, S.; Lautenschlager, M.; Ludwig, T.

    2012-12-01

    We propose a wide adoption of structural elements (typed links, collections, trees) in the Handle System to improve identification and access of scientific data, metadata and software as well as traceability of data provenance. Typed links target the issue of data provenance as a means to assess the quality of scientific data. Data provenance is seen here as a directed acyclic graph with nodes representing data and vertices representing derivative operations (Moreau 2010). Landing pages can allow a human user to explore the provenance graph back to the primary unprocessed data, thereby also giving credit to the original data producer. As in Earth System Modeling no single infrastructure with complete data lifecycle coverage exists, we propose to split the problem domain in two parts. Project-specific infrastructures such as the German project C3-Grid or the Earth System Grid Federation (ESGF) for CMIP5 data are aware of data and data operations (Toussaint et al. 2012) and can thus detect and accumulate single nodes and vertices in the provenance graph, assigning Handles to data, metadata and software. With a common schema for typed links, the provenance graph is established as downstream infrastructures refer incoming Handles. Data in this context is for example hierarchically structured Earth System model output data, which receives DataCite DOIs only for the most coarse-granular elements. Using Handle tree structures, the lower levels of the hierarchy can also receive Handles, allowing authors to more precisely identify the data they used (Lawrence et al. 2011). We can e.g. define a DOI for just the 2m-temperature variable of CMIP5 data across many CMIP5 experiments or a DOI for model and observational data coming from different sources. The structural elements should be implemented through Handle values at the Handle infrastructure level for two reasons. Handle values are more durable than downstream websites or databases, and thus the provenance chain does not break if individual links become unavailable. Secondly, a single service cannot interpret links if downstream solutions differ in their implementation schemas. Emerging efforts driven by the European Persistent Identifier Consortium (EPIC) aim to establish a default mechanism for structural elements at the Handle level. We motivate to make applications, which take part in the data lifecycle, aware of data derivation provenance and let them provide additional elements to the provenance graph. Since they are also Handles, DataCite DOIs can act as a corner stone and provide an entry point to discover the provenance graph. References B. Lawrence, C. Jones, B. Matthews, S. Pepler, and S. Callaghan, "Citation and peer review of data: Moving towards formal data publication," Int. J. of Digital Curation, vol. 6, no. 2, 2011. L. Moreau, "The foundations for provenance on the web," Foundations and Trends® in Web Science, vol. 2, no. 2-3, pp. 99-241, 2010. F. Toussaint, T. Weigel, H. Thiemann, H. Höck, M. Stockhause: "Application Examples for Handle System Usage", submitted to AGU 2012 session IN009.

  6. First Principles Calculation on Equilibrium Si Isotope Fractionation Factors and its Implementation on Si Isotope Distributions in Earth Surface Environments

    NASA Astrophysics Data System (ADS)

    Liu, Y.; He, H. T.; Zhu, C.

    2014-12-01

    Several important equilibrium Si isotope fractionation factors are calculated here. We use a so-called volume-variable-cluster-model (VVCM) method for solids and the "water-droplet" method for aqueous species for isotope fractionation calculation at the same quantum chemistry level. The calculation results show that several silicate minerals, such as quartz, feldspar, kaolinite, etc., all enrich heavy Si isotopes relative to aqueous H4SiO4 and can be up to 3.3‰ at 25°C, different from most field observations. Meanwhile stable organosilicon complexes can enrich even lighter Si isotopes than aqueous H4SiO4. For explaining the difference between the calculation results and field observations, we calculate the kinetic isotope effect (KIE) associated with the formation of amorphous silica, and find that amorphous silica will enrich extremely light Si isotopes. From amorphous silica to crystalline quartz, the structural adjustment & transition needs getting rid of small amount of Si to re-organize the structure. Light Si isotopes will be preferentially lost and let the final crystalline quartz with a little bit more heavy Si isotopes. However, such late-stage Si heavy isotope enrichment cannot erase the total isotopic signal, crystalline quartz still inherit much light Si isotopic composition from amorphous quartz. That is the reason for the discrepancy between the calculation results and the field observations, because the formation of amorphous quartz is under a non-equilibrium process but theoretical calculations are for equilibrium isotope fractionations. With accurate equilibrium fractionation factors provided here, Si isotope distributions in earth surface environments including soil, groundwater and plants can be further interpreted. We find that δ30Si variations in soil are mainly driven by secondary minerals precipitation and adsorption. Also, bulk soil δ30Si maybe have a parabolic distribution with soil age, with a minimum value at where allophane is completely dissolved and the total amount of sesqui-oxides and poorly crystalline minerals reach their maximum. Similarly, precipitation of clay minerals can explain δ30Si variation in ground water profile.

  7. Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau, East Sea

    NASA Astrophysics Data System (ADS)

    Kang, Jeongwon; Jeong, Kap-Sik; Cho, Jin Hyung; Lee, Jun Ho; Jang, Seok; Kim, Seong Ryul

    2014-03-01

    We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.

  8. Seawater-derived rare earth element addition to abyssal peridotites during serpentinization

    NASA Astrophysics Data System (ADS)

    Frisby, Carl; Bizimis, Michael; Mallick, Soumen

    2016-04-01

    Serpentinized abyssal peridotites are evidence for active communication between the Earth's hydrosphere and the upper mantle, where exchange and retention of both major and trace elements occur. Bulk rock Nd isotopes in serpentinized abyssal peridotites imply interaction of seawater with the peridotite. In contrast, the Nd isotopes of clinopyroxenes from serpentinized abyssal peridotites retain their primary magmatic signature. It is currently unclear if, how and where seawater-derived Nd and other REE are being added or exchanged with the mantle peridotite minerals during serpentinization. To remedy this knowledge gap, we present in situ trace and major element concentrations, bulk rock and sequential leaching experiment trace element concentrations as well as Nd, Sr isotope data on refertilized and depleted serpentinized abyssal peridotites from the Southwest Indian Ridge. The secondary serpentine matrix and magnetite veins in these peridotites have elevated LREE concentrations, with variable negative Ce anomalies and large Rb, Sr, Pb and U enrichments that resemble seawater trace element patterns. The LREE concentrations in the serpentine phase are higher than those expected for the primary mantle mineralogy (olivine, orthopyroxene) based on data from relic clinopyroxenes and equilibrium partition coefficients. These data are consistent with seawater-derived REE addition to the peridotite during serpentinization. The bulk rocks have more radiogenic Sr and more unradiogenic Nd isotopes than their clinopyroxene (up to 8 εNd units lower than clinopyroxene). Sequential leaching experiments designed to mobilize secondary carbonates and Fe-oxides show even more unradiogenic Nd isotope ratios in the leachates than the bulk rock and clinopyroxene, approaching seawater compositions (up to 15 εNd units lower than clinopyroxene). Mass balance calculations using trace elements or Nd isotopes suggest that up to 30% of the bulk peridotite Nd budget is of seawater origin and was added to the peridotite, as opposed to being exchanged. These data allows for more accurate constraints of the water/rock mass exchange ratios during serpentinization in these rocks (~ 1000 to 17,000) that are at least an order of magnitude lower than using typical mantle and seawater endmembers. These data provide strong evidence that serpentinization may also be a sink for the light REE, with implications for the refertilization of the peridotite during serpentinization, and the cycling of these elements through the subduction system and into the upper mantle.

  9. Distribution and size fractionation of elemental sulfur in aqueous environments: The Chesapeake Bay and Mid-Atlantic Ridge

    NASA Astrophysics Data System (ADS)

    Findlay, Alyssa J.; Gartman, Amy; MacDonald, Daniel J.; Hanson, Thomas E.; Shaw, Timothy J.; Luther, George W.

    2014-10-01

    Elemental sulfur is an important intermediate of sulfide oxidation and may be produced via abiotic and biotic pathways. In this study the concentration and size fractionation of elemental sulfur were measured in two different sulfidic marine environments: the Chesapeake Bay and buoyant hydrothermal vent plumes along the Mid-Atlantic Ridge. Nanoparticulate sulfur (<0.2 ?m) was found to comprise up to 90% of the total elemental sulfur in anoxic deep waters of the Chesapeake Bay. These data were compared with previous studies of elemental sulfur, and represent one of the few reports of nanoparticulate elemental sulfur in the environment. Additionally, a strain of phototrophic sulfide oxidizing bacteria isolated from the Chesapeake Bay was shown to produce elemental sulfur as a product of sulfide oxidation. Elemental sulfur concentrations are also presented from buoyant hydrothermal vent plumes located along the Mid-Atlantic Ridge. In the Mid-Atlantic Ridge plume, S0 concentrations up to 33 ?M were measured in the first meter of rising plumes at three different vent sites, and nanoparticulate S0 was up to 44% of total elemental sulfur present.

  10. Tracing irradiation-induced defect state of monazite by photoluminescence of rare Earth elements

    NASA Astrophysics Data System (ADS)

    Panczer, G.; Seydoux-Guillaume, A. M.; Montel, J. M.; Champagnon, B.

    2003-04-01

    Natural monazite is known in contrast to zircon, to almost never be found in the metamict state (Ewing, 1975) despite the fact that it received intensive radiation doses during geologic history by U and Th incorporation. Radiation damages in natural monazite seems to be limited to isolated domains within the crystal (Meldrum et al., 1998). Such property controlled the fact that the monazite lattice is easily healed even at low temperature as it was shown by TEM, XRD and Raman spectrometry (Seydoux-Guillaume et al., 2002). In order to estimate the degree of disorder and the healing of defects we used trivalent neodymium as an internal luminescent probe (Gaft et al., 2001). As a matter of fact the radiative electronic transitions of rare earth elements are very sensible to the short-range crystallographic order around them. Three natural monazites thermally untreated and quenched at 450, 500, 700, 800 and 1000^oC were analyzed under 514 nm Argon laser excitation with a Renishaw microspectrometer. Nd3+ emission was recorded in the range of 750 nm to 1 ?m. The ^4F3/2 rightarrow ^4I9/2 transition parameters (position and width) show that 1) the position of the Stark levels do not change during thermal treatment, and 2) that the emission line widths decrease continuously (from 25 to 37%) from room temperature to 1000^oC. These results indicates that before annealing, sub sites of Nd were present with slight different environments induced by internal irradiation induced displacement of ions around them (short range disorder). After thermal treatment a continuous reorganization of the lattice occurs up to 1000^oC with quite strong rearrangement of the environment around the rare-earth leading to a decrease of the Nd sub site number. Thus, the luminescent probe reveals that defect healing continue at much higher temperatures than what was previously reported indicating that luminescence is a very sensible tool to appreciate the degree of disorder in mineral phases. Gaft M., Panczer G., Reisfeld R. &Uspensky E. (2001) Laser-induced time-resolved luminescence as a tool for rare-earth element identification in minerals., Phys. Chem. Minerals, 28, 347-363.

  11. Developing alternative resources of rare earth elements in Europe - EURARE and the red mud challenge

    NASA Astrophysics Data System (ADS)

    Deady, Eimear; Mouchos, Evangelos; Goodenough, Kathryn; Wall, Frances; Williamson, Ben

    2015-04-01

    Rare earth elements (REE) are considered to be highly "critical" by the European Commission [1], owing to the concentration of global supply [2] and their use in a wide range of emerging technologies (e.g. smart phones, electric cars and wind turbines). The main source of REE is the mineral bastnäsite, which is primarily extracted from carbonatites. Alternative resources of REE have been identified in a variety of other environments such as alluvial placers, bauxites and ore tailings. The EURARE project (www.eurare.eu), funded by the European Commission, aims to improve understanding of potential REE resources in Europe with the overall objective of establishing the basis for a European REE industry. As a part of this project, alternative sources of rare earth elements in Europe are being considered. REE have been identified as being particularly enriched in karst-bauxites and hence in the red muds generated as a waste product from the processing of these bauxites to alumina through the Bayer process [3]. Karst-bauxites are widely distributed with deposits known across the Mediterranean and with intermittent exploitation occurring over many decades. REE become concentrated in the bauxite deposits by the bauxitisation process and are retained due to the geochemical barrier created by the limestone bedrock below. This can result in several processes, including the crystallisation of authigenic REE-bearing minerals, the accumulation of residual phases and the adsorption of ions onto clays and other mineral surfaces [4]. Red muds produced from alumina processing represent a potentially important concentration of REE as it has been demonstrated that the REE pass through the alumina extraction process into the waste, and the total REE concentrations are typically enriched by a factor of two compared with the original bauxite ore [5]. Bauxites and red muds from the Parnassus Ghiona region of Greece [6] and the Seydişehir-Akseki region of Turkey have been assessed as part of this study. Red muds from these deposits contain on average 900 ppm REE compared with typical values of <100 ppm to ~500 ppm REE in the bauxites. Extraction of REE from red muds has been shown to be feasible [5,7] although it is challenging due to the heterogeneous spatial distribution of REE in the primary bauxite deposits [8], an unclear understanding of the mobility of REE in red mud tailings ponds, and the need for development of appropriate processing methods. However, the resource potential of red muds in Europe is significant with approximately 3.5 Mt of bauxite ore extracted in 2012 [2], resulting in approximately 1.4 Mt of red mud from the production of alumina. In addition a large volume of stockpiled red muds exists from historical processing of bauxites, the total of which is not well constrained. Understanding the REE potential of both bauxites and red muds is integral to an assessment of European REE resources. References [1] European Commission, "Report on critical raw materials for the EU. Report of the Ad hoc Working Group on defining critical raw materials". May 2014. [2] T. Brown, N. Idoine, E. Raycraft, R. Shaw, E. Deady, J. Rippingale, T. Bide, C. Wrighton, J. Rodley, "World Mineral Production 2008-12" British Geological Survey, Keyworth, Nottingham, 2014. [3] Z. Maksimović and G. Pantó, "Authigenic rare earth minerals in karst-bauxites and karstic nickel deposits". In: A.P. Jones, F. Wall and C.T. Williams, Rare earth minerals, chemistry, origin and ore deposits, Chapter 10, pp. 257-279, 1996. [4] G. Bárdossy, "Karst Bauxites, Bauxite Deposits on Carbonate Rocks". Elsevier, 444pp, 1982. [5] M. Ochsenkühn-Petropoulou, T. Lyberopoulou, and G. Parissakis, "Direct determination of lanthanides, yttium and scandium in bauxites and red mud from alumina production", Analytica Chimica Acta, vol. 296, no. 3, pp. 305-313, October 1994. [6] É. Deady, E. Mouchos, K. Goodenough, B. Williamson and F. Wall. "Rare Earth Elements in Karst-Bauxites: a Novel Untapped European Resource?" ERES 1st European Rare Earth Resources conference, Milos, Greece, (5-6/09/2014). [7] A. Wagh and W. Pinnock, "Occurrence of scandium and rare earth elements in Jamaican bauxite waste", Economic Geology, vol. 82, no. 3, pp. 757-761, May 1987. [8] G. Mongelli, "Ce-anomalies in the textural components of Upper Cretaceous karst bauxites from the Apulian carbonate platform (southern Italy)", Chemical Geology, vol. 140, no. 1, pp. 69-79, June 1997. Additional resources: www.eurare.eu; www.redmud.org.

  12. Subduction Zone Redox and the Deep Earth Cycles of Sulfur and Chalcophile Elements

    NASA Astrophysics Data System (ADS)

    Canil, D.

    2013-12-01

    Subduction at convergent plate margins is a return flux to the mantle of rocks influenced by weathering, hydrothermal activity, atmospheric exchange, or bio-mineralization in the exosphere. The latter exogenic processes modify the long-term abundance and behaviour of certain elements in the deeper earth that can be traced over time in the chemistry of mantle-derived magmas. The redox budget of subduction is controlled by the flux of oxidized versus reduced forms of Fe, S, H, or C, and impacts the long-term evolution of oxygen on the planet, critical for life in the exosphere. In particular, the sulfur cycle is specifically tied to the evolution of oxygen on Earth's surface over time and critical to biogeochemical cycles on the surface. The behaviour of sulfur in the exogenic system is well-studied and fairly well understood using sedimentary records. An originally sulfidic ocean on Earth gave way with time and oxygenation to one that is sulfate dominated over the last two billion years. In contrast, far less is known of the deep earth cycle of S, and more so its history. The record of the endogenic cycle can only be monitored via what comes out of the mantle (magmas and their gases), or what goes down via subduction (hydrothermally-altered or weathered subducted lithosphere). Interest in the endogenic cycle of S is not new but several outstanding conundrums remain for sulfur in arc magmas that point to the importance of the subduction process. A hitherto ignored component of the paradox of the sulfur cycle is the sedimentary veneer that sits atop the subducted oceanic basalt crust. Compilations show only 0.12 wt% S in altered ocean basalt crust, but up to 10 times that amount in oceanic sediments, tied to their Fe content (in pyrite). These abundances may seem trivial, but the behaviour of this small amount of S in subduction is not fully appreciated and its oxidation potential in the arc mantle is enormous. The conversion of subducted sulfide to sulfate is a 8-electron change in redox state, with significant oxidation/ reduction capacity. The concomitant higher fO2 can in turn facilitate the mobility and/or extraction of chalcophile metals from the arc mantle into magmas by the melting process in arcs. Sedimentary records show that through most of Earth's history sulfur has mostly been subducted in reduced form as sulfide. The fate of sulfide in ocean sediments during subduction (and subsequent dehydration or melting) has not been thoroughly investigated, nor its interplay with other redox couples (C, H, Fe) in sediments, subducted basalt or in the mantle. I examine the redox controls on sulfate versus sulfide stability in subducted oceanic crust, and their disposition relative to other redox couples in the mantle. Sulfate-sulfide equilibria impact the fate of sulfur and chalcophile elements in subducted lithologies, especially if dehydrated or melted depending on a variety subduction P-T trajectories. In this light, new high P-T experiments show the utility of Cu as a proxy for S in the subduction system . These proxies can potentially be applied to examine the deep S cycle, subduction redox and its role in arc magmatism over geologic time.

  13. Water-soluble fraction of mercury, arsenic and other potentially toxic elements in highly contaminated sediments and soils.

    PubMed

    Rodrigues, S M; Henriques, B; Coimbra, J; Ferreira da Silva, E; Pereira, M E; Duarte, A C

    2010-03-01

    The water-soluble contents of mercury, arsenic and other potentially toxic elements in highly contaminated sediment and soil samples from Portugal were determined. Mercury and arsenic concentrations were detectable and reproducible among replicate experiments. Despite the acidic pH, the low organic carbon content and the exceptionally high levels of contamination of certain samples (total mercury contents varied between 0.15 and 3180 mg kg(-1) while total arsenic concentrations ranged from 11 to 6365 mg kg(-1)), the water-soluble percentages of both mercury (<1.2%) and arsenic (<4.6%) were generally low. The variability of the water-soluble fractions of these two elements among these samples and at the occurring pH conditions seems not to be associated with the release of other potentially toxic elements. The highest water-soluble concentrations of the remaining potentially toxic elements were generally observed in the 15-25 cm depth layer of sediments from areas colonised with plants (Halimione portulacoides) and in mining soil samples. Zinc, cobalt, copper and cadmium showed the highest water-soluble percentages of elements in relation to total metal contents. Given the high contamination levels, the availability of potentially toxic elements in these areas as well as possible risks to the environment and humans should be further investigated. The presence of plants (H. portulacoides) appears to cause significant changes in the sediment matrix that increase the mobility of several potentially toxic elements, particularly in the 15-25 cm depth layer. The effects of vegetation on the fractionation of potentially toxic elements on these sediments should be further studied. PMID:20122712

  14. A New Fungal Isolate, Penidiella sp. Strain T9, Accumulates the Rare Earth Element Dysprosium

    PubMed Central

    Horiike, Takumi

    2015-01-01

    With an aim to develop a highly efficient method for the recovery of rare earth elements (REEs) by using microorganisms, we attempted to isolate dysprosium (Dy)-accumulating microorganisms that grow under acidic conditions from environmental samples containing high concentrations of heavy metals. One acidophilic strain, T9, which was isolated from an abandoned mine, decreased the concentration of Dy in medium that contained 100 mg/liter Dy to 53 mg/liter Dy after 3 days of cultivation at pH 2.5. The Dy content in the cell pellet of the T9 strain was 910 μg/mg of dry cells. The T9 strain also accumulated other REEs. Based on the results of 28S-D1/D2 rRNA gene sequencing and morphological characterization, we designated this fungal strain Penidiella sp. T9. Bioaccumulation of Dy was observed on the cell surface of the T9 strain by elemental mapping using scanning electron microscopy-energy dispersive X-ray spectroscopy. Our results indicate that Penidiella sp. T9 has the potential to recover REEs such as Dy from mine drainage and industrial liquid waste under acidic conditions. PMID:25710372

  15. A new fungal isolate, Penidiella sp. strain T9, accumulates the rare earth element dysprosium.

    PubMed

    Horiike, Takumi; Yamashita, Mitsuo

    2015-05-01

    With an aim to develop a highly efficient method for the recovery of rare earth elements (REEs) by using microorganisms, we attempted to isolate dysprosium (Dy)-accumulating microorganisms that grow under acidic conditions from environmental samples containing high concentrations of heavy metals. One acidophilic strain, T9, which was isolated from an abandoned mine, decreased the concentration of Dy in medium that contained 100 mg/liter Dy to 53 mg/liter Dy after 3 days of cultivation at pH 2.5. The Dy content in the cell pellet of the T9 strain was 910 μg/mg of dry cells. The T9 strain also accumulated other REEs. Based on the results of 28S-D1/D2 rRNA gene sequencing and morphological characterization, we designated this fungal strain Penidiella sp. T9. Bioaccumulation of Dy was observed on the cell surface of the T9 strain by elemental mapping using scanning electron microscopy-energy dispersive X-ray spectroscopy. Our results indicate that Penidiella sp. T9 has the potential to recover REEs such as Dy from mine drainage and industrial liquid waste under acidic conditions. PMID:25710372

  16. Geochemistry of the rare earth elements in ferromanganese nodules from DOMES Site A, northern equatorial Pacific

    USGS Publications Warehouse

    Calvert, S.E.; Piper, D.Z.; Baedecker, P.A.

    1987-01-01

    The distribution of rare earth elements (REE) in ferromanganese nodules from DOMES Site A has been determined by instrumental neutron activation methods. The concentrations of the REE vary markedly. Low concentrations characterize samples from a depression (the valley), in which Quaternary sediments are thin or absent; high concentrations are found in samples from the surrounding abyssal hills (the highlands) where the Quaternary sediment section is relatively thick. Moreover, the valley nodules are strongly depleted in the light trivalent REE (LREE) and Ce compared with nodules from the highlands, some of the former showing negative Ce anomalies. The REE abundances in the nodules are strongly influenced by the REE abundances in coexisting bottom water. Some controls on the REE chemistry of bottom waters include: a) the more effective removal of the LREE relative to the HREE from seawater because of the greater degree of complexation of the latter elements with seawater ligands, b) the very efficient oxidative scavenging of Ce on particle surfaces in seawater, and c) the strong depletion of both Ce and the LREE in, or a larger benthic flux of the HREE into, the Antarctic Bottom Water (AABW) which flows through the valley. The distinctive REE chemistry of valley nodules is a function of their growth from geochemically evolved AABW. In contrast, the REE chemistry of highland nodules indicates growth from a local, less evolved seawater source. ?? 1987.

  17. Study of K?2 /K?1 RYIED in closed and open shell Rare Earth Elements

    NASA Astrophysics Data System (ADS)

    Chaves, P. C.; Tribolet, A. D.; Reis, M. A.

    2016-01-01

    Relative Yield Ion Energy Dependence (RYIED) was observed, named and reported as phenomenological evidence in 2005 (Reis et al., 2005). Since then, it was observed in transitions to the same subshell, and plausible explanations for the physics behind the phenomena have been proposed. In this work we present experimental evidence of the RYIED effect on the most inner transition possible in two Rare Earth Elements (REE), namely variations in the intensity ratio of K?2 /K?1 X-rays from Tm and Yb irradiated under different conditions. These REE are particularly interesting to start with since Yb has an electronic configuration where all the subshells are completely filled, whilst Tm misses one electron in the 4f subshell. Ultrapure oxides of each element were irradiated using proton beams having energies in the range of 0.9-3.6 MeV, in steps of 100 keV. Spectra were collected using the CdTe detector of the HRHE-PIXE set-up of C2TN and analysed using the DT2 code. Finally, the vanishing of the effect upon charging up of the target has been observed and will be discussed.

  18. The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earths mantle: New evidence from in situ analyses of mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Witt-Eickschen, G.; Palme, H.; O'Neill, H. St. C.; Allen, C. M.

    2009-03-01

    The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb. The data yield new and more reliable mantle abundances for Cd (35 7 ppb), In (18 3 ppb) and Sn (91 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.

  19. Using rare earth elements for the identification of the geographic origin of food

    NASA Astrophysics Data System (ADS)

    Meisel, T.; Bandoniene, D.; Joebstl, D.

    2009-04-01

    The European Union defined regimes within the Protected Geographical Status (PGS) framework to protect names of regional food specialities. Thus only food produced in a specific geographical area with a specific way of production or quality can be protected by a protected geographical indication (PGI) label. As such Styrian Pumpkin Seed Oil has been approved with this label, but as with many other high priced regional specialities, fraud cannot be excluded or nor identified. Thus the aim of this work is, to develop an analytical method for the control of the geographic origin of pumpkin seed oil and also to test the method for other protected products. The development of such a method is not only of interest for scientists, but also of importance for the consumer wanting to know the origin of the food products and the assurance of the purity and quality. The group of rare earth elements (REE) in plants also have a characteristic distribution pattern similar to upper crustal REE distributions. Since the REE concentrations are extremely low in pumpkin seed oil (ppt to low ppb), ICP-MS was the only sensitive tool able to produce validated results. The carrier of the REE are most likely small particles distributed within the pumpkin seed oil. Unlike, e.g., olive oil, pumpkin seed oil is bottled and sold unfiltered, which makes this Styrian speciality an interesting sampling target. As pumpkin seed oils from different geographic origin show variable trace element and rare earth distribution patterns, is should possible to trace the origin of these oils. In the current project pumpkin seeds from different regions in Austria and from abroad were sampled. The trace element patterns in the extracted oil of these seeds were determined and a preliminary classification with discriminate analysis was successfully done on a statistical basis. In addition to the study of the geographic origin it was demonstrated that REE distribution patterns can also be used for the identification of adulteration of high priced pumpkin seed oil with cheap neutral tasting refined oils. Interestingly enough, the variations of the REE patterns between oils from different regions are much more pronounced than their host soils. Thus we assume that microbiological processes in the rhizosphere are in control of the REE uptake into the plant. Regional variations of the microbiological composition of the soils and probably not only a priori the bulk soil composition of the minerals in the soil are the cause of the regional variations making it possible to identify the geographic origin of pumpkin seeds and as a consequence the pumpkin seed oil.

  20. Fractionation of fluorine, chlorine and other trace elements during differentiation of a tholeiitic magma.

    NASA Technical Reports Server (NTRS)

    Greenland, L.; Lovering, J. F.

    1966-01-01

    Fluorine, chlorine and other trace elements determined through differentiated tholeiitic dolerite sill from Tasmania using statistical techniques, showing hydroxyl lattice sites by chlorine and fluorine

  1. Linking rare earth element zoning in major and accessory minerals to better understand metasedimentary migmatites

    NASA Astrophysics Data System (ADS)

    Matthews, J. A.; Kelly, N. M.; Koenig, A.; Harley, S. L.

    2011-12-01

    Trace element signatures from major and accessory minerals are increasingly used to place constraints on the ages of tectonothermal events and gain insights into processes operating in the deep continental crust. Minerals such as garnet, zircon or monazite represent sensitive recorders of events if a solid understanding exists of what trace element signatures represent. A study underway on granulite facies migmatites is providing insights into trace element signatures in garnet, and when integrated with in situ, microbeam analysis of zircon and monazite, is allowing a complex polymetamorphic history to be deciphered. The Larsemann Hills, east Antarctica, are composed of felsic orthogneisses and metasediments that were affected by high-grade metamorphism and partial melting at c. 7 kbar and >800 C. Initially interpreted to have experienced a single cycle of metamorphism at c. 550-530 Ma, recent ages suggest that the area was affected by an earlier high-grade event at c. 900 Ma; the timing of migmatization relative to these two events remains uncertain. To address this, a detailed study has targeted metasedimentary migmatites. Garnet, zircon and monazite were analysed from melanosome, leucosome and selvage domains. Garnet (predominantly almandine-pyrope) preserves little, if any, major element zoning. In contrast, it records systematic within-grain variations in heavy rare earth element (HREE) concentration depending on textural context. Garnet within residuum domains displays broad cores with flat HREE slopes in chondrite-normalized plots, but are HREE-depleted (negative slopes) at boundaries adjacent to leucosome. In contrast, garnet boundaries adjacent to cordierite-rich selvages are typically HREE-enriched, with positive-sloping patterns. It is interpreted that core-rim depletions in HREE may reflect evolution of the whole-rock reservoir towards depletion during migmatization and garnet growth. Enrichment in garnet HREE adjacent to selvage domains likely resulted from local reaction between solids and melts either during melt transit and/or crystallization. Monazite, which is preferentially located in leucosome domains, preserves ages that reflect growth at c. 900 Ma and c. 530 Ma, although trace element signatures are ambiguous. However, zircon, which is preferentially located in selvage domains, preserves c. 530 Ma rims with depleted, flat to negatively sloping HREE patterns. It is interpreted that these zircon rims grew in, or near to equilibrium with garnet cores and rims during partial melting, and may date at least part of migmatite formation in the Larsemann Hills. They do not date the final crystallization of melts and development of selvage domains. Preliminary results of this study have shown that the trace element composition of garnet from high-temperature terrains can be a powerful tool in tracking metamorphic and melting processes where major elements zoning is no longer preserved. This study also demonstrates the utility of textural context when interpreting trace element patterns and ages from dateable accessory minerals in rocks from polycyclic metamorphic terrains.

  2. Trace Element Fractional Solubility in Ultrapure Water From Samples Collected During the US GEOTRACES Eastern Tropical South Pacific Section

    NASA Astrophysics Data System (ADS)

    Buck, C. S.; Landing, W. M.; Aguilar-Islas, A. M.; Rember, R.

    2014-12-01

    The US GEOTRACES section cruise to the Eastern Tropical South Pacific (GP16) embarked from Manta, Ecuador on October 25, 2013 and terminated in Papeete, Tahiti on December 22, 2013. Bulk and size fractionated aerosol samples were collected over seventeen 72-hour periods on cellulose filters using Tisch high volume samplers. The bulk samples were collected on 47mm W41 filters and the size fractionated samples on slotted impactor filters. The Sierra-style slotted cascade impactor cutoffs are >7m, >3m, >1.5m, >0.95m and >0.49m. Particles <0.49m were collected on a 20 x 25cm W41 backing filter. The soluble bulk aerosol fraction was extracted aboard ship by passing 100mL of ultrapure water (>18.2M? cm) through the sample filter under vacuum. The extract was acidified for storage and later analyzed by ICP-MS to quantify the soluble aerosol fraction. Replicate bulk filters collected simultaneously were digested and analyzed by ICP-MS to provide the total aerosol concentration. Our data will provide insight into the nature of aerosols transported across the South Pacific and describe their potential as a source for trace elements to the surface ocean. The results will aid in the interpretation of surface water trace element concentrations. We will also characterize the alteration of aerosol fractional solubility with transport in the atmosphere as well as investigate the relationship between aerosol concentration and aerosol fractional solubility. All of our observations will be discussed in the context of the larger global dataset of aerosol solubility data and compared with assumptions currently applied in global models of atmospheric deposition.

  3. Rare earth elements (REEs): effects on germination and growth of selected crop and native plant species.

    PubMed

    Thomas, Philippe J; Carpenter, David; Boutin, Cline; Allison, Jane E

    2014-02-01

    The phytotoxicity of rare earth elements (REEs) is still poorly understood. The exposure-response relationships of three native Canadian plant species (common milkweed, Asclepias syriaca L., showy ticktrefoil, Desmodium canadense (L.) DC. and switchgrass, Panicum virgatum L.) and two commonly used crop species (radish, Raphanus sativus L., and tomato, Solanum lycopersicum L.) to the REEs lanthanum (La), yttrium (Y) and cerium (Ce) were tested. In separate experiments, seven to eight doses of each element were added to the soil prior to sowing seeds. Effects of REE dose on germination were established through measures of total percent germination and speed of germination; effects on growth were established through determination of above ground biomass. Ce was also tested at two pH levels and plant tissue analysis was conducted on pooled samples. Effects on germination were mostly observed with Ce at low pH. However, effects on growth were more pronounced, with detectable inhibition concentrations causing 10% and 25% reductions in biomass for the two native forb species (A. syriaca and D. canadense) with all REEs and on all species tested with Ce in both soil pH treatments. Concentration of Ce in aboveground biomass was lower than root Ce content, and followed the dose-response trend. From values measured in natural soils around the world, our results continue to support the notion that REEs are of limited toxicity and not considered extremely hazardous to the environment. However, in areas where REE contamination is likely, the slow accumulation of these elements in the environment could become problematic. PMID:23978671

  4. Extreme trace elements fractionation in Cenozoic nephelinites and phonolites from the Moroccan Anti-Atlas (Eastern Saghro)

    NASA Astrophysics Data System (ADS)

    Berger, Julien; Ennih, Nasser; Ligeois, Jean-Paul

    2014-12-01

    Nephelinites and phonolites from the Moroccan Anti-Atlas form a cogenetic series of volcanic rocks linked by a fractional crystallization process and showing continuous evolutionary trends for trace-elements. According to partial melting calculations, minor element data in olivine and review of published experimental studies, the most primitive nephelinites are low degree (~ 2%) partial melts from a carbonated LREE-rich spinel lherzolite. Sr-Nd-Pb isotopic compositions indicate the participation of both DM and HIMU end-members in the mantle source of nephelinites; the HIMU component is here interpreted as a relic of the shallow metasomatized Pan-African mantle. The phonolites show similar isotopic composition except for slightly more radiogenic Sr isotopic values. Fractional crystallization calculations were performed using trace-element mineral/bulk rock coefficients determined with new LA-ICP-MS data on minerals together with published equilibrium partition coefficients. The decrease of LREE, Sr and Ba with increasing differentiation is explained by fractionation of large amounts of apatite. Th, Nb and Zr display a behavior of very incompatible elements, reaching extreme concentration in most differentiated phonolites. Ta, Hf and MREE by contrast are characterized by a moderately incompatible to compatible behavior during differentiation. Fractionation of small amount of titanite, in which Ta, Hf and MREE are highly compatible compared to Nb, Zr and LREE (DNb/DTa: 2, DZr/DHf: 1.5 for titanite/phonolite ratios), explains the observed increase in Nb/Ta and Zr/Hf ratios with increasing silica content, from 18 and 40 in nephelinites to 70 and 80 in phonolites, respectively. Clinopyroxene also contributed to the fractionation of Hf from Zr in the very first steps of crystallization. The low values of Nb/Ta and Zr/Hf ratios observed in the two most differentiated Si-rich phonolites are probably a consequence of late stage segregation of volatile-rich agpaitic assemblages in the underlying magma chamber. Two phonolites with extreme Sr contents plot outside fractionation trends, as a result of the remelting of previously crystallized nephelinitic rocks in depth.

  5. Rare-earth elements enrichment of Pacific seafloor sediments: the view from volcanic islands of Polynesia

    NASA Astrophysics Data System (ADS)

    Melleton, Jérémie; Tuduri, Johann; Pourret, Olivier; Bailly, Laurent; Gisbert, Thierry

    2014-05-01

    Rare-earth elements (REEs) are key metals for «green» technologies such as energy saving lamps or permanent magnets used in, e.g., wind turbines, hard disk drives, portable phone or electric or hybrid vehicles. Since several years, world demand for these metals is therefore drastically increasing. The quasi-monopolistic position of China, which produces around 95 % of global REEs production, generates risks for the industries that depend on a secure supply of REEs. In response, countries are developing and diversifying their supply sources, with new mining projects located outside China and efforts in the area of REEs recycling. Most of these projects focus on deposits related to carbonatites and alkaline-peralkaline magmatism, which are generally enriched in light REEs (LREEs) compared to the heavy REEs (HREEs)-enriched deposits of the ion-adsorption types, located in southern China. However, a recent study revealed new valuable resources corresponding to seafloor sediments located in the south-eastern and north-central Pacific. The deep-sea mud described by these authors show a higher HREE/LREE ratio than ion-adsorption deposits, a feature which significantly increases their economic interest. The authors suggest mid-ocean ridge hydrothermal activity as an explanation to this anomalous enrichment. However, several contributions have documented considerable REEs enrichment in basalts and peridotitic xenoliths from French Polynesia. Several arguments have been exposed in favour of a supergene origin, with a short migration, suggesting that REEs were collected from weathered basalts. The Tahaa volcanic island (Sous-le-Vent Island, Society Archipelago, French Polynesia) is the first location where such enrichment has been described. New petrographic and mineralogical investigations confirm a supergene mobilization of this abnormal occurrence. REE-bearing minerals (mainly phosphates of the rhabdophane group) are primarily located within basalt vesicles but also in crack that cross-cut the calcite filling the vesicles or the volcanic glass. They are also closely associated with Ni-Mg bearing phyllosilicates, which appear to nucleate from alteration of olivine and clinopyroxenes. Further investigations are done to evidence and confirm an anterior magmatic enrichment. On the basis of these observations, we believe that the anomalous enrichment observed in seafloor sediments could derive from abnormally-rich provinces corresponding to aerial basaltic formations from oceanic islands primarily enriched during weathering processes (Melleton et al., 2014). Melleton et al. (2014). Rare-earth elements enrichment of Pacific sea-floor sediments: the view from volcanic islands of Polynesia. In preparation.

  6. Trace-element modeling of the magmatic evolution of rare-earth-rich carbonatite from the Miaoya deposit, Central China

    NASA Astrophysics Data System (ADS)

    Xu, Cheng; Kynicky, Jindrich; Chakhmouradian, Anton R.; Campbell, Ian H.; Allen, Charlotte M.

    2010-07-01

    Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock-forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100-260 ppm) and relatively flat chondrite-normalized REE distribution patterns [average (La/Yb) CN = 1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and fluorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing fluorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb) CN ? 0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates ? calcite ? REE-fluorocarbonates) from an initially REE-rich carbonatitic liquid.

  7. Utilizing rare earth elements as tracers in high TDS reservoir brines in CCS applications

    SciTech Connect

    McLing, Travis; Smith, William; Smith, Robert

    2014-12-31

    In this paper we report the result of research associated with the testing of a procedures necessary for utilizing natural occurring trace elements, specifically the Rare Earth Elements (REE) as geochemical tracers in Carbon Capture and Storage (CCS) applications. Trace elements, particularly REE may be well suited to serve as in situ tracers for monitoring geochemical conditions and the migration of CO₂-charged waters within CCS storage systems. We have been conducting studies to determine the efficacy of using REE as a tracer and characterization tool in the laboratory, at a CCS analogue site in Soda Springs, Idaho, and at a proposed CCS reservoir at the Rock Springs Uplift, Wyoming. Results from field and laboratory studies have been encouraging and show that REE may be an effective tracer in CCS systems and overlying aquifers. In recent years, a series of studies using REE as a natural groundwater tracer have been conducted successfully at various locations around the globe. Additionally, REE and other trace elements have been successfully used as in situ tracers to describe the evolution of deep sedimentary Basins. Our goal has been to establish naturally occurring REE as a useful monitoring measuring and verification (MMV) tool in CCS research because formation brine chemistry will be particularly sensitive to changes in local equilibrium caused by the addition of large volumes of CO₂. Because brine within CCS target formations will have been in chemical equilibrium with the host rocks for millions of years, the addition of large volumes of CO₂ will cause reactions in the formation that will drive changes to the brine chemistry due to the pH change caused by the formation of carbonic acid. This CO₂ driven change in formation fluid chemistry will have a major impact on water rock reaction equilibrium in the formation, which will impart a change in the REE fingerprint of the brine that can measured and be used to monitor in situ reservoir conditions. Our research has shown that the REE signature imparted to the formation fluid by the introduction of CO₂ to the formation, can be measured and tracked as part of an MMV program. Additionally, this REE fingerprint may serve as an ideal tracer for fluid migration, both within the CCS target formation, and should formation fluids migrate into overlying aquifers. However application of REE and other trace elements to CCS system is complicated by the high salt content of the brines contained within the target formations. In the United States by regulation, in order for a geologic reservoir to be considered suitable for carbon storage, it must contain formation brine with total dissolved solids (TDS) > 10,000 ppm, and in most cases formation brines have TDS well in excess of that threshold. The high salinity of these brines creates analytical problems for elemental analysis, including element interference with trace metals in Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) (i.e. element mass overlap due to oxide or plasma phenomenon). Additionally, instruments like the ICP-MS that are sensitive enough to measure trace elements down to the parts per trillion level are quickly oversaturated when water TDS exceeds much more than 1,000 ppm. Normally this problem is dealt with through dilution of the sample, bringing the water chemistry into the instruments working range. However, dilution is not an option when analyzing these formation brines for trace metals, because trace elements, specifically the REE, which occur in aqueous solutions at the parts per trillion levels. Any dilution of the sample would make REE detection impossible. Therefore, the ability to use trace metals as in situ natural tracers in high TDS brines environments requires the development of methods for pre-concentrating trace elements, while reducing the salinity and associated elemental interference such that the brines can be routinely analyzed by standard ICP-MS methods. As part of the Big Sky Carbon Sequestration Project the INL-CAES has developed a rapid, easy to use process that pre-concentrates trace metals, including REE, up to 100x while eliminating interfering ions (e.g. Ba, Cl). The process is straightforward, inexpensive, and requires little infrastructure, using only a single chromatography column with inexpensive, reusable, commercially available resins and wash chemicals. The procedure has been tested with synthetic brines (215,000 ppm or less TDS) and field water samples (up to 5,000 ppm TDS). Testing has produced data of high quality with REE capture efficiency exceeding 95%, while reducing interfering elements by > 99%.

  8. Utilizing rare earth elements as tracers in high TDS reservoir brines in CCS applications

    DOE PAGESBeta

    McLing, Travis; Smith, William; Smith, Robert

    2014-12-31

    In this paper we report the result of research associated with the testing of a procedures necessary for utilizing natural occurring trace elements, specifically the Rare Earth Elements (REE) as geochemical tracers in Carbon Capture and Storage (CCS) applications. Trace elements, particularly REE may be well suited to serve as in situ tracers for monitoring geochemical conditions and the migration of CO₂-charged waters within CCS storage systems. We have been conducting studies to determine the efficacy of using REE as a tracer and characterization tool in the laboratory, at a CCS analogue site in Soda Springs, Idaho, and at amore » proposed CCS reservoir at the Rock Springs Uplift, Wyoming. Results from field and laboratory studies have been encouraging and show that REE may be an effective tracer in CCS systems and overlying aquifers. In recent years, a series of studies using REE as a natural groundwater tracer have been conducted successfully at various locations around the globe. Additionally, REE and other trace elements have been successfully used as in situ tracers to describe the evolution of deep sedimentary Basins. Our goal has been to establish naturally occurring REE as a useful monitoring measuring and verification (MMV) tool in CCS research because formation brine chemistry will be particularly sensitive to changes in local equilibrium caused by the addition of large volumes of CO₂. Because brine within CCS target formations will have been in chemical equilibrium with the host rocks for millions of years, the addition of large volumes of CO₂ will cause reactions in the formation that will drive changes to the brine chemistry due to the pH change caused by the formation of carbonic acid. This CO₂ driven change in formation fluid chemistry will have a major impact on water rock reaction equilibrium in the formation, which will impart a change in the REE fingerprint of the brine that can measured and be used to monitor in situ reservoir conditions. Our research has shown that the REE signature imparted to the formation fluid by the introduction of CO₂ to the formation, can be measured and tracked as part of an MMV program. Additionally, this REE fingerprint may serve as an ideal tracer for fluid migration, both within the CCS target formation, and should formation fluids migrate into overlying aquifers. However application of REE and other trace elements to CCS system is complicated by the high salt content of the brines contained within the target formations. In the United States by regulation, in order for a geologic reservoir to be considered suitable for carbon storage, it must contain formation brine with total dissolved solids (TDS) > 10,000 ppm, and in most cases formation brines have TDS well in excess of that threshold. The high salinity of these brines creates analytical problems for elemental analysis, including element interference with trace metals in Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) (i.e. element mass overlap due to oxide or plasma phenomenon). Additionally, instruments like the ICP-MS that are sensitive enough to measure trace elements down to the parts per trillion level are quickly oversaturated when water TDS exceeds much more than 1,000 ppm. Normally this problem is dealt with through dilution of the sample, bringing the water chemistry into the instruments working range. However, dilution is not an option when analyzing these formation brines for trace metals, because trace elements, specifically the REE, which occur in aqueous solutions at the parts per trillion levels. Any dilution of the sample would make REE detection impossible. Therefore, the ability to use trace metals as in situ natural tracers in high TDS brines environments requires the development of methods for pre-concentrating trace elements, while reducing the salinity and associated elemental interference such that the brines can be routinely analyzed by standard ICP-MS methods. As part of the Big Sky Carbon Sequestration Project the INL-CAES has developed a rapid, easy to use process that pre-concentrates trace metals, including REE, up to 100x while eliminating interfering ions (e.g. Ba, Cl). The process is straightforward, inexpensive, and requires little infrastructure, using only a single chromatography column with inexpensive, reusable, commercially available resins and wash chemicals. The procedure has been tested with synthetic brines (215,000 ppm or less TDS) and field water samples (up to 5,000 ppm TDS). Testing has produced data of high quality with REE capture efficiency exceeding 95%, while reducing interfering elements by > 99%.« less

  9. A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

    USGS Publications Warehouse

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

    1954-01-01

    In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80??0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5??0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error. ?? 1954.

  10. Using Rare Earth Element (REE) tracers to identify perferential micro-sites of post-fire aeolian erosion

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant communities in desert environments are spatially anisotropic. We applied Rare Earth Element (REE) tracers to different landscape positions of an anisotropic Northern Chihuahua Desert ecosystem in an effort to study preferential sediment source areas. We delineated three 0.5 m by 6 m plots of...

  11. The Fe-Ni-(S) System at 23 GPa: The Possibility of Strong Chemical Fractionation Between Phases in the Cores of the Earth, Mars and Mercury

    NASA Astrophysics Data System (ADS)

    Stewart, A. J.; Schmidt, M. W.

    2004-12-01

    The presence of nickel in the Earths core is widely accepted based on cosmochemical and seismological arguments. However, experimental studies into core compositions rarely include nickel, thus adding a degree of simplicity to otherwise complex experiments. Diamond-anvil cell studies have discovered that Fe-Ni alloys appear to separate into two phases upon heating above 10 GPa: from a single hexagonally close-packed (hcp) phase to the presence of both hcp and face centered cubic (fcc) phases (Lin et al., 2002). Unfortunately, due to the small size of diamond-anvil cell samples, meaningful quantitative analysis is commonly impossible. We have conducted multi-anvil experiments at 23 GPa into the Fe-Ni system and have confirmed the presence of two phases in the sub-solidus system. The starting material for these experiments contains 6 wt% nickel, approximating the amount expected to be found in the Earths core (McDonough, 2003). In experiments to 1500 C (the highest temperature thus far examined), electron microprobe analyses show dramatic phase fractionation with charges separating into an iron-rich phase containing less than 1 wt% Ni and a nickel-rich phase containing as much as 98 wt% Ni. We have observed the effect over a range of more than 500 C; further experiments are underway to determine whether these phases both persist toward the melting point of the alloy. Multi-anvil experiments at 23 GPa have also been conducted to examine the effect of nickel on the Fe-S system. Sulphur is an element favoured by many researchers as the light element component in the core of the Earth as well as that of Mars. Previous research has suggested that the addition of nickel to the Fe-S system results in the lowering of eutectic temperatures by about 75 C (Pike et al., 1999). The starting material for these experiments is the same as that used for the pure Fe-Ni experiments discussed above, with the addition of sulphur. Our results indicate a pseudo-binary, (Fe, Ni)-S, eutectic point lying slightly below 1200 C, roughly consistent with the results of Pike et al. (1999). The measured eutectic liquid composition contains 4.4 wt% Ni and 15.8 wt% S. This liquid composition fits closely to the ideal composition of a (Fe, Ni)3S compound (16.0 wt% S with 4.4 wt% Ni in the alloy), suggesting the possible importance of this structure in Fe-Ni-S melts. At subsolidus temperatures in the Fe-Ni-S system, our results become very interesting with each charge showing at least 3 coexisting phases. Based on these results, solid cores of Mercury and Mars containing iron, nickel and sulphur will hold at least 3 phases. Extrapolating our results to the inner core of the Earth would suggest that multiple phases occur in our planet as well.

  12. Health effects and toxicity mechanisms of rare earth elements-Knowledge gaps and research prospects.

    PubMed

    Pagano, Giovanni; Guida, Marco; Tommasi, Franca; Oral, Rahime

    2015-05-01

    In the recent decades, rare earth elements (REE) have undergone a steady spread in several industrial and medical applications, and in agriculture. Relatively scarce information has been acquired to date on REE-associated biological effects, from studies of bioaccumulation and of bioassays on animal, plant and models; a few case reports have focused on human health effects following occupational REE exposures, in the present lack of epidemiological studies of occupationally exposed groups. The literature is mostly confined to reports on few REE, namely cerium and lanthanum, whereas substantial information gaps persist on the health effects of other REE. An established action mechanism in REE-associated health effects relates to modulating oxidative stress, analogous to the recognized redox mechanisms observed for other transition elements. Adverse outcomes of REE exposures include a number of endpoints, such as growth inhibition, cytogenetic effects, and organ-specific toxicity. An apparent controversy regarding REE-associated health effects relates to opposed data pointing to either favorable or adverse effects of REE exposures. Several studies have demonstrated that REE, like a number of other xenobiotics, follow hormetic concentration-related trends, implying stimulatory or protective effects at low levels, then adverse effects at higher concentrations. Another major role for REE-associated effects should be focused on pH-dependent REE speciation and hence toxicity. Few reports have demonstrated that environmental acidification enhances REE toxicity; these data may assume particular relevance in REE-polluted acidic soils and in REE mining areas characterized by concomitant REE and acid pollution. The likely environmental threats arising from REE exposures deserve a new line of research efforts. PMID:25679485

  13. Significant Li isotope fractionation in geochemically evolved rare element-bearing pegmatites from the Little Nahanni Pegmatite Group, NWT, Canada

    NASA Astrophysics Data System (ADS)

    Barnes, Elspeth M.; Weis, Dominique; Groat, Lee A.

    2012-02-01

    Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier ? 7Li signatures within the broad range measured from whole rock LNPG samples (- 0.94 to + 11.36) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display ? 7Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H 2O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.

  14. The geochemistry of rare earth elements in groundwater from the Carnmenellis area, southwest England

    NASA Astrophysics Data System (ADS)

    Smedley, Pauline L.

    1991-10-01

    Shallow groundwater samples from the Carnmenellis area of southwest England collected from wells, boreholes, springs, adits and stream baseflow represent recently recharged waters of low salinity. Their major ion concentrations closely reflect the lithology of their host rocks which comprise the Carnmenellis granite and Devonian metasediments (and metabasite) of greenschist grade. Groundwaters from the granite are predominantly Na-Cl or Na-Ca-Cl type whilst those from the metasediment are Na-Ca-Mg-Cl-HCO 3 waters with a larger range of compositions. The major ion compositions are predominantly a function of water-rock interaction processes and the larger range of metasediment-water compositions probably reflects the greater lithological variation. The pH of groundwater samples circulating through granite is typically lower than that of groundwater in the metasediments, the range being 4.3 to 7.2 (median 5.7) and 4.7 to 8.0 (median 6.6) respectively. Rare earth element (REE) concentrations of 0.45 ?m-filtered groundwater samples have been determined by inductively coupled plasma mass spectrometry (ICP-MS). A large range of concentrations exists and many are below detection limits but levels reach up to 229 ?g/1 (1.6 ?m) total REEs. The REEs are strongly controlled by pH with higher levels in groundwaters of pH < 6. Chondrite-normalised profiles are light rare earth element (LREE) enriched compared to heavy rare earths (HREEs), with a common slight negative Eu anomaly: both features reflecting the compositions of their host rocks. REE profiles therefore appear to be controlled by water-rock interactions involving predominantly REE-enriched minerals. In the granite, the REEs are probably derived mainly from the accessory minerals monazite and apatite as well as the high-REE framework minerals biotite and muscovite. The source of REEs in groundwater from the metasediments is more uncertain but probably includes clay minerals, chlorite, and carbonate. REE compositions normalised to shale have flatter profiles, although many are slightly convex with higher normalised Sm, Eu, and Gd values. A few metasediment-derived waters with high total REE concentrations have LREE-enriched shale-normalised patterns. It is suggested that the bulk of the REEs in these few samples is colloidal rather than totally dissolved. Groundwaters from the metasediments have a notable depletion in Ce which is distinct from waters in the granite. This depletion is problematic in that it is difficult to see how redox processes could be the dominant control, since groundwaters from the metasediments are unlikely to be more oxidising than those from the granite. Likewise, variations in pH fail to totally explain the distinctions in Ce concentration and La/Ce ratios between the two water types. It is therefore suggested that the Ce contents are largely source-related rather than process-related. The observed REE compositions of granite- and metasedimentderived groundwaters from the Carnmenellis area are so distinctive that the REEs in general and Ce in particular might be useful as future tracers in studies of water-rock interaction and groundwater provenance.

  15. Examination of rare earth element concentration patterns in freshwater fish tissues.

    PubMed

    Mayfield, David B; Fairbrother, Anne

    2015-02-01

    Rare earth elements (REEs or lanthanides) were measured in ten freshwater fish species from a reservoir in Washington State (United States). The REE distribution patterns were examined within fillet and whole body tissues for three size classes. Total concentrations (?REE) ranged from 0.014 to 3.0 mg kg(-1) (dry weight) and averaged 0.243 mg kg(-1) (dry weight). Tissue concentration patterns indicated that REEs accumulated to a greater extent in organs, viscera, and bone compared to muscle (fillet) tissues. Benthic feeding species (exposed to sediments) exhibited greater concentrations of REEs than pelagic omnivorous or piscivorous fish species. Decreasing REE concentrations were found with increasing age, total length or weight for largescale and longnose suckers, smallmouth bass, and walleye. Concentration patterns in this system were consistent with natural conditions without anthropogenic sources of REEs. These data provide additional reference information with regard to the fate and transport of REEs in freshwater fish tissues in a large aquatic system. PMID:25000508

  16. Effect of Rare Earth Elements on Isothermal Transformation Kinetics in Si-Mn-Mo Bainite Steels

    NASA Astrophysics Data System (ADS)

    Liang, Yilong; Yi, Yanliang; Long, Shaolei; Tan, Qibing

    2014-12-01

    Isothermal heat treatments to Si-Mn-Mo steel specimens were performed, and time-temperature-transformation curves (C-curves) were plotted by DIL805A/D differential dilatometer. The effect of rare earth (RE) elements on bainite transformation kinetics was systematically studied by adopting the empirical electron theory of solids and molecules, Johnson-Mehl-Avrami equation calculation, dilatometry, and metallography. Experimental results show that the addition of RE in Si-Mn-Mo bainite steels leads to the C-curves moving to bottom right and prolongs incubation period of bainite transformation. Moreover, RE addition increases the values of phase structure factors ( n A, F {C/D}) and activation energy of bainite transformation, inhibits the formation of granular bainite, and refines microstructures of bainitic ferrite and substructures. During the bainite transformation process, bainite transformation is delayed due to the drag effect, which is induced by the segregation of RE at the ferrite interphase and the retardation of Fe-C-RE (segregation units) on carbon diffusion.

  17. Effect of Rare Earth Elements on Isothermal Transformation Kinetics in Si-Mn-Mo Bainite Steels

    NASA Astrophysics Data System (ADS)

    Liang, Yilong; Yi, Yanliang; Long, Shaolei; Tan, Qibing

    2014-09-01

    Isothermal heat treatments to Si-Mn-Mo steel specimens were performed, and time-temperature-transformation curves (C-curves) were plotted by DIL805A/D differential dilatometer. The effect of rare earth (RE) elements on bainite transformation kinetics was systematically studied by adopting the empirical electron theory of solids and molecules, Johnson-Mehl-Avrami equation calculation, dilatometry, and metallography. Experimental results show that the addition of RE in Si-Mn-Mo bainite steels leads to the C-curves moving to bottom right and prolongs incubation period of bainite transformation. Moreover, RE addition increases the values of phase structure factors (n A, F {C/D}) and activation energy of bainite transformation, inhibits the formation of granular bainite, and refines microstructures of bainitic ferrite and substructures. During the bainite transformation process, bainite transformation is delayed due to the drag effect, which is induced by the segregation of RE at the ferrite interphase and the retardation of Fe-C-RE (segregation units) on carbon diffusion.

  18. Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control

    USGS Publications Warehouse

    Morgan, J.W.; Wandless, G.A.

    1980-01-01

    Rare earth element (REE) abundances were measured by neutron activation analysis in anhydrite (CaSO4), barite (BaSO4), siderite (FeCO3) and galena (PbS). A simple crystal-chemical model qualitatively describes the relative affinities for REE substitution in anhydrite, barite, and siderite. When normalized to 'crustal' abundances (as an approximation to the hydrothermal fluid REE pattern), log REE abundance is a surprisingly linear function of (ionic radius of major cation-ionic radius of REE)2 for the three hydrothermal minerals, individually and collectively. An important exception, however, is Eu, which is anomalously enriched in barite and depleted in siderite relative to REE of neighboring atomic number and trivalent ionic radius. In principle, REE analyses of suitable pairs of co-existing hydrothermal minerals, combined with appropriate experimental data, could yield both the REE content and the temperature of the parental hydrothermal fluid. The REE have only very weak chalcophilic tendencies, and this is reflected by the very low abundances in galena-La, 0.6 ppb; Sm, 0.06 ppb; the remainder are below detection limits. ?? 1980.

  19. Remediation of Rare Earth Element Pollutants by Sorption Process Using Organic Natural Sorbents

    PubMed Central

    Butnariu, Monica; Negrea, Petru; Lupa, Lavinia; Ciopec, Mihaela; Negrea, Adina; Pentea, Marius; Sarac, Ionut; Samfira, Ionel

    2015-01-01

    The effects of the sorption of environmental applications by various source materials of natural organic matter, i.e., bone powder, was examined. Sorption capacities and subsequent rare earth element retention characteristics of all metals tested were markedly increased by ionic task-specific. In this study, the abilities of three models’ isotherms widely were used for the equilibrium sorption data: Langmuir, Freundlich and Redlich-Peterson. For all studied metal ions the maximum adsorption capacity is close to those experimentally determined. The characteristic parameters for each isotherm and related coefficients of determination have been determined. The experimental data achieved excellent fits within the following isotherms in the order: Langmuir > Redlich-Peterson > Freundlich, based on their coefficient of determination values. The bone powder has developed higher adsorption performance in the removal process of Nd(III), Eu(III), La(III) from aqueous solutions than in the case of the removal process of Cs(I), Sr(II) and Tl(I) from aqueous solutions. The described relationships provide direct experimental evidence that the sorption-desorption properties of bone powder are closely related to their degree of the type of the metal. The results suggest a potential for obtaining efficient and cost-effective engineered natural organic sorbents for environmental applications. PMID:26378553

  20. Rare earth element geochemistry of massive sulfides-sulfates and gossans on the Southern Explorer Ridge

    SciTech Connect

    Barrett, T.J. ); Jarvis, I. ); Jarvis, K.E. )

    1990-07-01

    Massive sulfide-sulfate deposits on the Southern Explorer Ridge were analyzed for 14 rare earth elements (REE) by a modified inductively coupled plasma-mass spectrometric technique that included a correction for high Ba content. Bulk samples of finely intermixed sulfides, sulfate, and amorphous silica contain {Sigma}REE concentrations of {le} 6 ppm. REE patterns range from (1) strongly enriched in light REE with positive Eu anomalies, to (2) relatively flat with positive Eu anomalies and slightly negative Ce anomalies, to (3) slightly enriched in light REE with moderately negative Ce anomalies. Pattern 1 is similar to that of 300-350 C solutions discharging at vents on the East Pacific Rise and the Mid-Atlantic Ridge, whereas pattern 3 resembles REE distributions in normal oceanic bottom waters. The sulfide-sulfate patterns are interpreted to result from variable mixtures of hydrothermal and normal seawater. Barite in gossans capping the mounds has an REE pattern almost identical to patterns of high-temperature vent solutions. Hydrothermal barite has lower REE contents and a different REE pattern relative to hydrogenous barite formed slowly on the sea floor.

  1. Remediation of Rare Earth Element Pollutants by Sorption Process Using Organic Natural Sorbents.

    PubMed

    Butnariu, Monica; Negrea, Petru; Lupa, Lavinia; Ciopec, Mihaela; Negrea, Adina; Pentea, Marius; Sarac, Ionut; Samfira, Ionel

    2015-09-01

    The effects of the sorption of environmental applications by various source materials of natural organic matter, i.e., bone powder, was examined. Sorption capacities and subsequent rare earth element retention characteristics of all metals tested were markedly increased by ionic task-specific. In this study, the abilities of three models' isotherms widely were used for the equilibrium sorption data: Langmuir, Freundlich and Redlich-Peterson. For all studied metal ions the maximum adsorption capacity is close to those experimentally determined. The characteristic parameters for each isotherm and related coefficients of determination have been determined. The experimental data achieved excellent fits within the following isotherms in the order: Langmuir > Redlich-Peterson > Freundlich, based on their coefficient of determination values. The bone powder has developed higher adsorption performance in the removal process of Nd(III), Eu(III), La(III) from aqueous solutions than in the case of the removal process of Cs(I), Sr(II) and Tl(I) from aqueous solutions. The described relationships provide direct experimental evidence that the sorption-desorption properties of bone powder are closely related to their degree of the type of the metal. The results suggest a potential for obtaining efficient and cost-effective engineered natural organic sorbents for environmental applications. PMID:26378553

  2. Innovative Application of Mechanical Activation for Rare Earth Elements Recovering: Process Optimization and Mechanism Exploration.

    PubMed

    Tan, Quanyin; Deng, Chao; Li, Jinhui

    2016-01-01

    With the rapidly expanding use of fluorescent lamps (FLs) and increasing interest in conservation and sustainable utilization of critical metals such as rare earth elements (REEs), the recovering of REEs from phosphors in waste FLs is becoming a critical environmental and economic issue. To effectively recycle REEs with metallurgical methods, mechanical activation by ball milling was introduced to pretreat the waste phosphors. This current study put the emphasis on the mechanical activation and leaching processes for REEs, and explored the feasibility of the method from both theoretical and practical standpoints. Results showed physicochemical changes of structural destruction and particle size reduction after mechanical activation, leading to the easy dissolution of REEs in the activated samples. Under optimal conditions, dissolution yields of 89.4%, 93.1% and 94.6% for Tb, Eu and Y, respectively, were achieved from activated waste phosphors using hydrochloric acid as the dissolution agent. The shrinking core model proved to be the most applicable for the leaching procedure, with an apparent activation energy of 10.96 ± 2.79 kJ/mol. This novel process indicates that mechanical activation is an efficient method for recovering REEs from waste phosphors, and it has promising potential for REE recovery with low cost and high efficiency. PMID:26819083

  3. Composition and evolution of the eucrite parent body - Evidence from rare earth elements. [extraterrestrial basaltic melts

    NASA Technical Reports Server (NTRS)

    Consolmagno, G. J.; Drake, M. J.

    1977-01-01

    Quantitative modeling of the evolution of rare earth element (REE) abundances in the eucrites, which are plagioclase-pigeonite basalt achondrites, indicates that the main group of eucrites (e.g., Juvinas) might have been produced by approximately 10% equilibrium partial melting of a single type of source region with initial REE abundances which were chondritic relative and absolute. Since the age of the eucrites is about equal to that of the solar system, extensive chemical differentiation of the eucrite parent body prior to the formation of eucrites seems unlikely. If homogeneous accretion is assumed, the bulk composition of the eucrite parent body can be estimated; two estimates are provided, representing different hypotheses as to the ratio of metal to olivine in the parent body. Since a large number of differentiated olivine meteorites, which would represent material from the interior of the parent body, have not been detected, the eucrite parent body is thought to be intact. It is suggested that the asteroid 4 Vesta is the eucrite parent body.

  4. Determination of Rare Earth Elements in Hypersaline Solutions Using Low-Volume, Liquid-Liquid Extraction.

    PubMed

    Noack, Clinton W; Dzombak, David A; Karamalidis, Athanasios K

    2015-08-18

    Complex, hypersaline brines-including those coproduced with oil and gas, rejected from desalination technologies, or used as working fluids for geothermal electricity generation-could contain critical materials such as the rare earth elements (REE) in valuable concentrations. Accurate quantitation of these analytes in complex, aqueous matrices is necessary for evaluation and implementation of systems aimed at recovering those critical materials. However, most analytical methods for measuring trace metals have not been validated for highly saline and/or chemically complex brines. Here we modified and optimized previously published liquid-liquid extraction (LLE) techniques using bis(2-ethylhexyl) phosphate as the extractant in a heptane diluent, and studied its efficacy for REE recovery as a function of three primary variables: background salinity (as NaCl), concentration of a competing species (here Fe), and concentration of dissolved organic carbon (DOC). Results showed that the modified LLE was robust to a range of salinity, Fe, and DOC concentrations studied as well as constant, elevated Ba concentrations. With proper characterization of the natural samples of interest, this method could be deployed for accurate analysis of REE in small volumes of hyper-saline and chemically complex brines. PMID:25920439

  5. Template polymerization synthesis of hydrogel and silica composite for sorption of some rare earth elements.

    PubMed

    Borai, E H; Hamed, M G; El-kamash, A M; Siyam, T; El-Sayed, G O

    2015-10-15

    New sorbents containing 2-acrylamido 2-methyl propane sulphonic acid monomer onto poly(vinyl pyrilidone) P(VP-AMPS) hydrogel and P(VP-AMPS-SiO2) composite have been synthesized by radiation template polymerization. The effect of absorbed dose rate (kGy), crosslinker concentration and polymer/monomer ratio on the degree of template polymerization of P(VP-AMPS) hydrogel was studied. The degree of polymerization was evaluated by the calculated percent conversion and swelling degree. The maximum capacity of P(VP-AMPS) hydrogel toward Cu(+2) metal ion found to be 91 mg/gm. The polymeric composite P(VP-AMPS-SiO2) has been successfully synthesized. The structure of the prepared hydrogel and composite were confirmed by FTIR, thermal analysis (TGA and DTA) and SEM micrograph. Batch adsorption studies for La(3+), Ce(3+), Nd(3+), Eu(3+) and Pb(+2) metal ions on the prepared hydrogel and composite were investigated as a function of shaking time, pH and metal ion concentration. The sorption efficiency of the prepared hydrogel and composite toward light rare earth elements (LREEs) are arranged in the order La(3+)>Ce(3+)>Nd(3+)>Eu(3+). The obtained results demonstrated the superior adsorption capacity of the composite over the polymeric hydrogel. The maximum capacity of the polymeric composite was found to be 116, 103, 92, 76, 74 mg/gm for La(3+), Ce(3+), Nd(3+), Eu(3+) and Pb(2+) metal ions respectively. PMID:26141170

  6. Ionic conductivity of binary fluorides of potassium and rare earth elements

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.

    2016-01-01

    The ionic conductivity s of KYF4 and K2 RF5 single crystals ( R = Gd, Ho, Er) and KNdF4 and K2 RF5 ceramic samples ( R = Dy, Er) has been studied in the temperature range of 340-500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100-150 MPa) in the R 2O3-KF-H2O systems. The σ values of tetraf luorides are 3 × 10-5 S/cm (KYF4 single crystal) and 3 × 10-6 S/cm (KNdF4 ceramics) at 435°C. A K2ErF5 single crystal with σ = 1.2 × 10-4 S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K2HoF5 single crystals, σ∥ c /σ⊥ c = 2.5, where σ∥ c and σ⊥ c are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.

  7. Effect of Ca and Rare Earth Elements on Impression Creep Properties of AZ91 Magnesium Alloy

    NASA Astrophysics Data System (ADS)

    Nami, B.; Razavi, H.; Mirdamadi, S.; Shabestari, S. G.; Miresmaeili, S. M.

    2010-08-01

    Creep properties of AZ91 magnesium alloy and AZRC91 (AZ91 + 1 wt pct RE + 1.2 wt pct Ca) alloy were investigated using the impression creep method. It was shown that the creep properties of AZ91 alloy are significantly improved by adding Ca and rare earth (RE) elements. The improvement in creep resistance is mainly attributed to the reduction in the amount and continuity of eutectic ?(Mg17Al12) phase as well as the formation of new Al11RE3 and Al2Ca intermetallic compounds at interdendritic regions. It was found that the stress exponent of minimum creep rate, n, varies between 5.69 and 6 for AZ91 alloy and varies between 5.81 and 6.46 for AZRC91 alloy. Activation energies of 120.9 8.9 kJ/mol and 100.6 7.1 kJ/mol were obtained for AZ91 and AZRC91 alloys, respectively. It was shown that the lattice and pipe-diffusion-controlled dislocation climb are the dominant creep mechanisms for AZ91 and AZRC91 alloys, respectively. The constitutive equations, correlating the minimum creep rate with temperature and stress, were also developed for both alloys.

  8. Red Phosphorus: An Earth-Abundant Elemental Photocatalyst for "Green" Bacterial Inactivation under Visible Light.

    PubMed

    Xia, Dehua; Shen, Zhurui; Huang, Guocheng; Wang, Wanjun; Yu, Jimmy C; Wong, Po Keung

    2015-05-19

    Earth-abundant red phosphorus was found to exhibit remarkable efficiency to inactivate Escherichia coli K-12 under the full spectrum of visible light and even sunlight. The reactive oxygen species (OH, O2(-), H2O2), which were measured and identified to derive mainly from photogenerated electrons in the conduction band using fluorescent probes and scavengers, collectively contributed to the good performance of red phosphorus. Especially, the inactivated-membrane function enzymes were found to be associated with great loss of respiratory and ATP synthesis activity, the kinetics of which paralleled cell death and occurred much earlier than those of cytoplasmic proteins and chromosomal DNA. This indicated that the cell membrane was a vital first target for reactive oxygen species oxidation. The increased permeability of the cell membrane consequently accelerated intracellular protein carboxylation and DNA degradation to cause definite bacterial death. Microscopic analyses further confirmed the cell destruction process starting with the cell envelope and extending to the intracellular components. The red phosphorus still maintained good performance even after recycling through five reaction cycles. This work offers new insight into the exploration and use of an elemental photocatalyst for "green" environmental applications. PMID:25894494

  9. Sorption from slurries—A promising method in the processing of rare earth elements

    NASA Astrophysics Data System (ADS)

    Kosynkin, V. D.; Molchanova, T. V.; Peganov, V. A.; Zharova, E. V.

    2015-09-01

    The article presents the results of sorptive extraction of rare-earth elements (REE) from the solutions and slurries of complex salt compositions using sulfocationites and carboxyl cationites with a predominant content of the latter on laboratory and pilot scales. Upon REE sorption from hydrate slurry on KM-2p carboxyl cationite, the REE extraction rate of at least 98% has been achieved, and the following factors of ΣREE purification from impurities have been obtained: K REE/Al = 1.7, K REE/Th = 2.3, K REE/Ca ≈ 20, K REE/Zr = 15, K REE/Fe ≈ 40, and K REE/P,F ≈ 90. It is demonstrated that the REE capacity of cationite SG-1m is higher than that of cationite KM-2p by 10%; moreover, the content of thorium on KM-2p cationite is lower by 2.5 times and that of zirconium by 6 times. After the recovery of saturated cationites by 1.5-2.0 M HNO3 solutions, strippants have been extracted with a REE concentration of 15-20 g/L. The factors of REE purification from impurities upon desorption are as follows: K REE/Al = 2.5, K REE/Th = 0.5, K REE/Ca = 5.3, K REE/Zr = 5.6, and K REE/Fe = 0.8. The REE recovery rate is ≥99%.

  10. Selective Extraction of Rare Earth Elements from Permanent Magnet Scraps with Membrane Solvent Extraction.

    PubMed

    Kim, Daejin; Powell, Lawrence E; Delmau, Lætitia H; Peterson, Eric S; Herchenroeder, Jim; Bhave, Ramesh R

    2015-08-18

    The rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acid solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. The resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets. PMID:26107531

  11. Gupta potential for rare earth elements of the fcc phase: lanthanum and cerium

    NASA Astrophysics Data System (ADS)

    Fu, Jie; Zhao, Jijun

    2013-09-01

    The potential parameters for a Gupta-type many-body potential are fitted for the first two rare earth elements, La and Ce. The experimental cohesive energies, lattice parameters and elastic constants of ?-La and ?-Ce solids of the face-centered cubic (fcc) phase are well reproduced. The theoretical P-V curves, sound velocities and Debye temperatures of ?-La and ?-Ce solids are in reasonable agreement with experimental data. The vacancy formation energies and surface energies are also predicted. In particular, the phonon dispersion relationship and vibrational frequencies at high symmetric points within the first Brillouin zone from our potential are consistent with experimental ones. Molecular dynamics simulation are performed to determine the melting temperature of La and Ce solids as well as the radial distribution function of liquid La, which are also in line with experimental data. All these agreements indicate the validity of the current set of potential parameters. Thus, the Gupta potential developed here would be useful in future simulation of La, Ce solids and their alloys.

  12. Rare earth elements in sediments off southern California: a new Anthropogenic indicator

    SciTech Connect

    Olmez, I. ); Sholkovitz, E.R.; Hermann, D. ); Eganhouse, R.P. )

    1990-01-09

    The rare earth element (REE) composition of dated sediment cores from the San Pedro Shelf (60 m) and the Santa Barbara Basin (588 m) are contrasted. The Santa Barbara Basin cores has relatively uniform REE concentrations throughout it's 60 cm length and a REE composition similar to the crustal abundance. In contrast, the upper 20 cm of the 36 cm deep San Pedro Shelf core is enriched in the concentrations of the light REE (La, Cd, Nd and Sm) but not in the middle REE (Eu) and the heavy REE (Yb, Lu). These upper sediments have a REE signature which is very different from crustal material and which corresponds to anthropogenic inputs beginning in the early 1960's delivered from the Joint Water Pollution Control Plant wastewater outfall located 6 km upcurrent from the San Pedro Shelf Core. The sources of the light REE enrichment are petroleum cracking catalysts and their products; these include emissions, bottom ash, fly ash and wastewater from oil-burning powerplants and oil-refineries. Cracking catalysts are produced from Bastnasite and Monazite, REE ore minerals strongly enriched in light REE. With their unique signature and source, light REE may be a new tool for tracing anthropogenic inputs to the Santa Monica and San Pedro Basins.

  13. On the non-uniform distribution of the angular elements of near-Earth objects

    NASA Astrophysics Data System (ADS)

    JeongAhn, Youngmin; Malhotra, Renu

    2014-02-01

    We examine the angular distributions of near-Earth objects (NEOs) which are often regarded as uniform. The apparent distribution of the longitude of ascending node, ?, is strongly affected by well-known seasonal effects in the discovery rate of NEOs. The deviation from the expected ?-periodicity in the apparent distribution of ? indicates that its intrinsic distribution is slightly enhanced along a mean direction, ??=111; approximately 53% of NEOs have ? values within 90 of ??. We also find that each subgroup of NEOs (Amors, Apollos and Atens) has different observational selection effects which cause different non-uniformities in the apparent distributions of their arguments of perihelion ?, and longitudes of perihelion ?. For their intrinsic distributions, our analysis reveals that the Apollo asteroids have non-uniform ? due to secular dynamics associated with inclination-eccentricity-? coupling, and the Amors ? distribution is peaked towards the secularly forced eccentricity vector. The Apollos ? distribution is axial, favoring values near 0 and 180; the two quadrants centered at 0 and 180 account for 55% of the Apollos ? values. The Amors ? distribution peaks near ??=4; 61% of Amors have ? within 90 of this peak. We show that these modest but statistically significant deviations from uniform random distributions of angular elements are owed to planetary perturbations, primarily Jupiters. It is remarkable that this strongly chaotic population of minor planets reveals the presence of Jupiter in its angular distributions.

  14. Cerium redox cycles and rare earth elements in the Sargasso Sea

    SciTech Connect

    Sholkovitz, E.R.; Schneider, D.L. )

    1991-10-01

    Two profiles of the rare earth elements (REEs) are reported for the upper water column of the Sargasso Sea. The trivalent-only REEs have remarkably constant concentrations in the upper 500m of an April 1989 profile and in the upper 200m of a May 1989 profile. In contrast, Ce concentrations decrease smoothly with increasing depth. In April 1989 Ce decreases from 15.7 pmol/kg at 20 m to 5.1 pmol/kg at 750 m. Cerium, which has Redox transformations in seawater, behaves anomalously with respect to its REE(III) neighbors. While both dissolved Ce and Mn have elevated concentrations in the upper 200m, their vertical gradients are distinctly different. In contrast to Mn, which reaches a minimum dissolved concentration near the zone (150-250 m) of a particulate Mn maximum, Ce is being removed both near this zone and to depths of at least 750m. These new profiles indicate that Ce is involved in an upper ocean redox cycle. This interpretation is consistent with the MOFFETT (1990) incubation tracer experiments on the same May 1989 seawater. He showed that Ce(III) oxidation is biologically mediated, probably light inhibited, increases with depth, and 3-4 times slower than Mn(II) oxidation in the 100-200 m zone. CERoclines provide new information into the fine scale zonation of redox process operating in the upper columns of oligotrophic oceans.

  15. Determination of the rare-earth elements in geological materials by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Lichte, F.E.; Meier, A.L.; Crock, J.G.

    1987-01-01

    A method of analysis of geological materials for the determination of the rare-earth elements using the Inductively coupled plasma mass spectrometric technique (ICP-MS) has been developed. Instrumental parameters and factors affecting analytical results have been first studied and then optimized. Samples are analyzed directly following an acid digestion, without the need for separation or preconcentration with limits of detection of 2-11 ng/g, precision of ?? 2.5% relative standard deviation, and accuracy comparable to inductively coupled plasma emission spectrometry and instrumental neutron activation analysis. A commercially available ICP-MS instrument is used with modifications to the sample introduction system, torch, and sampler orifice to reduce the effects of high salt content of sample solutions prepared from geologic materials. Corrections for isobaric interferences from oxide ions and other diatomic and triatomic ions are made mathematically. Special internal standard procedures are used to compensate for drift in metahmetal oxide ratios and sensitivity. Reference standard values are used to verify the accuracy and utility of the method.

  16. New fission fragment distributions and r-process origin of the rare-earth elements.

    PubMed

    Goriely, S; Sida, J-L; Lemaître, J-F; Panebianco, S; Dubray, N; Hilaire, S; Bauswein, A; Janka, H-T

    2013-12-13

    Neutron star (NS) merger ejecta offer a viable site for the production of heavy r-process elements with nuclear mass numbers A≳140. The crucial role of fission recycling is responsible for the robustness of this site against many astrophysical uncertainties, but calculations sensitively depend on nuclear physics. In particular, the fission fragment yields determine the creation of 110≲A≲170 nuclei. Here, we apply a new scission-point model, called SPY, to derive the fission fragment distribution (FFD) of all relevant neutron-rich, fissioning nuclei. The model predicts a doubly asymmetric FFD in the abundant A≃278 mass region that is responsible for the final recycling of the fissioning material. Using ejecta conditions based on relativistic NS merger calculations, we show that this specific FFD leads to a production of the A≃165 rare-earth peak that is nicely compatible with the abundance patterns in the Sun and metal-poor stars. This new finding further strengthens the case of NS mergers as possible dominant origin of r nuclei with A≳140. PMID:24483647

  17. Innovative Application of Mechanical Activation for Rare Earth Elements Recovering: Process Optimization and Mechanism Exploration

    PubMed Central

    Tan, Quanyin; Deng, Chao; Li, Jinhui

    2016-01-01

    With the rapidly expanding use of fluorescent lamps (FLs) and increasing interest in conservation and sustainable utilization of critical metals such as rare earth elements (REEs), the recovering of REEs from phosphors in waste FLs is becoming a critical environmental and economic issue. To effectively recycle REEs with metallurgical methods, mechanical activation by ball milling was introduced to pretreat the waste phosphors. This current study put the emphasis on the mechanical activation and leaching processes for REEs, and explored the feasibility of the method from both theoretical and practical standpoints. Results showed physicochemical changes of structural destruction and particle size reduction after mechanical activation, leading to the easy dissolution of REEs in the activated samples. Under optimal conditions, dissolution yields of 89.4%, 93.1% and 94.6% for Tb, Eu and Y, respectively, were achieved from activated waste phosphors using hydrochloric acid as the dissolution agent. The shrinking core model proved to be the most applicable for the leaching procedure, with an apparent activation energy of 10.96 ± 2.79 kJ/mol. This novel process indicates that mechanical activation is an efficient method for recovering REEs from waste phosphors, and it has promising potential for REE recovery with low cost and high efficiency. PMID:26819083

  18. Determination of the rare-earth elements in geological materials by inductively coupled plasma mass spectrometry

    SciTech Connect

    Lichte, F.E.; Meier, A.L.; Crock, J.G.

    1987-04-15

    A method of analysis of geological materials for the determination of the rare-earth elements using the inductively coupled plasma mass spectrometric technique (ICP-MS) has been developed. Instrumental parameters and factors affecting analytical results have been first studied and then optimized. Samples are analyzed directly following an acid digestion, without the need for separation or preconcentration with limits of detection of 2-11 ng/g, precision of +/-2.5% relative standard deviation, and accuracy comparable to inductively coupled plasma emission spectrometry and instrumental neutron activation analysis. A commercially available ICP-MS instrument is used with modifications to the sample introduction system, torch, and sampler orifice to reduce the effects of high salt content of sample solutions prepared from geologic materials. Corrections for isobaric interferences from oxide ions and other diatomic and triatomic ions are made mathematically. Special internal standard procedures are used to compensate for drift in metal:metal oxide ratios and sensitivity. Reference standard values are used to verify the accuracy and utility of the method.

  19. Effect of paleosol formation on rare earth element signatures in fossil bone

    NASA Astrophysics Data System (ADS)

    Metzger, Christine A.; Terry, Dennis O., Jr.; Grandstaff, David E.

    2004-06-01

    The rare earth element (REE) content of fossil bones was analyzed and compared with the degree of ancient pedogenic development and depositional environments from several locations in the Orellan Scenic Member of the Oligocene Brule Formation in Badlands National Park, South Dakota. Paleosols ranged from weakly developed Entisols to more strongly developed Inceptisols, all typical of fluvial environments and possible paleocatena variation. Paleosols were alkaline and well drained. Sediments with sparse soil features from an oxbow lake system suggest that conditions were too waterlogged and sedimentation rates too rapid for significant pedogenesis. The variance of REE signatures in fossil bones from the paleosol sites was significantly greater than that of fossils from minimally altered sediments of the former oxbow lake. Positive Ce anomalies were associated with low U concentrations and indicate paleoredox conditions. Greater degrees of pedogenesis, regardless of the horizon in which the bone was found, systematically correlated with increased heavy REE enrichment in fossil bones. The fossil-bone REE signatures from the different paleosols and depositional environments were significantly different and distinguishable.

  20. LiYF4 (YLF) single crystals doped with rare-earth elements

    NASA Astrophysics Data System (ADS)

    Kowalczyk, E.; Kowalczyk, Z.; Grasza, K.; Gala, M.; Lukasiewicz, Tadeusz

    1995-10-01

    LiYF4 (YLF) is a very promising host material for lasers. Investigation of the spectroscopic and physical properties of YLF:Nd has suggested that this material may be a better candidate than Nd:YAG for generating short pulses with high peak power. This is a distinct advantage for many applications. Stimulated emission is attained at 1053 nm and 1047 nm. Also upconservation laser action in YLF and YLF:Er crystals is reported. More recently YLF doped with rare-earth elements has gained some attention. Pulsed room-temperature laser action at 2.06 micrometer has been achieved using YLF:Ho sensitized with Er and Tm. Using YLF:Pr blue light emission at 479 nm at room temperature was observed. Growth experiments of YLF:Nd crystals were carried by the Bridgman method. A vacuum furnace with cylindrical molybdenum heater and graphite crucible have been used. The temperature gradient of 25 degrees Celsius/cm has been achieved by using a stainless steel liner in the lower part of the furnace. The growth was performed in a nitrogen atmosphere. First crystals of YLF:Nd have been obtained.

  1. New Fission Fragment Distributions and r-Process Origin of the Rare-Earth Elements

    NASA Astrophysics Data System (ADS)

    Goriely, S.; Sida, J.-L.; Lematre, J.-F.; Panebianco, S.; Dubray, N.; Hilaire, S.; Bauswein, A.; Janka, H.-T.

    2013-12-01

    Neutron star (NS) merger ejecta offer a viable site for the production of heavy r-process elements with nuclear mass numbers A?140. The crucial role of fission recycling is responsible for the robustness of this site against many astrophysical uncertainties, but calculations sensitively depend on nuclear physics. In particular, the fission fragment yields determine the creation of 110?A?170 nuclei. Here, we apply a new scission-point model, called SPY, to derive the fission fragment distribution (FFD) of all relevant neutron-rich, fissioning nuclei. The model predicts a doubly asymmetric FFD in the abundant A?278 mass region that is responsible for the final recycling of the fissioning material. Using ejecta conditions based on relativistic NS merger calculations, we show that this specific FFD leads to a production of the A?165 rare-earth peak that is nicely compatible with the abundance patterns in the Sun and metal-poor stars. This new finding further strengthens the case of NS mergers as possible dominant origin of r nuclei with A?140.

  2. Elements of a new Global Water Strategy for the Group on Earth Observations

    NASA Astrophysics Data System (ADS)

    Lawford, Richard; Koike, Toshio; Ochiai, Osamu; Cripe, Douglas

    2013-04-01

    In order to address the need to review the scope and direction of GEO activities related to water and to provide guidance for the post-2015 GEO planning, the Integrated Global Water Cycle Observations (IGWCO) Community of Practice and the Committee on Earth Observation Satellites (CEOS) are working together to develop a strategy for GEO water activities over the next decade. This presentation will review the elements of the strategy which include topics as comprehensive as user needs and engagement, water cycle observational systems, assessment of water quality, data issues, interoperability and integration of water information systems and capacity building. Impediments in the flow of information and technological capabilities from the providers of new technologies, innovations and data products to the end users will be explored in terms of the nature of these impediments and how they can be overcome. To be successful in GEO's framework of volunteerism, the water strategy should build on activities that are on-going in related programmes at the international and national levels. In addition, implementation of the strategy will need to be supported through new initiatives and policies that promote greater integration. Suggestions for achieving these goals will be outlined at the end of the talk.

  3. Innovative Application of Mechanical Activation for Rare Earth Elements Recovering: Process Optimization and Mechanism Exploration

    NASA Astrophysics Data System (ADS)

    Tan, Quanyin; Deng, Chao; Li, Jinhui

    2016-01-01

    With the rapidly expanding use of fluorescent lamps (FLs) and increasing interest in conservation and sustainable utilization of critical metals such as rare earth elements (REEs), the recovering of REEs from phosphors in waste FLs is becoming a critical environmental and economic issue. To effectively recycle REEs with metallurgical methods, mechanical activation by ball milling was introduced to pretreat the waste phosphors. This current study put the emphasis on the mechanical activation and leaching processes for REEs, and explored the feasibility of the method from both theoretical and practical standpoints. Results showed physicochemical changes of structural destruction and particle size reduction after mechanical activation, leading to the easy dissolution of REEs in the activated samples. Under optimal conditions, dissolution yields of 89.4%, 93.1% and 94.6% for Tb, Eu and Y, respectively, were achieved from activated waste phosphors using hydrochloric acid as the dissolution agent. The shrinking core model proved to be the most applicable for the leaching procedure, with an apparent activation energy of 10.96 ± 2.79 kJ/mol. This novel process indicates that mechanical activation is an efficient method for recovering REEs from waste phosphors, and it has promising potential for REE recovery with low cost and high efficiency.

  4. Trace elements and REE fractionation in subsoils developed on sedimentary and volcanic rocks: case study of the Mt. Vulture area, southern Italy

    NASA Astrophysics Data System (ADS)

    Mongelli, Giovanni; Paternoster, Michele; Rizzo, Giovanna; Sinisi, Rosa

    2014-06-01

    There is an increasing interest in the distribution of rare earth elements (REEs) within soils, primarily as these elements can be used to identify pedogenetic processes and because soils may be future sources for REE extraction, despite much attention should be paid to the protection and preservation of present soils. Here, we evaluate the processes that control the distribution of REEs in subsoil horizons developed over differing lithologies in an area of low anthropogenic contamination, allowing estimates of the importance of source rocks and weathering. Specifically, this study presents new data on the distribution of REEs and other trace elements, including transition and high-field-strength elements, in subsoils developed on both Quaternary silica-undersaturated volcanic rocks and Pliocene siliciclastic sedimentary rocks within the Mt. Vulture area of the southern Apennines in Italy. The subsoils in the Mt. Vulture area formed during moderate weathering (as classified using the chemical index of alteration) and contain an assemblage of secondary minerals that is dominated by trioctahedral illite with minor vermiculite. The REEs, high-field-strength elements, and transition metals have higher abundances in subsoils that developed from volcanic rocks, and pedogenesis caused the Mt. Vulture subsoils to have REE concentrations that are an order of magnitude higher than typical values for the upper continental crust. This result indicates that the distribution of REEs in soils is a valuable tool for mineral exploration. A statistical analysis of inter-elemental relationships indicates that REEs are concentrated in clay-rich fractions that also contain significant amounts of low-solubility elements such as Zr and Th, regardless of the parent rock. This suggests that low-solubility refractory minerals, such as zircon, play a significant role in controlling the distribution of REEs in soils. The values of (La/Yb)N and (Gd/Yb)N fractionation indices are dependent on the intensity of pedogenesis; soils in the study area have values that are higher than typical upper continental crust ratios, suggesting that soils, especially those that formed during interaction with near neutral to acidic organic-rich surface waters, may represent an important source of both light REEs and medium REEs (MREEs). In comparison, MREE/heavy REE fractionation in soils that form during moderate weathering may be affected by variations in parent rock lithologies, primarily as MREE-hosting minerals, such as pyroxenes, may control (La/Sm)N index values. Eu anomalies are thought to be the most effective provenance index for sediments, although the anomalies within the soils studied here are not related to the alteration of primary minerals, including feldspars, to clay phases. In some cases, Eu/Eu* values may have a weak correlation with elements hosted by heavy minerals, such as Zr; this indicates that the influence of mechanical sorting of clastic particles during sedimentary transport on the Eu/Eu* values of siliciclastic sediments needs to be considered carefully.

  5. Rare earth elements in the water column of Lake Vanda, McMurdo Dry Valleys, Antarctica

    NASA Astrophysics Data System (ADS)

    De Carlo, Eric Heinen; Green, William J.

    2002-04-01

    We present data on the composition of water from Lake Vanda, Antarctica. Vanda and other lakes in the McMurdo Dry Valleys of Antarctica are characterized by closed basins, permanent ice covers, and deep saline waters. The meromictic lakes provide model systems for the study of trace metal cycling owing to their pristine nature and the relative simplicity of their biogeochemical systems. Lake Vanda, in the Wright Valley, is supplied by a single input, the Onyx River, and has no output. Water input to the lake is balanced by sublimation of the nearly permanent ice cap that is broken only near the shoreline during the austral summer. The water column is characterized by an inverse thermal stratification of anoxic warm hypersaline water underlying cold oxic freshwater. Water collected under trace-element clean conditions was analyzed for its dissolved and total rare earth element (REE) concentrations by inductively coupled plasma mass spectrometry. Depth profiles are characterized by low dissolved REE concentrations (La, Ce, <15 pM) in surface waters that increase slightly (La, 70 pM; Ce, 20 pM) with increasing depth to ˜55 m, the limit of the fresh oxic waters. Below this depth, a sharp increase in the concentrations of strictly trivalent REE (e.g., La, 5 nM) is observed, and a submaximum in redox sensitive Ce (2.6 nM) is found at 60- to 62-m depth. At a slightly deeper depth, a sharper Ce maximum is observed with concentrations exceeding 11 nM at a 67-m depth, immediately above the anoxic zone. The aquatic concentrations of REE reported here are ˜50-fold higher than previously reported for marine oxic/anoxic boundaries and are, to our knowledge, the highest ever observed at natural oxic/anoxic interfaces. REE maxima occur within stable and warm saline waters. All REE concentrations decrease sharply in the sulfidic bottom waters. The redox-cline in Lake Vanda is dominated by diffusional processes and vertical transport of dissolved species driven by concentration gradients. Furthermore, because the ultraoligotrophic nature of the lake limits the potential for organic phases to act as metal carriers, metal oxide coatings and sulfide phases appear to largely govern the distribution of trace elements. We discuss REE cycling in relation to the roles of redox reactions and competitive scavenging onto Mn- and Fe-oxides coatings on clay sized particles in the upper oxic water column and their release by reductive dissolution near the anoxic/oxic interface.

  6. Source and mobility of Rare Earth Elements in a sedimentary aquifer system: Aquitaine basin (Southern France)

    NASA Astrophysics Data System (ADS)

    Negrel, P. J.; Petelet-Giraud, E.; Millot, R.; Malcuit, E.

    2011-12-01

    The study of rare earth elements (REEs) in natural waters initially involved an examination of their occurrence and behavior in seawater and coastal waters such as estuaries. Since the 1990s, REE geochemistry has been applied to continental waters such as rivers and lakes and groundwaters. Rare earth elements) are of great interest because of their unique characteristics and have been used in the study of many geological processes like weathering and water-rock interaction processes, provenance of sediments, etc... With the evolution of analytical techniques like new generation ICP-MS, much attention had been paid towards the water geochemistry of REEs. However, there is a need of more investigations devoted to REEs in large groundwater systems, especially on the understanding of the distribution of REEs and their evolution in such systems. In this frame, large sedimentary aquifer systems often constitute strategic water resources for drinking water supply, agriculture irrigation and industry, but can also represent an energetic resource for geothermal power. Large water abstractions can induce complete modification of the natural functioning of such aquifer systems. These large aquifer systems thus require water management at the basin scale in order to preserve both water quantity and quality. The large Eocene Sand aquifer system of the Aquitaine sedimentary basin was studied through various hydrological, chemical and isotopic tools. This system extends over 116,000 km2 in the South west part of the French territory. The aquifer being artesian in the west of the district and confined with piezometric levels around 250-m depth in the east. The 'Eocene Sands', composed of sandy Tertiary sediments alternating with carbonate deposits, is a multi-layer system with high permeability and a thickness of several tens of metres to a hundred metres. The Eocene Sand aquifer system comprises at least five aquifers: Paleocene, Eocene infra-molassic sands (IMS), early Eocene, middle Eocene, and late Eocene. One important feature, in these confined systems isolated from anthropogenic influence, is the range in salinities by a factor of 10, from 250 mg/L up to 2.5 g/L. The ?REE, in the range 2-54 ng/L, with a dependence on salinity when expressed in % HCO3 or SO4, reflect the carbonate or evaporite source of REEs. The UCC normalized-REE patterns show a large variability as exemplified by the REE flat patterns-low SREE associated with salinity controlled by HCO3. In the present work, the REEs are investigated in terms of saturation indices, speciation modelling, REE patterns in order to recognize the aquifer type hosting groundwater and decipher the origin of the salinity of the groundwater as some part of the aquifer display in the groundwater concentration of chemical element exceeding the drinking water standard (SO4, F...). Such high concentrations of naturally-occurring substances (e.g. unaffected by human activities) can have negative impacts on groundwater thresholds and deciphering their origin by means of geochemical tools like REE is a remaining challenge.

  7. Rare earth and major element geochemistry of Eocene fine-grained sediments in oil shale- and coal-bearing layers of the Meihe Basin, Northeast China

    NASA Astrophysics Data System (ADS)

    Bai, Yueyue; Liu, Zhaojun; Sun, Pingchang; Liu, Rong; Hu, Xiaofeng; Zhao, Hanqing; Xu, Yinbo

    2015-01-01

    The Meihe Basin is a Paleogene pull-apart basin. Long-flame coal, lignite and oil shale are coexisting energy resources deposited in this basin. Ninety-seven samples, including oil shales, coals, brown to gray silt and mudstone, have been collected from the oil shale- and coal-bearing layers to discover the rare earth element geochemistry. The total REE contents of oil shales and coals are 137-256 μg/g and 64-152 μg/g respectively. The chondrite-normalized patterns of oil shales and coals show LREE enrichments, HREE deficits, negative Eu anomalies and negligible Ce anomalies. The chemical index of alteration (CIA) as well as some trace elements is often used to reflect the paleoenvironment at the time of deposition. The results show that fine-grained sediments in both layers were deposited in dysoxic to oxic conditions and in a warm and humid climate, and coals were deposited in a warmer and more humid climate than oil shales. Oil shales and coals are both in the early stage of diagenesis and of terrigenous origin. Besides, diagrams of some major, trace and rare earth elements show that the fine-grained sediments of both layers in the Meihe Basin are mainly from the felsic volcanic rocks and granite, and that their source rocks are mostly deposited in the continental inland arc setting. The analysis of major elements shows that Si, Al, K and Ti, in both layers, are found mainly in a mixed clay mineral assemblage and that Si is also found in quartz. Sodium occurs primarily in clay minerals, whereas Ca is found mainly in the organic matter. In the coal-bearing layer, iron is mainly controlled by organic matter rather than detrital minerals. In contrast, in the oil shale-bearing layer, neither detrital minerals nor organic matter exert a control on the iron content. Analyzing the relationship between rare earth elements and major elements shows that REEs in the oil shales and the coals are both of terrigenous origin and are mainly controlled by detrital minerals rather than by organic matter. In both layers, REEs have no relationship with fine-grained phosphates, and during the weathering process, the REEs were not very mobile and were resistant to fractionation.

  8. Assessment of Bioavailable Concentrations of Germanium and Rare Earth Elements in the Rhizosphere of White Lupin (Lupinus albus L.)

    NASA Astrophysics Data System (ADS)

    Wiche, Oliver; Fischer, Ronny; Moschner, Christin; Székely, Balázs

    2015-04-01

    Concentrations of Germanium (Ge) and Rare Earth Elements in soils are estimated at 1.5 mg kg -1 (Ge), 25 mg kg -1 (La) and 20 mg kg -1 (Nd), which are only roughly smaller than concentrations of Pb and Zn. Germanium and rare earth elements are thus not rare but widely dispersed in soils and therefore up to date, only a few minable deposits are available. An environmental friendly and cost-effective way for Ge and rare earth element production could be phytomining. However, the most challenging part of a phytomining of these elements is to increase bioavailable concentrations of the elements in soils. Recent studies show, that mixed cultures with white lupine or other species with a high potential to mobilize trace metals in their rhizosphere due to an acidification of the soil and release of organic acids in the root zone could be a promising tool for phytomining. Complexation of Ge and rare earth elements by organic acids might play a key role in controlling bioavailability to plants as re-adsorption on soil particles and precipitation is prevented and thus, concentrations in the root zone of white lupine increase. This may also allow the complexes to diffuse along a concentration gradient to the roots of mixed culture growing species leading to enhanced plant uptake. However, to optimize mixed cultures it would be interesting to know to which extend mobilization of trace metals is dependent from chemical speciation of elements in soil due to the interspecific interaction of roots. A method for the identification of complexes of germanium and rare earth elements with organic acids, predominantly citric acid in the rhizosphere of white lupine was developed and successfully tested. The method is based on coupling of liquid chromatography with ICP-MS using a zic-philic column (SeQuant). As a preliminary result, we were able to show that complexes of germanium with citric acid exist in the rhizosphere of white lupin, what may contribute to the bioavailability of this element. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.

  9. Experimental determination of carbon isotope fractionation between iron carbide melt and carbon: 12C-enriched carbon in the Earth's core?

    NASA Astrophysics Data System (ADS)

    Satish-Kumar, Madhusoodhan; So, Hayato; Yoshino, Takashi; Kato, Mutsumi; Hiroi, Yoshikuni

    2011-10-01

    We report here new experimental data on equilibrium carbon isotope fractionation between graphite/diamond and iron carbide melt at 5 and 10 GPa and in the temperature range between 1200 and 2000 C. Carbon isotope equilibrium was tested using morphological features of graphite and also by performing a longer duration experiment, both of which suggested that equilibrium carbon isotope fractionation is present. The results suggest that iron carbide melt will preferentially accumulate 12C rather than 13C. An equilibrium temperature dependent fractionation between iron carbide melt and graphite/diamond is proposed based on the relation ?C=8.8510/T(K)+0.99. Our results are consistent with the carbon isotope distribution between graphite and cohenite (Fe 3C) observed in iron meteorites. We propose that temperature-dependent fractionation of carbon isotopes between iron carbide melt and graphite/diamond might have created a " 12C-enriched core" with a significant difference in the distribution of carbon isotopes between the carbon in the metallic core and bulk silicate Earth during the accretion and differentiation of early Earth. Recent findings of low ? 13C carbonados and diamonds of deep mantle origin supports the presence of a 12C enriched source. The possible presence of a reservoir of 12C-enriched carbon in the Earth's core implies that it can generate large perturbations in the surface and shallow carbon-isotope system by the flux of lighter carbon from the core-mantle boundary.

  10. Rare earth and trace element mobility in mid-crustal shear zones: insights from the Mont Blanc Massif (Western Alps)

    NASA Astrophysics Data System (ADS)

    Rolland, Yann; Cox, Stephen; Boullier, Anne-Marie; Pennacchioni, Giorgio; Mancktelow, Neil

    2003-09-01

    The behaviour of rare earth elements (REE) during fluid-rock interaction in mid-crustal shear zones has received little attention, despite their potential for mass balance calculation and isotopic tracing during deformation. In this study, several cases of large REE mobility during Alpine fluid-driven shear zone development in the pre-Alpine granitic basement of the Mont Blanc Massif are considered. On a regional scale, the undeformed granite compositions range within 5 wt% SiO 2 (70.5-75.3 wt%) and magmatic chemical variations are of the order of 10-20%, ascribed to minor effects of crystal fractionation. Major and trace element mobility observed in shear zones largely exceeds these initial variations. Shear zones developed a range of mineral assemblages as a result of shearing at mid-crustal depths (at 0.5 GPa, 400C). Five main shear zone assemblages involve muscovite, chlorite, epidote, actinolite and calcite, respectively, as major phases. In most cases, selective enrichments of light or heavy REE (and Y, Ta, Hf) are observed. REE mobility is unrelated to deformation style (cataclastic, mylonitic), the intensity of strain, and to the shear zone's major metamorphic mineral assemblages. Instead, the changes in REE concentrations are ascribed to the alteration of pre-existing magmatic REE-bearing minerals during deformation-related fluid-rock interaction and to the syntectonic precipitation of metamorphic REE-bearing minerals (mainly monazite, bastnsite, aeschynite and tombarthite). Minor proportions (<2%) of these accessory phases, with grain sizes mostly <20 ?m, account for enrichments of up to 5:1 compared to the initial granite whole-rock REE budget. The stability of the REE phases appears to be largely dependent on the altering fluid composition. REE mobility is ascribed to changes in pH and to the availability of CO 32-, PO 42-, and SO 42-ligands in the fluid. Such processes are likely to influence the mobility of REE, Y, Hf and Ta in shear zones.

  11. Rare earth elements in the sedimentary cycle - A pilot study of the first leg

    NASA Technical Reports Server (NTRS)

    Basu, A.; Blanchard, D. P.; Brannon, J. C.

    1982-01-01

    The effects of source rock composition and climate on the natural abundances of rare elements (REE) in the first leg of the sedimentary cycle are evaluated using a study with Holocene fluvia sands. The medium grained sand fraction of samples collected from first order streams exclusively draining granitic plutons in Montana (semi-arid), Georgia (humid), and South Carolina (humid) are analyzed. It is found that the REE distribution patterns (but not the total absolute abundances) of the daughter sands are very similar, despite compositional differences between parent plutons. Averages of the three areas are determined to have a La/Lu ratio of about 103, showing a depletion of heavy REE with respect to an average granite (La/Lu = 79) or the composition of North American Shales (La/Lu = 55). However, the Eu/Sm ratio in sands from these areas is about 0.22, which is very close to this ratio in North American Shales (0.21), although the overall REE distribution of these sands is not similar to that of the North American Shales in any way. It is concluded that the major rock type, but neither its minor subdivisions nor the climate, controls the REE distribution patterns in first cycle daughter sands, although the total and the parent rock-normalized abundances of REE in sands from humid areas are much lower than those in sands from arid areas.

  12. Rare earth element mineralogy, geochemistry, and preliminary resource assessment of the Khanneshin carbonatite complex, Helmand Province, Afghanistan

    USGS Publications Warehouse

    Tucker, Robert D.; Belkin, Harvey E.; Schulz, Klaus J.; Peters, Stephen G.; Buttleman, Kim P.

    2011-01-01

    There is increased concern about the future availability of rare earth elements (REE) because of China's dominance as the supplier of more than 95 percent of world REE output, their decision to restrict exports of rare earth products, and the rapid increase in world-wide consumption of rare earth product. As a result, countries such as the United States, Japan, and member nations of the European Union face a future of tight supplies and high prices for rare earth products unless other sources of REE are found and developed (Long and others, 2010; U.S. Geological Survey, 2011, p. 128-129, 184-185). We report and describe a significant new deposit of light rare earth elements (LREE), estimated at 1 Mt, within the Khanneshin carbonatite complex of south Afghanistan. The potential resource is located in a remote and rugged part of the igneous complex in a region previously identified by Soviet geologists in the 1970s. This report reviews the geologic setting of LREE deposit, presents new geochemical data documenting the grade of LREE mineralization, briefly describes the mineralogy and mineralogical associations of the deposit, and presents a preliminary estimate of LREE resources based on our current understanding of the geology.

  13. Trace elements and their distribution in protein fractions of camel milk in comparison to other commonly consumed milks.

    PubMed

    Al-Awadi, F M; Srikumar, T S

    2001-08-01

    Studies on camels' milk, whether with respect to concentration or bioavailability of trace elements from this milk, are limited and warrant further investigation. The object of this study was to analyse the concentration and distribution of zinc, copper, selenium, manganese and iron in camel milk compared to those in human milk, cows' milk and infant formula under similar experimental conditions. Camels' milk and cows' milk were collected from local farms, human milk samples were obtained from healthy donors in Kuwait and infant formula was purchased locally. Milk fractionation was performed by ultra-centrifugation and gelcolumn chromatography. The concentration of trace elements was analysed by atomic absorption spectrometry and that of protein was determined spectrophotometrically. The concentration of manganese and iron in camels' milk was remarkably higher (7-20-fold and 4-10-fold, respectively) than in human milk, cows' milk and infant formula. The zinc content of camels' milk was higher than that of human milk but slightly lower than in cows' milk and infant formula. The concentration of copper in camels' milk was similar to that of cows' milk but lower than in human milk and infant formula. The selenium content of camels' milk was comparable to those of other types of milk, Approximately 50-80% of zinc, copper and manganese in camels' milk were associated with the casein fraction, similar to that of cows' milk, The majority of selenium and iron in camels' milk was in association with the low molecular weight fraction, It is recommended that camels' milk be considered as a potential source of manganese, selenium and iron, perhaps not only for infants, but also for other groups suspected of mild deficiency of these elements. Further investigations are required to confirm this proposal. PMID:11694048

  14. [Indirect determination of rare earth elements in Chinese herbal medicines by hydride generation-atomic fluorescence spectrometry].

    PubMed

    Zeng, Chao; Lu, Jian-Ping; Xue, Min-Hua; Tan, Fang-Wei; Wu, Xiao-Yan

    2014-07-01

    Based on their similarity in chemical properties, rare earth elements were able to form stable coordinated compounds with arsenazo III which were extractable into butanol in the presence of diphenylguanidine. The butanol was removed under reduced pressure distillation; the residue was dissolved with diluted hydrochloric acid. As was released with the assistance of KMnO4 and determined by hydrogen generation-atomic fluorescence spectrometry in terms of rare earth elements. When cesium sulfate worked as standard solution, extraction conditions, KMnO4 amount, distillation temperature, arsenazo III amount, interfering ions, etc were optimized. The accuracy and precision of the method were validated using national standard certified materials, showing a good agreement. Under optimum condition, the linear relationship located in 0.2-25 microg x mL(-1) and detection limit was 0.44 microg x mL(-1). After the herbal samples were digested with nitric acid and hydrogen peroxide, the rare earth elements were determined by this method, showing satisfactory results with relative standard deviation of 1.3%-2.5%, and recoveries of 94.4%-106.0%. The method showed the merits of convenience and rapidness, simple instrumentation and high accuracy. With the rare earths enriched into organic phase, the separation of analytes from matrix was accomplished, which eliminated the interference. With the residue dissolved by diluted hydrochloric acid after the solvent was removed, aqueous sample introduction eliminated the impact of organic phase on the tubing connected to pneumatic pump. PMID:25269316

  15. Provenance of KREEP and the exotic component - Elemental and isotopic studies of grain size fractions in lunar soils

    NASA Technical Reports Server (NTRS)

    Evensen, N. M.; Murthy, V. R.; Coscio, M. R., Jr.

    1974-01-01

    Sieve fraction analyses of lunar soils reveal the presence of a fine-grained exotic component enriched in K, Rb, Sr, Ba, and in radiogenic Sr in all soils. The probable source of this exotic component is the areas of high-surficial radioactivity observed by orbital gamma ray spectrometry, such as those at Fra Mauro and Archimedes. If the exotic component is fine-grained KREEP, the origin and distribution of KREEP fragments in the soils are identified. It is suggested that the exotic component represents trace element enriched material located at some depth in the Imbrium area which was surficia