Enhanced separation of rare earth elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyon, K.; Greenhalgh, M.; Herbst, R. S.

2016-09-01

Industrial rare earth separation processes utilize PC88A, a phosphonic acid ligand, for solvent extraction separations. The separation factors of the individual rare earths, the equipment requirements, and chemical usage for these flowsheets are well characterized. Alternative ligands such as Cyanex® 572 and the associated flowsheets are being investigated at the pilot scale level to determine if significant improvements to the current separation processes can be realized. These improvements are identified as higher separation factors, reduced stage requirements, or reduced chemical consumption. Any of these improvements can significantly affect the costs associated with these challenging separation proccesses. A mid/heavy rare earthmore » element (REE) separations flowsheet was developed and tested for each ligand in a 30 stage mixer-settler circuit to compare the separation performance of PC88A and Cyanex® 572. The ligand-metal complex strength of Cyanex® 572 provides efficient extraction of REE while significantly reducing the strip acid requirements. Reductions in chemical consumption have a significant impact on process economics for REE separations. Partitioning results summarized Table 1 indicate that Cyanex® 572 offers the same separation performance as PC88A while reducing acid consumption by 30% in the strip section for the mid/heavy REE separation. Flowsheet Effluent Compositions PC88A Cyanex® 572 Raffinate Mid REE Heavy REE 99.40% 0.60% 99.40% 0.60% Rich Mid REE Heavy REE 2.20% 97.80% 0.80% 99.20% Liquor Strip Acid Required 3.4 M 2.3 M Table 1 – Flowsheet results comparing separation performance of PC88A and Cyanex® 572 for a mid/heavy REE separation.« less

Neodymium isotopic study of rare earth element sources and mobility in hydrothermal Fe oxide (Fe-P-REE) systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gleason, J.D.; Marikos, M.A.; Barton, M.D.

2000-03-01

Rare earth element (REE)-enriched, igneous-related hydrothermal Fe-oxide hosted (Fe-P-REE) systems from four areas in North America have been analyzed for their neodymium iosotopic composition to constrain REE sources and mobility in these systems. The Nd isotopic results evidence a common pattern of REE concentration from igneous sources despite large differences in age (Proterozoic to Tertiary), tectonic setting (subduction vs. intraplate), and magmatic style (mafic vs. felsic). In the Middle Proterozoic St. Francois Mountains terrane of southeastern Missouri, {epsilon}{sub Nd} for Fe-P-REE (apatite, monazite, xenotime) deposits ranges from +3.5 to +5.1, similar to associated felsic to intermediate igneous rocks of themore » same age ({epsilon}{sub Nd} = +2.6 to +6.2). At the mid-Jurassic Humboldt mafic complex in western Nevada, {epsilon}{sub Nd} for Fe-P-REE (apatite) mineralization varies between +1.1 and +2.4, similar to associated mafic igneous rocks ({minus}1.0 to +3.5). In the nearby Cortez Mountains in central Nevada, mid-Jurassic felsic volcanic and plutonic rocks ({epsilon}{sub Nd} = {minus}2.0 to {minus}4.4) are associated with Fe-P-REE (apatite-monazite) mineralization having similar {epsilon}{sub Nd}({minus}1.7 to {minus}2.4). At Cerro de Mercado, Durango, Mexico, all assemblages analyzed in this Tertiary rhyolite-hosted Fe oxide deposit have identical isotopic compositions with {epsilon}{sub Nd} = {minus}2.5. These data are consistent with coeval igneous host rocks being the primary source of REE in all four regions, and are inconsistent with a significant contribution of REE from other sources. Interpretations of the origin of these hydrothermal systems and their concomitant REE mobility must account for nonspecialized igneous sources and varied tectonic settings.« less

A first report of rare earth elements in northwestern Mediterranean seaweeds.

PubMed

Squadrone, Stefania; Brizio, Paola; Battuello, Marco; Nurra, Nicola; Sartor, Rocco Mussat; Benedetto, Alessandro; Pessani, Daniela; Abete, Maria Cesarina

2017-09-15

The concentrations of rare earth elements (REE) were determined by ICP-MS in dominant seaweed species, collected from three locations of the northwestern Mediterranean Sea. This is the first study to define levels and patterns of REE in macro algae from these coastal areas. Rare elements are becoming emerging inorganic contaminants in marine ecosystems, due to their worldwide increasing applications in industry, technology, medicine and agriculture. Significant inter-site and interspecies differences were registered, with higher levels of REE in brown and green macro algae than in red seaweeds. Levels of light REE were also observed to be greater compared to heavy REE in all samples. One of the investigated locations (Bergeggi, SV) had higher REE and ΣREE concentrations, probably due to its proximity to an important commercial and touristic harbor, while the other two sites were less affected by anthropogenic contaminations, and showed comparable REE patterns and lower concentrations. Rare earth elements in seaweeds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rare-earth elements

USGS Publications Warehouse

Van Gosen, Bradley S.; Verplanck, Philip L.; Seal, Robert R.; Long, Keith R.; Gambogi, Joseph; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

2017-12-19

The rare-earth elements (REEs) are 15 elements that range in atomic number from 57 (lanthanum) to 71 (lutetium); they are commonly referred to as the “lanthanides.” Yttrium (atomic number 39) is also commonly regarded as an REE because it shares chemical and physical similarities and has affinities with the lanthanides. Although REEs are not rare in terms of average crustal abundance, the concentrated deposits of REEs are limited in number.Because of their unusual physical and chemical properties, the REEs have diverse defense, energy, industrial, and military technology applications. The glass industry is the leading consumer of REE raw materials, which are used for glass polishing and as additives that provide color and special optical properties to the glass. Lanthanum-based catalysts are used in petroleum refining, and cerium-based catalysts are used in automotive catalytic converters. The use of REEs in magnets is a rapidly increasing application. Neodymium-iron-boron magnets, which are the strongest known type of magnets, are used when space and weight are restrictions. Nickel-metal hydride batteries use anodes made of a lanthanum-based alloys.China, which has led the world production of REEs for decades, accounted for more than 90 percent of global production and supply, on average, during the past decade. Citing a need to retain its limited REE resources to meet domestic requirements as well as concerns about the environmental effects of mining, China began placing restrictions on the supply of REEs in 2010 through the imposition of quotas, licenses, and taxes. As a result, the global rare-earth industry has increased its stockpiling of REEs; explored for deposits outside of China; and promoted new efforts to conserve, recycle, and substitute for REEs. New mine production began at Mount Weld in Western Australia, and numerous other exploration and development projects noted in this chapter are ongoing throughout the world.The REE-bearing minerals are

Extraction of rare earth elements from low-grade Bauxite via precipitation reaction

NASA Astrophysics Data System (ADS)

Kusrini, E.; Nurani, Y.; Bahari, ZJ

2018-03-01

The aim of this research was to determine the optimum hydrometallurgical parameters to extract the rare earth elements (REE) from low-grade bauxite through acid leaching and precipitation reaction. REE or lanthanide recovery by a precipitation method with sodium sulphate and sodium phosphate as precipitation agents is reported where the effect of pH and recovery of REE are described. The metal composition of REE in low-grade bauxite after treatment were analyzed by ICP-OES. The total recovery values of REE elements at the first precipitation reaction using sodium sulphate as the precipitation agent at pH 3.5 showed ~68.2% of lanthanum, ~18.9% cerium, and ~7.8% yttrium. Lanthanum was the rare-earth element present at the highest concentration in the low-grade bauxite after the series treatments. An optimum pH of 3.5 for precipitation of rare-earth elements using sodium sulphate was demonstrated where this method is recommended for the extraction of REE elements from low-grade bauxite.

Assessing anthropogenic levels, speciation, and potential mobility of rare earth elements (REEs) in ex-tin mining area.

PubMed

Khan, Aysha Masood; Yusoff, Ismail; Bakar, Nor Kartini Abu; Bakar, Ahmad Farid Abu; Alias, Yatimah

2016-12-01

A study was carried out to determine the level of rare earth elements (REEs) in water and sediment samples from ex-mining lakes and River in Kinta Valley, Perak, Malaysia. Surface water and sediments from an ex-mining lake and Kinta River water samples were analyzed for REEs by inductively coupled plasma mass spectrometry. The total concentration of REEs in the ex-mining lake water samples and sediments were found to be 3685 mg/l and 14159 mg/kg, respectively, while the total concentration of REEs in Kinta River water sample was found to be 1224 mg/l. REEs in mining lake water were found to be within 2.42 mg/l (Tb) to 46.50 mg/l (Ce), while for the Kinta River, it was 1.33 mg/l (Ho) to 29.95 mg/l (Ce). Sediment samples were also found with REEs from 9.81 mg/kg (Ho) to 765.84 mg/kg (Ce). Ce showed the highest average concentrations for mining lake (3.88 to 49.08 mg/l) and Kinta River (4.44 to 33.15 mg/l) water samples, while the concentration of La was the highest (11.59 to 771.61 mg/kg) in the mining lake sediment. Lu was shown to have the highest enrichment of REEs in ex-mining lake sediments (107.3). Multivariate statistical analyses such as factor analysis and principal component analysis indicated that REEs were associated and controlled by mixed origin, with similar contributions from anthropogenic and geogenic sources. The speciation study of REEs in ex-tin mining sediments using a modified five-stage sequential extraction procedure indicated that yttrium (Y), gadolinium (Gd), and lanthanum (La) were obtained at higher percentages from the adsorbed/exchanged/carbonate fraction. The average potential mobility of the REEs was arranged in a descending order: Yb > Gd > Y = Dy > Pr > Er > Tm > Eu > Nd > Tb > Sc > Lu > Ce > La, implying that under favorable conditions, these REEs could be released and subsequently pollute the environment.

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

Techno-Economic Assessment for Integrating Biosorption into Rare Earth Recovery Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiao, Yongqin; Sutherland, John; Jin, Hongyue

The current uncertainty in the global supply of rare earth elements (REEs) necessitates the development of novel extraction technologies that utilize a variety of REE source materials. Herein, we examined the techno-economic performance of integrating a biosorption approach into a large-scale process for producing salable total rare earth oxides (TREOs) from various feedstocks. An airlift bioractor is proposed to carry out a biosorption process mediated by bioengineered rare earth-adsorbing bacteria. Techno-econmic asssements were compared for three distinctive categories of REE feedstocks requiring different pre-processing steps. Key parameters identified that affect profitability include REE concentration, composition of the feedstock, and costsmore » of feedstock pretreatment and waste management. Among the 11 specific feedstocks investigated, coal ash from the Appalachian Basin was projected to be the most profitable, largely due to its high-value REE content. Its cost breakdown includes pre-processing (primarily leaching) (8077.71%), biosorption (1619.04%), and oxalic acid precipitation and TREO roasting (3.35%). Surprisingly, biosorption from the high-grade Bull Hill REE ore is less profitable due to high material cost and low production revenue. Overall, our results confirmed that the application of biosorption to low-grade feedstocks for REE recovery is economically viable.« less

Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carlson, Gary

This final report provides a complete summary of the activities, results, analytical discussion, and overall evaluation of the project titled “Economical and Environmentally Benign Extraction of Rare Earth Elements (REES) from Coal & Coal Byproducts” under DOE Award Number DE-FE-0027155 that started in March 2016 and ended December 2017. Fly ash was selected as the coal-byproduct source material due to fact that it is readily available with no need for extensive methods to obtain the material, it is produced in large quantities (>50 million tons per year) and had REE concentrations similar to other coal-byproducts. The selected fly ash usedmore » throughout this project was from the Mill Creek power generating facility operated by Louisville Gas and Electric located in Louisville, KY and was subjected to a variety of physical and chemical characterization tests. Results from fusion extractions showed that the selected fly-ash had a TREE+Y concentration of 480 ppm with critical REEs concentration of 200 ppm. The fly ash had an outlook ratio of 1.25 and an estimated value of $16-$18 worth of salable REEs per 1-tonne of fly ash. Additional characterizations by optical evaluation, QEMSCAN, XRD, size fractionation, and SEM analysis showed the fly ash consisted of small glassy spherules with a size range between 1 to 110 µm (ave. diam. of 13 um), was heterogeneous in chemical composition (main crystalline phases: aluminum oxides and iron oxides) and was primarily an amorphous material (75 to 80%). A simple stepped approach was completed to estimate the total REE resource quantity. The approach included REE characterization of the representative samples, evaluation of fly-ash availability, and final determination estimated resource availability with regards to REE grade on a regional and national scale. This data represents the best available information and is based upon the assumptions that the power generating facility where the fly-ash was obtained will use the

Global demand for rare earth resources and strategies for green mining

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Tanushree

Rare earth elements (REEs) are essential raw materials for emerging renewable energy resources and ‘smart’ electronic devices. Global REE demand is slated to grow at an annual rate of 5% by 2020. This high growth rate will require a steady supply base of REEs in the long run. At present, China is responsible for 85% of global rare earth oxide (REO) production. To overcome this monopolistic supply situation, new strategies and investments are necessary to satisfy domestic supply demands. Concurrently, environmental, economic, and social problems arising from REE mining must be addressed. There is an urgent need to develop efficientmore » REE recycling techniques from end-of-life products, technologies to minimize the amount of REEs required per unit device, and methods to recover them from fly ash or fossil fuel-burning wastes.« less

Global demand for rare earth resources and strategies for green mining.

PubMed

Dutta, Tanushree; Kim, Ki-Hyun; Uchimiya, Minori; Kwon, Eilhann E; Jeon, Byong-Hun; Deep, Akash; Yun, Seong-Taek

2016-10-01

Rare earth elements (REEs) are essential raw materials for emerging renewable energy resources and 'smart' electronic devices. Global REE demand is slated to grow at an annual rate of 5% by 2020. This high growth rate will require a steady supply base of REEs in the long run. At present, China is responsible for 85% of global rare earth oxide (REO) production. To overcome this monopolistic supply situation, new strategies and investments are necessary to satisfy domestic supply demands. Concurrently, environmental, economic, and social problems arising from REE mining must be addressed. There is an urgent need to develop efficient REE recycling techniques from end-of-life products, technologies to minimize the amount of REEs required per unit device, and methods to recover them from fly ash or fossil fuel-burning wastes. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Alaska's rare earth deposits and resource potential

USGS Publications Warehouse

Barker, James C.; Van Gosen, Bradley S.

2012-01-01

Alaska’s known mineral endowment includes some of the largest and highest grade deposits of various metals, including gold, copper and zinc. Recently, Alaska has also been active in the worldwide search for sources of rare earth elements (REE) to replace exports now being limitedby China. Driven by limited supply of the rare earths, combined with their increasing use in new ‘green’ energy, lighting, transportation, and many other technological applications, the rare earth metals neodymium, europium and, in particular, the heavy rare earth elements terbium, dysprosium and yttrium are forecast to soon be in critical short supply (U.S. Department of Energy, 2010).

Uptake and Effects of Six Rare Earth Elements (REEs) on Selected Native and Crop Species Growing in Contaminated Soils

PubMed Central

Carpenter, David; Boutin, Céline; Allison, Jane E.; Parsons, Jessica L.; Ellis, Deanna M.

2015-01-01

Rare earth elements (REEs) have become increasingly important metals used in modern technology. Processes including mining, oil refining, discarding of obsolete equipment containing REEs, and the use of REE-containing phosphate fertilizers may increase the likelihood of environmental contamination. However, there is a scarcity of information on the toxicity and accumulation of these metals to terrestrial primary producers in contaminated soils. The objective of this work was to assess the phytotoxicity and uptake from contaminated soil of six REEs (chloride forms of praseodymium, neodymium, samarium, terbium, dysprosium, and erbium) on three native plants (Asclepias syriaca L., Desmodium canadense (L.) DC., Panicum virgatum L.) and two crop species (Raphanus sativus L., Solanum lycopersicum L.) in separate dose-response experiments under growth chamber conditions. Limited effects of REEs were found on seed germination and speed of germination. Effects on aboveground and belowground biomass were more pronounced, especially for the three native species, which were always more sensitive than the crop species tested. Inhibition concentrations (IC25 and IC50) causing 25 or 50% reductions in plant biomass respectively, were measured. For the native species, the majority of aboveground biomass IC25s (11 out of 18) fell within 100 to 300 mg REE/kg dry soil. In comparison to the native species, IC25s for the crops were always greater than 400 mg REE/kg, with the majority of results (seven out of 12) falling above 700 mg REE/kg. IC50s were often not detected for the crops. Root biomass of native species was also affected at lower doses than in crops. REE uptake by plants was higher in the belowground parts than in the above-ground plant tissues. Results also revealed that chloride may have contributed to the sensitivity of the native species, Desmodium canadense, one of the most sensitive species studied. Nevertheless, these results demonstrated that phytotoxicity may be a

Uptake and Effects of Six Rare Earth Elements (REEs) on Selected Native and Crop Species Growing in Contaminated Soils.

PubMed

Carpenter, David; Boutin, Céline; Allison, Jane E; Parsons, Jessica L; Ellis, Deanna M

2015-01-01

Rare earth elements (REEs) have become increasingly important metals used in modern technology. Processes including mining, oil refining, discarding of obsolete equipment containing REEs, and the use of REE-containing phosphate fertilizers may increase the likelihood of environmental contamination. However, there is a scarcity of information on the toxicity and accumulation of these metals to terrestrial primary producers in contaminated soils. The objective of this work was to assess the phytotoxicity and uptake from contaminated soil of six REEs (chloride forms of praseodymium, neodymium, samarium, terbium, dysprosium, and erbium) on three native plants (Asclepias syriaca L., Desmodium canadense (L.) DC., Panicum virgatum L.) and two crop species (Raphanus sativus L., Solanum lycopersicum L.) in separate dose-response experiments under growth chamber conditions. Limited effects of REEs were found on seed germination and speed of germination. Effects on aboveground and belowground biomass were more pronounced, especially for the three native species, which were always more sensitive than the crop species tested. Inhibition concentrations (IC25 and IC50) causing 25 or 50% reductions in plant biomass respectively, were measured. For the native species, the majority of aboveground biomass IC25s (11 out of 18) fell within 100 to 300 mg REE/kg dry soil. In comparison to the native species, IC25s for the crops were always greater than 400 mg REE/kg, with the majority of results (seven out of 12) falling above 700 mg REE/kg. IC50s were often not detected for the crops. Root biomass of native species was also affected at lower doses than in crops. REE uptake by plants was higher in the belowground parts than in the above-ground plant tissues. Results also revealed that chloride may have contributed to the sensitivity of the native species, Desmodium canadense, one of the most sensitive species studied. Nevertheless, these results demonstrated that phytotoxicity may be a

Application of stochastic approach based on Monte Carlo (MC) simulation for life cycle inventory (LCI) of the rare earth elements (REEs) in beneficiation rare earth waste from the gold processing: case study

NASA Astrophysics Data System (ADS)

Bieda, Bogusław; Grzesik, Katarzyna

2017-11-01

The study proposes an stochastic approach based on Monte Carlo (MC) simulation for life cycle assessment (LCA) method limited to life cycle inventory (LCI) study for rare earth elements (REEs) recovery from the secondary materials processes production applied to the New Krankberg Mine in Sweden. The MC method is recognizes as an important tool in science and can be considered the most effective quantification approach for uncertainties. The use of stochastic approach helps to characterize the uncertainties better than deterministic method. Uncertainty of data can be expressed through a definition of probability distribution of that data (e.g. through standard deviation or variance). The data used in this study are obtained from: (i) site-specific measured or calculated data, (ii) values based on literature, (iii) the ecoinvent process "rare earth concentrate, 70% REO, from bastnäsite, at beneficiation". Environmental emissions (e.g, particulates, uranium-238, thorium-232), energy and REE (La, Ce, Nd, Pr, Sm, Dy, Eu, Tb, Y, Sc, Yb, Lu, Tm, Y, Gd) have been inventoried. The study is based on a reference case for the year 2016. The combination of MC analysis with sensitivity analysis is the best solution for quantified the uncertainty in the LCI/LCA. The reliability of LCA results may be uncertain, to a certain degree, but this uncertainty can be noticed with the help of MC method.

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).

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Madhavi Z; Fox, Dr. Richard V; Miziolek, Andrzej W

2015-01-01

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 bemore » able to quantify the concentrations of various REEs in real-world 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Madhavi Z; Fox, Dr. Richard V; Miziolek, Andrzej W

2015-01-01

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 bemore » 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.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madhavi Z. Martin; Robert V. Fox; Andrzej W. Miziolek

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 bemore » 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.« less

Interactions of microorganisms with rare earth ions and their utilization for separation and environmental technology.

PubMed

Moriwaki, Hiroshi; Yamamoto, Hiroki

2013-01-01

In recent years, rare earth elements (REEs) have been widely used in various modern technological devices and the global demand for REE has been increasing. The increased demand for REEs has led to environmental exposure or water pollution from rare earth metal mines and various commercial products. Therefore, the development of a safe technology for the separation and adsorption of REEs is very important from the perspective of green chemistry and environmental pollution. In this review, the application and mechanisms of microorganisms for the removal and extraction of REEs from aqueous solutions are described. In addition, the advantages in using microorganisms for REE adsorption and future studies on this topic are discussed.

Global demand for rare earth resources and strategies for green mining

USDA-ARS?s Scientific Manuscript database

Rare earths elements (REEs) are essential raw materials for the emerging green (low-carbon) energy technologies and ‘smart’ electronic devices. Global REE demand is slated to grow at a compound annual rate of 5% by 2020. Such high growth rate would require a steady supply base of REEs in the long ru...

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

PubMed

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

2015-11-01

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

RARE EARTH ELEMENTS IN FLY ASHES AS POTENTIAL INDICATORS OF ANTHROPOGENIC SOIL CONTAMINATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mattigod, Shas V.

2003-08-01

Studies of rare earth element (REE) content of disposed fly ashes and their potential mobility were neglected for decades because these elements were believed to be environmentally benign. A number of recent studies have now shown that REE may pose a long-term risk to the biosphere. Therefore, there is a critical need to study the REE concentrations in fly ash and their potential mobilization and dispersal upon disposal in the environment. We analyzed the REE content of bulk, size fractionated, and density separated fractions of three fly ash samples derived from combustion of sub bituminous coals from the western Unitedmore » States and found that the concentrations of these elements in bulk ashes were within the range typical of fly ashes derived from coals from the North American continent. The concentrations of light rare earth elements (LREE) such as La, Ce, and Nd, however, tended towards the higher end of the concentration range whereas, the concentrations of middle rare earth elements (MREE) (Sm and Eu) and heavy rare earth elements (HREE) (Lu) were closer to the lower end of the observed range for North American fly ashes. The concentrations of REE did not show any significant enrichment with decreasing particle size, this is typical of nonvolatile lithophilic element behavior during the combustion process. The lithophilic nature of REE was also confirmed by their concentrations in heavy density fractions of these fly ashes being on average about two times more enriched than the concentrations in the light density fractions. Shale normalized average of REE concentrations of fly ashes and coals revealed significant positive anomalies for Eu and Dy. Because of these distinctive positive anomalies of Eu and Dy, we believe that fly ash contamination of soils can be fingerprinted and distinguished from other sources of anthropogenic REE inputs in to the environment.« less

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.

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.

China’s Rare Earth Policies: Economic Statecraft or Interdependence?

DTIC Science & Technology

2012-12-01

statecraft. As evident towards the beginning of the 21st century, China’s policies associated with the rare earths market (e.g., resource quotas...controls approximately 97% of the world’s REE market . These rare earths, which are not widely known because they are so low on the production chain...rare earths as well as access to the developing Chinese market . Additionally, safety and environmental factors will likely raise the cost of

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.

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.

Bioadsorption of rare earth elements through cell surface display of lanthanide binding tags

DOE PAGES

Park, Dan M.; Reed, David W.; Yung, Mimi C.; ...

2016-02-02

In this study, 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 usingmore » 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.« less

Rare Earth Elements in Alberta Oil Sand Process Streams

DOE PAGES

Roth, Elliot; Bank, Tracy; Howard, Bret; ...

2017-04-05

The concentrations of rare earth elements in Alberta, Canada oil sands and six oil sand waste streams were determined using inductively coupled plasma mass spectrometry (ICP–MS). The results indicate that the rare earth elements (REEs) are largely concentrated in the tailings solvent recovery unit (TSRU) sample compared to the oil sand itself. The concentration of lanthanide elements is ~1100 mg/kg (1100 ppm or 0.11 weight %), which represents a >20× increase in the concentration compared to the oil sand itself and a >7× increase compared to the North American Shale Composite (NASC). The process water, which is used to extractmore » the oil from oil sands, and the water fraction associated with the different waste streams had very low concentrations of REEs that were near or below the detection limits of the instrument, with the highest total concentration of REEs in the water fraction being less than 10 μg/L (ppb). Size and density separations were completed, and the REEs and other potentially interesting and valuable metals, such as Ti and Zr, were concentrated in different fractions. These results give insights into the possibility of recovering REEs from waste streams generated from oil sand processing.« less

Rare Earth Elements in Alberta Oil Sand Process Streams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roth, Elliot; Bank, Tracy; Howard, Bret

The concentrations of rare earth elements in Alberta, Canada oil sands and six oil sand waste streams were determined using inductively coupled plasma mass spectrometry (ICP–MS). The results indicate that the rare earth elements (REEs) are largely concentrated in the tailings solvent recovery unit (TSRU) sample compared to the oil sand itself. The concentration of lanthanide elements is ~1100 mg/kg (1100 ppm or 0.11 weight %), which represents a >20× increase in the concentration compared to the oil sand itself and a >7× increase compared to the North American Shale Composite (NASC). The process water, which is used to extractmore » the oil from oil sands, and the water fraction associated with the different waste streams had very low concentrations of REEs that were near or below the detection limits of the instrument, with the highest total concentration of REEs in the water fraction being less than 10 μg/L (ppb). Size and density separations were completed, and the REEs and other potentially interesting and valuable metals, such as Ti and Zr, were concentrated in different fractions. These results give insights into the possibility of recovering REEs from waste streams generated from oil sand processing.« less

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.

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.

Rare earth elements in human hair from a mining area of China.

PubMed

Wei, Binggan; Li, Yonghua; Li, Hairong; Yu, Jiangping; Ye, Bixiong; Liang, Tao

2013-10-01

Rare earth minerals have been mined for more than 50 years in Inner Mongolia of China. In the mining area rare earth elements (REE) may be significantly accumulated in humans. Therefore, the aim of this paper is to characterize the REE concentrations in hair of local residents. REE concentrations in hair of 118 subjects were determined. The results showed that the mean concentrations of the determined REE in the hair of both females and males were usually higher from mining area than from control area. The mean concentrations of all the fifteen REE were much higher in hair of males than in hair of females from mining area. This suggested that males might be more sensitive to REE than females. In addition, the mean contents of the REE in hair of miners, particularly light REE (La, Ce, Pr and Nd), were usually much higher than the values in hair of non-miners from both mining area and control area, indicating that the miners were exposed to higher concentrations of REE in occupational environment. Among age groups, the relationships between REE concentrations and age groups showed that more and more concentrations of light REE accumulated in body of both females and males with age until 60 years, while heavy REE concentrations decreased with age in males who were exposed to low concentrations of heavy REE. Copyright © 2013 Elsevier Inc. All rights reserved.

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

NASA Astrophysics Data System (ADS)

Leybourne, Matthew I.; Johannesson, Karen H.

2008-12-01

We have collected ˜500 stream waters and associated bed-load sediments over an ˜400 km 2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into "dissolved" (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm] NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce ∗] NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu ∗] NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm] NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb] NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce ∗] NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu ∗] NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm] NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb] NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced. The partial extraction recovered, on average ˜20% of the Fe in the total sediment, ˜80% of the Mn, and 21-29% of the REEs (Ce = 19

Effects of organic ligands on fractionation of rare earth elements (REEs) in hydroponic plants: an application to the determination of binding capacities by humic acid for modeling.

PubMed

Ding, ShiMing; Liang, Tao; Zhang, ChaoSheng; Yan, JunCai; Zhang, ZiLi

2006-12-01

Previous studies have revealed the fractionation processes of rare earth elements (REEs) in hydroponic plants, with a heavy REE (HREE, the elements from Gd to Lu) enrichment in leaves. In this study, effects on the HREE enrichment in soybean leaves with additions of carboxylic acids (acetate, malate, citrate, NTA, EDTA and DTPA) and two soil humic acids (HAs) were investigated. REE speciation in carboxylic acid and HA solutions was simulated using Visual MINTEQ and Model V, respectively. The results showed that the effects caused by carboxylic acids were strongly dependent on the differences between their binding strengths for light REEs (LREEs, the elements from La to Eu) and those for HREEs. A good correlation existed between these effects and the changes of free REE ions in solutions. This relationship was also observed for the HA treatments, provided that the intrinsic equilibrium constants of REEs for cation-proton exchange with HA (i.e., pK(MHA)) in Model V were estimated using a free-energy relationship with the stability constants for REE complexation with lactic acid. It is suggested that this set of pK(MHA) values is more suitable for use in Model V for the simulation of REE complexation with HA.

Chromatographic Techniques for Rare Earth Elements Analysis

NASA Astrophysics Data System (ADS)

Chen, Beibei; He, Man; Zhang, Huashan; Jiang, Zucheng; Hu, Bin

2017-04-01

The present capability of rare earth element (REE) analysis has been achieved by the development of two instrumental techniques. The efficiency of spectroscopic methods was extraordinarily improved for the detection and determination of REE traces in various materials. On the other hand, the determination of REEs very often depends on the preconcentration and separation of REEs, and chromatographic techniques are very powerful tools for the separation of REEs. By coupling with sensitive detectors, many ambitious analytical tasks can be fulfilled. Liquid chromatography is the most widely used technique. Different combinations of stationary phases and mobile phases could be used in ion exchange chromatography, ion chromatography, ion-pair reverse-phase chromatography and some other techniques. The application of gas chromatography is limited because only volatile compounds of REEs can be separated. Thin-layer and paper chromatography are techniques that cannot be directly coupled with suitable detectors, which limit their applications. For special demands, separations can be performed by capillary electrophoresis, which has very high separation efficiency.

RARE EARTH ELEMENT IMPACTS ON BIOLOGICAL WASTEWATER TREATMENT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujita, Y.; Barnes, J.; Fox, S.

Increasing demand for rare earth elements (REE) is expected to lead to new development and expansion in industries processing and or recycling REE. For some industrial operators, sending aqueous waste streams to a municipal wastewater treatment plant, or publicly owned treatment works (POTW), may be a cost effective disposal option. However, wastewaters that adversely affect the performance of biological wastewater treatment at the POTW will not be accepted. The objective of our research is to assess the effects of wastewaters that might be generated by new rare earth element (REE) beneficiation or recycling processes on biological wastewater treatment systems. Wemore » have been investigating the impact of yttrium and europium on the biological activity of activated sludge collected from an operating municipal wastewater treatment plant. We have also examined the effect of an organic complexant that is commonly used in REE extraction and separations; similar compounds may be a component of newly developed REE recycling processes. Our preliminary results indicate that in the presence of Eu, respiration rates for the activated sludge decrease relative to the no-Eu controls, at Eu concentrations ranging from <10 to 660 µM. Yttrium appears to inhibit respiration as well, although negative impacts have been observed only at the highest Y amendment level tested (660 µM). The organic complexant appears to have a negative impact on activated sludge activity as well, although results are variable. Ultimately the intent of this research is to help REE industries to develop environmentally friendly and economically sustainable beneficiation and recycling processes.« less

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.

Rare earth patterns in shergottite phosphates and residues

NASA Technical Reports Server (NTRS)

Laul, J. C.

1987-01-01

Leaching experiments with 1M HCl on ALHA 77005 powder show that rare earth elements (REE) are concentrated in accessory phosphate phases (whitlockite, apatite) that govern the REE patterns of bulk shergottites. The REE patterns of whitlockite are typically light REE-depleted with a negative Eu anomaly and show a hump at the heavy REE side, while the REE pattern of apatite (in Shergotty) is light REE-enriched. Parent magmas are calculated from the modal compositions of residues of ALHA 77005, Shergotty, and EETA 79001. The parent magmas lack a Eu anomaly, indicating that plagioclase was a late-stage crystallizing phase and that it probably crystallized before the phosphates. The parent magmas of ALHA 77005 and Shergotty have similar REE patterns, with a subchondritic Nd/Sm ratio. However, the Sm/Nd isotopoics require a light REE-depleted source for ALHA 77005 (if the crystallization age is less than 600 Myr) and a light REE-enriched source for Shergotty. Distant Nd and Sr isotopic signatures may suggest different source regions for shergottites.

Not all Rare Earths are the Same to Microbes

NASA Astrophysics Data System (ADS)

Fujita, Y.; Reed, D. W.; St Jeor, J.; Das, G.; Anderko, A.

2017-12-01

Rare earth elements (REE) are important for modern technologies including smart phones and energy efficient lighting, electric and hybrid vehicles, and advanced wind turbines. Greater demand and usage of REE leads to increased potential for ecosystem impacts, as human activities generate higher concentrations of these metals through mining, industrial processing and waste generation than are normally present in natural environments. Biological modules in wastewater treatment plants are among the ecosystems likely to be impacted by higher REE loads because these poorly soluble metals often accumulate in sludges. We have been examining the effects of adding REE to laboratory cultures of Sporacetigenium mesophilum, a fermenting bacterium originally isolated from an anaerobic sludge digester. We observed that the addition of 60 µM ( 9 ppm) europium stimulated growth and hydrogen production by S. mesophilum. The addition of the equivalent amount of samarium, separately, appeared to be even more beneficial to S. mesophilum. However, when we measured soluble metal concentrations in the cultures, we found strikingly different results. After 24 hours, essentially all of the added Eu remained in the aqueous phase, but 60-65% of the added Sm was no longer soluble. To better understand the relationship between the solubility of REE and their impact on microbiological processes, a thermodynamic model was established for Eu and Sm species in simulated aqueous environments. The model was calibrated to reproduce the solubility of both crystalline and amorphous rare earth hydroxides, which control the availability of rare earths in solution. The primary factors influencing solubility are the solution pH, crystallinity of the hydroxide mineral and redox conditions. In the case of Eu, transition between trivalent and divalent cations occurs at moderate potentials and, therefore, it is possible that divalent cations contribute to the solubilization of Eu. In the case of Sm, divalent

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

DOE Data Explorer

Dean Stull

2016-05-24

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

Novel approach in k0-NAA for highly concentrated REE Samples.

PubMed

Abdollahi Neisiani, M; Latifi, M; Chaouki, J; Chilian, C

2018-04-01

The present paper presents a new approach for k 0 -NAA for accurate quantification with short turnaround analysis times for rare earth elements (REEs) in high content mineral matrices. REE k 0 and Q 0 values, spectral interferences and nuclear interferences were experimentally evaluated and improved with Alfa Aesar Specpure Plasma Standard 1000mgkg -1 mono-rare earth solutions. The new iterative gamma-ray self-attenuation and neutron self-shielding methods were investigated with powder standards prepared from 100mg of 99.9% Alfa Aesar mono rare earth oxide diluted with silica oxide. The overall performance of the new k 0 -NAA method for REEs was validated using a certified reference material (CRM) from Canadian Certified Reference Materials Project (REE-2) with REE content ranging from 7.2mgkg -1 for Yb to 9610mgkg -1 for Ce. The REE concentration was determined with uncertainty below 7% (at 95% confidence level) and proved good consistency with the CRM certified concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

Uncovering the end uses of the rare earth elements.

PubMed

Du, Xiaoyue; Graedel, T E

2013-09-01

The rare earth elements (REE) are a group of fifteen elements with unique properties that make them indispensable for a wide variety of emerging and conventional established technologies. However, quantitative knowledge of REE remains sparse, despite the current heightened interest in future availability of the resources. Mining is heavily concentrated in China, whose monopoly position and potential restriction of exports render primary supply vulnerable to short term disruption. We have drawn upon the published literature and unpublished materials in different languages to derive the first quantitative annual domestic production by end use of individual rare earth elements from 1995 to 2007. The information is illustrated in Sankey diagrams for the years 1995 and 2007. Other years are available in the supporting information. Comparing 1995 and 2007, the production of the rare earth elements in China, Japan, and the US changed dramatically in quantities and structure. The information can provide a solid foundation for industries, academic institutions and governments to make decisions and develop strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Towards the challenging REE exploration in Indonesia

NASA Astrophysics Data System (ADS)

Setiawan, Iwan

2018-02-01

Rare earth elements (REE) are the seventeen elements, including fifteen from 57La to 71Lu, in addition to 21Sc and 39Y. In rock-forming minerals, rare earth elements typically occur in compounds as trivalent cations in carbonates, oxides, phosphates, and silicates. The REE occur in a wide range of rock types: igneous, sedimentary and metamorphic rocks. REE are one of the critical metals in the world. Their occurrences are important to supply the world needs on high technology materials. Indonesia has a lot of potential sources of REE that are mainly from residual tin mining processes in Bangka islands, which are associated with radioactive minerals e.g. monazite and xenotime. However, the REE from monazite and xenotime are difficult to extract and contain high radioactivity. Granitoids are widely distributed in Sumatra, Sulawesi, Kalimantan and Papua. They also have a very thick weathering crusts. Important REE-bearing minerals are allanite and titanite. Their low susceptibilities during weathering result an economically potential REE concentration. I-/A- type granitoids and their weathered crusts are important REE sources in Indonesia. Unfortunately, their distribution and genesis have not been deeply studied. Future REE explorations challenge are mainly of the granitoids their weathered crusts. Geochemical and mineralogical characterization of type of granitoids and their weathered crusts, the hydrothermally altered rocks, and clear REE regulation will help discover REE deposits in Indonesia.

A survey of 16 rare Earth elements in the major foods in China.

PubMed

Jiang, Ding Guo; Yang, Jie; Zhang, Shuo; Yang, Da Jin

2012-06-01

The aim of this survey was to investigate the level of contamination of the most consumed foods in China with 16 rare earth elements (REEs), and to provide the basic data for establishing and revising food safety standards for REEs. Sixteen REEs in foods were measured by inductively coupled plasma-mass spectrometry (ICP-MS) in the labs of the Centers for Disease Control and Prevention of four provinces and two municipalities, during 2009-2010. 1 231 samples were analyzed and 19 121 concentration data of 16 REEs were collected. The REEs levels in the investigated foods varied significantly. The concentrations of cerium (Ce), dysprosium (Dy), yttrium (Y), lanthanum (La), and neodymium (Nd) were relatively high, while the remaining eleven REEs were at low levels. The mean values of total rare earth element oxides (REOs) in cereals, fresh vegetables, fresh aquatic products, fresh meats and eggs varied from 0.052 mg/kg to 0.337 mg/kg. 16 REEs in the major foods were at very low contamination levels in the investigated regions. Copyright © 2012 The Editorial Board of Biomedical and Environmental Sciences. Published by Elsevier B.V. All rights reserved.

Origin of heavy rare earth mineralization in South China

PubMed Central

Xu, Cheng; Kynický, Jindřich; Smith, Martin P.; Kopriva, Antonin; Brtnický, Martin; Urubek, Tomas; Yang, Yueheng; Zhao, Zheng; He, Chen; Song, Wenlei

2017-01-01

Heavy rare earth elements (HREE) are dominantly mined from the weathering crusts of granites in South China. Although weathering processes occur globally, no economic HREE resources of this type have yet been found outside China. Here, we report the occurrence of unidentified REE minerals in the granites from South Chinese deposits. They contain high levels of both HREE and light REE, but are strongly depleted in Ce, implying high oxidation state. These REE minerals show higher initial Nd isotope than primary REE-rich minerals (ɛNd(t)=0.9±0.8 versus −11.5±0.5). The mineralized weathering crusts inherited REE signature of the granites, but show more Ce depletion and more overall concentration of the REE. We propose, therefore, that highly oxidized, REE-rich fluids, derived from external, isotopically depleted sources, metasomatized the granites, which resulted in Ce depletion as Ce4+ and enrichment of the remaining REE, especially the HREE, contributing to formation of a globally important REE resource. PMID:28220784

Sources of Extraterrestrial Rare Earth Elements:To the Moon and Beyond

NASA Astrophysics Data System (ADS)

McLeod, C. L.; Krekeler, M. P. S.

2017-08-01

The resource budget of Earth is limited. Rare-earth elements (REEs) are used across the world by society on a daily basis yet several of these elements have <2500 years of reserves left, based on current demand, mining operations, and technologies. With an increasing population, exploration of potential extraterrestrial REE resources is inevitable, with the Earth's Moon being a logical first target. Following lunar differentiation at 4.50-4.45 Ga, a late-stage (after 99% solidification) residual liquid enriched in Potassium (K), Rare-earth elements (REE), and Phosphorus (P), (or "KREEP") formed. Today, the KREEP-rich region underlies the Oceanus Procellarum and Imbrium Basin region on the lunar near-side (the Procellarum KREEP Terrain, PKT) and has been tentatively estimated at preserving 2.2 × 10^8 km^3 of KREEP-rich lithologies. The majority of lunar samples (Apollo, Luna, or meteoritic samples) contain REE-bearing minerals as trace phases, e.g., apatite and/or merrillite, with merrillite potentially contributing up to 3% of the PKT. Other lunar REE-bearing lunar phases include monazite, yittrobetafite (up to 94,500 ppm yttrium), and tranquillityite (up to 4.6 wt % yttrium, up to 0.25 wt % neodymium), however, lunar sample REE abundances are low compared to terrestrial ores. At present, there is no geological, mineralogical, or chemical evidence to support REEs being present on the Moon in concentrations that would permit their classification as ores. However, the PKT region has not yet been mapped at high resolution, and certainly has the potential to yield higher REE concentrations at local scales (<10s of kms). Future lunar exploration and mapping efforts may therefore reveal new REE deposits. Beyond the Moon, Mars and other extraterrestrial materials are host to REEs in apatite, chevkinite-perrierite, merrillite, whitlockite, and xenotime. These phases are relatively minor components of the meteorites studied to date, constituting <0.6% of the total sample

Rare-earth abundances in chondritic meteorites

NASA Technical Reports Server (NTRS)

Evensen, N. M.; Hamilton, P. J.; Onions, R. K.

1978-01-01

Fifteen chondrites, including eight carbonaceous chondrites, were analyzed for rare earth element abundances by isotope dilution. Examination of REE for a large number of individual chondrites shows that only a small proportion of the analyses have flat unfractionated REE patterns within experimental error. While some of the remaining analyses are consistent with magmatic fractionation, many patterns, in particular those with positive Ce anomalies, can not be explained by known magmatic processes. Elemental abundance anomalies are found in all major chondrite classes. The persistence of anomalies in chondritic materials relatively removed from direct condensational processes implies that anomalous components are resistant to equilibrium or were introduced at a late stage of chondrite formation. Large-scale segregation of gas and condensate is implied, and bulk variations in REE abundances between planetary bodies is possible.

Rare earth elements as a fingerprint of soil components solubilization

NASA Astrophysics Data System (ADS)

Davranche, M.; Grybos, M.; Gruau, G.; Pédrot, 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

Addressing Criticality in Rare Earth Elements via Permanent Magnets Recycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nlebedim, I. C.; King, A. H.

Rare earth elements (REEs) are critical for many advanced technologies and are faced with potential supply disruptions. Recycling of permanent magnets (PMs) can be good sources for REEs which can help minimize global dependence on freshly mined REEs, but PMs are rarely recycled. Recycling of PMs has been discussed with respect to improving REEs resource sustainability. Some challenges to be addressed in order to establish industrially deployable technologies for PMs recycling have also been discussed, including profitability, energy efficiency and environmental impacts. Key considerations for promoting circular economy via PMs recycling is proposed with the focus on deciding the targetmore » points in the supply chain at which the recycled products will be inserted. Important technical considerations for recycling different forms of waste PMs, including swarfs, slags, shredded and intact hard disk drives magnets, have been presented. Lastly, the aspects of circular economy considered include reusing magnets, remanufacturing magnets and recovering of REEs from waste PMs.« less

Addressing Criticality in Rare Earth Elements via Permanent Magnets Recycling

DOE PAGES

Nlebedim, I. C.; King, A. H.

2017-12-12

Rare earth elements (REEs) are critical for many advanced technologies and are faced with potential supply disruptions. Recycling of permanent magnets (PMs) can be good sources for REEs which can help minimize global dependence on freshly mined REEs, but PMs are rarely recycled. Recycling of PMs has been discussed with respect to improving REEs resource sustainability. Some challenges to be addressed in order to establish industrially deployable technologies for PMs recycling have also been discussed, including profitability, energy efficiency and environmental impacts. Key considerations for promoting circular economy via PMs recycling is proposed with the focus on deciding the targetmore » points in the supply chain at which the recycled products will be inserted. Important technical considerations for recycling different forms of waste PMs, including swarfs, slags, shredded and intact hard disk drives magnets, have been presented. Lastly, the aspects of circular economy considered include reusing magnets, remanufacturing magnets and recovering of REEs from waste PMs.« less

Addressing Criticality in Rare Earth Elements via Permanent Magnets Recycling

NASA Astrophysics Data System (ADS)

Nlebedim, I. C.; King, A. H.

2017-12-01

Rare earth elements (REEs) are critical for many advanced technologies and are faced with potential supply disruptions. Recycling of permanent magnets (PMs) can be good sources for REEs which can help minimize global dependence on freshly mined REEs, but PMs are rarely recycled. Recycling of PMs has been discussed with respect to improving REEs resource sustainability. Some challenges to be addressed in order to establish industrially deployable technologies for PMs recycling have also been discussed, including profitability, energy efficiency and environmental impacts. Key considerations for promoting circular economy via PMs recycling is proposed with the focus on deciding the target points in the supply chain at which the recycled products will be inserted. Important technical considerations for recycling different forms of waste PMs, including swarfs, slags, shredded and intact hard disk drives magnets, have been presented. The aspects of circular economy considered include reusing magnets, remanufacturing magnets and recovering of REEs from waste PMs.

Addressing Criticality in Rare Earth Elements via Permanent Magnets Recycling

NASA Astrophysics Data System (ADS)

Nlebedim, I. C.; King, A. H.

2018-02-01

Rare earth elements (REEs) are critical for many advanced technologies and are faced with potential supply disruptions. Recycling of permanent magnets (PMs) can be good sources for REEs which can help minimize global dependence on freshly mined REEs, but PMs are rarely recycled. Recycling of PMs has been discussed with respect to improving REEs resource sustainability. Some challenges to be addressed in order to establish industrially deployable technologies for PMs recycling have also been discussed, including profitability, energy efficiency and environmental impacts. Key considerations for promoting circular economy via PMs recycling is proposed with the focus on deciding the target points in the supply chain at which the recycled products will be inserted. Important technical considerations for recycling different forms of waste PMs, including swarfs, slags, shredded and intact hard disk drives magnets, have been presented. The aspects of circular economy considered include reusing magnets, remanufacturing magnets and recovering of REEs from waste PMs.

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

USDA-ARS?s Scientific Manuscript database

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...

Rare Earth Element Concentrations in Submarine Hydrothermal Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fowler, Andrew; Zierenberg, Robert

Rare earth element concentrations in submarine hydrothermal fluids from Alarcon Rise, East Pacific Rise, REE concentrations in submarine hydrothermal fluids from Pescadero Basin, Gulf of California, and the Cleft vent field, southern Juan de Fuca Ridge. Data are not corrected to zero Mg.

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

USDA-ARS?s Scientific Manuscript database

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...

Modeling the Value Recovery of Rare Earth Permanent Magnets at End-of-Life

DOE PAGES

Cong, Liang; Jin, Hongyue; Fitsos, Pete; ...

2015-05-21

Permanent magnets containing rare earth elements (REEs) such as Dysprosium and Neodymium offer an advantage over non-REE containing magnets (e.g. ferrite or AlNiCo) in terms of power relative to size. However, REE availability has varied significantly in recent years leading to volatility in the cost of rare earth permanent magnets (REPMs). The supply of REEs can be increased by recycling consumer products and industrial machinery that contain REPMs at product end-of-life (EOL). This paper discusses the REE recovery process for EOL products. The optimal dismantling of products is examined with an emphasis placed on obtaining used REPMs. The challenge ofmore » collecting, managing, transporting, and processing used products is addressed through the development of a cost model for REPM recovery. This model is used to investigate several EOL strategies for recovering REPMs. Sensitivity analysis is conducted to identify the key factors that influence value recovery economics. A hard disk drive serves as a case study for model demonstration.« less

Rare earth elements and hypertension risk among housewives: A pilot study in Shanxi Province, China.

PubMed

Wang, Bin; Yan, Lailai; Huo, Wenhua; Lu, Qun; Cheng, Zixi; Zhang, Jingxu; Li, Zhiwen

2017-01-01

Studies have shown that residents living near rare earth mining areas have high concentrations of rare earth elements (REEs) in their hair. However, the adverse effects of REEs on human health have rarely been the focus of epidemiological studies. The goal of this study was to evaluate the relationship between REEs in hair and the risk of hypertension in housewives. We recruited 398 housewives in Shanxi Province, China, consisting of 163 women with hypertension (cases) and 235 healthy women without hypertension (controls). We analyzed 15 REEs (lanthanum (La), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), Yttrium (Y), cerium (Ce), praseodymium (Pr), and neodymium (Nd)) and calcium (Ca) accumulated in housewives hair over a period of two years. The results revealed that, with the exception of Eu, concentrations of the REEs in hair were higher in the cases than in the controls. The univariate odds ratios (ORs) of the 14 REEs were >1, and four of the REEs (Dy, Tm, Yb, and Y) also had adjusted ORs > 1. The increasing dose-response trends of the four REEs further indicated the potential for increased hypertension risk. Moreover, the REEs were negatively correlated with Ca content in hair. These results might suggest an antagonistic effect of REEs on Ca in the human body. It was concluded that high intake of REEs might increase the risk of hypertension among housewives. Copyright © 2016 Elsevier Ltd. All rights reserved.

Continental shelves as potential resource of rare earth elements.

PubMed

Pourret, Olivier; Tuduri, Johann

2017-07-19

The results of this study allow the reassessment of the rare earth elements (REE) external cycle. Indeed, the river input to the oceans has relatively flat REE patterns without cerium (Ce) anomalies, whereas oceanic REE patterns exhibit strong negative Ce anomalies and heavy REE enrichment. Indeed, the processes at the origin of seawater REE patterns are commonly thought to occur within the ocean masses themselves. However, the results from the present study illustrate that seawater-like REE patterns already occur in the truly dissolved pool of river input. This leads us to favor a partial or complete removal of the colloidal REE pool during estuarine mixing by coagulation, as previously shown for dissolved humic acids and iron. In this latter case, REE fractionation occurs because colloidal and truly dissolved pools have different REE patterns. Thus, the REE patterns of seawater could be the combination of both intra-oceanic and riverine processes. In this study, we show that the Atlantic continental shelves could be considered potential REE traps, suggesting further that shelf sediments could potentially become a resource for REE, similar to metalliferous deep sea sediments.

Influence of soil characteristics on rare earth fingerprints in mosses and mushrooms: Example of a pristine temperate rainforest (Slavonia, Croatia).

PubMed

Fiket, Željka; Medunić, Gordana; Furdek Turk, Martina; Ivanić, Maja; Kniewald, Goran

2017-07-01

The present study aims to investigate levels and distribution of rare earth elements (REE) in soils, mosses and mushrooms of a pristine temperate rainforest, a non-polluted natural system, in order to characterise their environmental availability and mobility. The multielement analysis of digested soil, moss and mushroom samples was performed by High Resolution Inductively Coupled Plasma Mass Spectrometry. The distribution of rare earths in mosses and mushrooms was found primarily affected by local pedological setting. Mosses displayed a consistent lithological signature with an almost insignificant REE fractionation compared to soils. Mushrooms showed differences in REE concentrations in certain parts of the fruiting body with regard to their main physiological function and indicated a significant impact of soil organic content on the overall REEs uptake. Results of our work highlight the importance of substrate characteristics on the initial levels of REEs in mosses and mushrooms. Moreover, this study provides baseline data on the rare earth element levels in mosses and mushrooms growing in a pristine forest area characterised by naturally elevated REE levels in the soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.

NASA Astrophysics Data System (ADS)

Johannesson, Kevin H.; Zhou, Xiaoping

1999-01-01

-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.

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

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

PubMed

Wang, Lingqing; Liang, Tao

2015-07-22

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.

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.

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.

Bioleaching of rare earth elements from waste phosphors and cracking catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, David W.; Fujita, Yoshiko; Daubaras, Dayna L.

Four microbial cultures were evaluated for organic acid production and their potential utility for leaching of rare earth elements (REE) from retorted phosphor powder (RPP) and spent fluidized cracking catalyst (FCC). Three of the cultures (2 bacterial, 1 fungal) were isolated from environmental and industrial materials known to contain rare earth elements. The other was the well-known and industrially important bacterium Gluconobacter oxydans. Gluconic acid was the predominant identified organic acid produced by all of the cultures; citric and acetic acid were among the other acids detected. There was also maximum REE leaching by cell free culture supernatants obtained withmore » Gluconobacter and the FCC; 49% of total REE was recovered, with preferential recovery of lanthanum over cerium. The phosphor powder was more difficult to leach; only ~2 % total REE was leached from RPP with Gluconobacter. Tests with the RPP indicated that the extent of REE solubilization was similar whether whole cell cultures or cell-free supernatants were used. However, Gluconobacter cell-free culture supernatants with 10-15 mM gluconic acid outperformed abiotically prepared leaching solutions with 30 mM gluconic acid concentrations. Abiotic tests showed that increasing gluconic acid concentrations increased leaching efficiency; for example, total REE leaching from FCC increased from 24 to 36 to 45% when gluconic acid was increased from 10 to 30 to 90 mM. Our research shows that utilizing microorganisms that produce gluconic acid can result in effective leaching of REE from waste materials, and optimizing gluconic acid production will improve recovery.« less

Bioleaching of rare earth elements from waste phosphors and cracking catalysts

DOE PAGES

Reed, David W.; Fujita, Yoshiko; Daubaras, Dayna L.; ...

2016-08-22

Four microbial cultures were evaluated for organic acid production and their potential utility for leaching of rare earth elements (REE) from retorted phosphor powder (RPP) and spent fluidized cracking catalyst (FCC). Three of the cultures (2 bacterial, 1 fungal) were isolated from environmental and industrial materials known to contain rare earth elements. The other was the well-known and industrially important bacterium Gluconobacter oxydans. Gluconic acid was the predominant identified organic acid produced by all of the cultures; citric and acetic acid were among the other acids detected. There was also maximum REE leaching by cell free culture supernatants obtained withmore » Gluconobacter and the FCC; 49% of total REE was recovered, with preferential recovery of lanthanum over cerium. The phosphor powder was more difficult to leach; only ~2 % total REE was leached from RPP with Gluconobacter. Tests with the RPP indicated that the extent of REE solubilization was similar whether whole cell cultures or cell-free supernatants were used. However, Gluconobacter cell-free culture supernatants with 10-15 mM gluconic acid outperformed abiotically prepared leaching solutions with 30 mM gluconic acid concentrations. Abiotic tests showed that increasing gluconic acid concentrations increased leaching efficiency; for example, total REE leaching from FCC increased from 24 to 36 to 45% when gluconic acid was increased from 10 to 30 to 90 mM. Our research shows that utilizing microorganisms that produce gluconic acid can result in effective leaching of REE from waste materials, and optimizing gluconic acid production will improve recovery.« less

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.

Rare Earth Desorption Test with Citrate and Bicarbonate

DOE Data Explorer

Jiao, Yongqin; Brewer, Aaron; Park, Dan

2017-06-01

LBT (lanthanide binding tag) cells were grown overnight in LB media with 0.05% Amp. 1:100 subculture taken from overnights, grown for 2 hours. LBT was induced with 0.002% arabinose added for 3 hours. REE adsorption was done by combining 350 ul (0.25% 1M MES, 12.5 uM Tb, and 12.5 uM La or Cu in sterile DI water) and 350 ul (LBT cells with OD = 1 in 10 mM MES), reacted for approx. 30 min. Following adsorption, citrate and bicarbonate solutions were used in desorption to recover rare earth from cell surface, and to further separate REE from non-REEs. The samples were then centrifuged and a fraction of the supernatant was collected for ICP-MS analysis.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

Dissolved Rare Earth Elements in the US GEOTRACES North Atlantic Section

NASA Astrophysics Data System (ADS)

Shiller, A. M.

2016-12-01

The rare earth elements (REEs) are a unique chemical set wherein there are systematic changes in geochemical behavior across the series. Furthermore, while most REEs are in the +III oxidation state, Ce and Eu can be in other oxidation states leading to distinct characteristics of those elements. Thus, the geochemical properties of the REEs make them particularly useful tools for inquiring into various geochemical processes. As part of the US GEOTRACES effort, we determined dissolved REEs and Y at 32 stations across the North Atlantic during US cruises GT10 and GT11 along a meridional transect from Lisbon to the Cape Verde Islands and a zonal transect from Cape Cod to the Mauritanian coast. While profiles are similar to previous reports, the high spatial resolution of the section allows for better elucidation of processes. Light rare earths (LREEs) show removal in the upper water column with a minimum at the chlorophyll maximum. LREE concentrations then increase into the oxygen minimum followed by a slight decrease and fairly constant concentrations in the mid-water column followed by an increase into the deep and bottom waters. Heavy rare earths (HREEs) show a more monotonic increase with depth. We also take advantage of a previously published water mass analysis for the section to estimate that most of the deep water changes can be explained by conservative mixing of waters with different pre-formed REE concentrations. Nonetheless, the pattern of LREE shallow water removal followed by regeneration, possible re-scavenging, and then deep water input is still preserved. Other features of note include an increase in LREEs in the strong oxygen minimum zone off Mauritania, consistent with an association of REE cycling with the redox cycles of Fe and Mn. Also along the eastern margin, but below the oxygen minimum, a small but distinct increase in the cerium and europium anomalies is observed, consistent with terrigenous input. In hydrothermally influenced waters along

Fractionations of rare earth elements in plants and their conceptive model.

PubMed

Ding, ShiMing; Liang, Tao; Yan, JunCai; Zhang, ZiLi; Huang, ZeChun; Xie, YaNing

2007-02-01

Fractionations of rare earth elements (REEs) and their mechanisms in soybean were studied through application of exogenous mixed REEs under hydroponic conditions. Significant enrichment of middle REEs (MREEs) and heavy REEs (HREEs) was observed in plant roots and leaves respectively, with slight fractionation between light REEs (LREEs) and HREEs in stems. Moreover, the tetrad effect was observed in these organs. Investigations into REE speciation in roots and in the xylem sap using X-ray absorption spectroscopy (XAS) and nanometer-sized TiO2 adsorption techniques, associated with other controlled experiments, demonstrated that REE fractionations should be dominated by fixation mechanism in roots caused by cell wall absorption and phosphate precipitation, and by the combined effects of fixation mechanism and transport mechanism in aboveground parts caused by solution complexation by intrinsic organic ligands. A conceptive model was established for REE fractionations in plants based on the above studies.

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

Determination of rare earth elements concentration at different depth profile of Precambrian pegmatites using instrumental neutron activation analysis.

PubMed

Sadiq Aliyu, Abubakar; Musa, Yahaya; Liman, M S; Abba, Habu T; Chaanda, Mohammed S; Ngene, Nnamani C; Garba, N N

2018-01-01

The Keffi area hosts abundant pegmatite bodies as a result of the surrounding granitic intrusions. Keffi is part of areas that are geologically classified as North Central Basement Complex. Data on the mineralogy and mineralogical zonation of the Keffi pegmatite are scanty. Hence the need to understand the geology and mineralogical zonation of Keffi pegmatites especially at different depth profiles is relevant as a study of the elemental composition of the pegmatite is essential for the estimation of its economic viability. Here, the relative standardization method of instrumental neutron activation analysis (INAA) has been used to investigate the vertical deviations of the elemental concentrations of rare earth elements (REEs) at different depth profile of Keffi pegmatite. This study adopted the following metrics in investigating the vertical variations of REEs concentrations. Namely, the total contents of rare earth elements (∑REE); ratio of light to heavy rare earth elements (LREE/HREE), which defines the enrichment or depletion of REEs; europium anomaly (Eu/Sm); La/Lu ratio relative to chondritic meteorites. The study showed no significant variations in the total content of rare elements between the vertical depth profiles (100-250m). However, higher total concentrations of REEs (~ 92.65ppm) were recorded at the upper depth of the pegmatite and the europium anomaly was consistently negative at all the depth profiles suggesting that the Keffi pegmatite is enriched with light REEs. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

EPA Science Inventory

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

Distribution and Geochemistry of Rare-Earth Elements in Rivers of Southern and Eastern Primorye (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chudaev, O. V.; Bragin, I. V.; A, Kharitonova N.; Chelnokov, G. A.

2016-03-01

The distribution and geochemistry of rare earth elements (REE) in anthropogenic, technogenic and natural surface waters of southern and eastern Primorye, Far East of Russia, are presented in this study. The obtained results indicated that most of REE (up to 70%) were transported as suspended matter, ratio between dissolved and suspended forms varing from the source to the mouth of rivers. It is shown that all REE (except Ce) in the source of the rivers are predominantly presented in dissolved form, however, the content of light and heavy REE is different. Short-term enrichment of light rare earth elements (LREE) caused by REE-rich runoff from waste dumps and mining is neutralized by the increase in river flow rate. Rivers in urban areas are characterized by high content of LREE in dissolved form and very low in suspended one.

The rare earth element compositions of the Changjiang (Yangtze) and Huanghe (Yellow) river sediments

NASA Astrophysics Data System (ADS)

Yang, Shou Ye; Jung, Hoi Soo; Choi, Man Sik; Li, Cong Xian

2002-07-01

Thirty-four samples from the Changjiang and Huanghe were analyzed to characterize their rare earth element (REE) compositions. Although REE concentrations in the Changjiang sediments are higher than those of the Huanghe sediments, the former are less variable. Bulk samples and acid-leachable fractions have convex REE patterns and middle REE enrichments relative to upper continental crust, whereas flat patterns are present in the residual fractions. Source rock composition is the primary control on REE composition, and weathering processes play a minor role. Grain size exerts some influence on REE composition, as demonstrated by the higher REE contents of clay minerals in sediments from both rivers. Heavy minerals contribute about 10-20% of the total REE in the sediments. Apatite is rare in the river sediments, and contributes less than 2% of the REE content, but other heavy minerals such as sphene, allanite and zircon are important reservoirs of residual REE fractions. The Fe-Mn oxides phase accounts for about 14% of bulk REE content in the Changjiang sediments, which could be one of the more important factors controlling REE fractionation in the leachable fraction.

Recovery of Rare Earths, Precious Metals and Other Critical Materials from Geothermal Waters with Advanced Sorbent Structures

DOE Data Explorer

Pamela M. Kinsey

2015-09-30

The work evaluates, develops and demonstrates flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The selected organic and inorganic sorbent materials demonstrated high performance for collection of trace REEs, precious and valuable metals. The nanostructured materials typically performed better than commercially available sorbents. Data contains organic and inorganic sorbent removal efficiency, Sharkey Hot Springs (Idaho) water chemsitry analysis, and rare earth removal efficiency from select sorbents.

Evaluation of rare earth elements in groundwater of Lagos and Ogun States, Southwest Nigeria.

PubMed

Ayedun, H; Arowolo, T A; Gbadebo, A M; Idowu, O A

2017-06-01

Rare earth elements in our environment are becoming important because of their utilization in permanent magnets, lamp phosphors, superconductors, rechargeable batteries, catalyst, ceramics and other applications. This study was conducted to evaluate the level of rare earth elements (REE) and the variability of their anomalous behavior in groundwater samples collected from Lagos and Ogun States, Southwest, Nigeria. REE concentrations were determined in 170 groundwater samples using inductively coupled plasma-mass spectrometry, while the physicochemical parameters were determined using standard methods. Lagos State groundwater is enriched with REE [sum REEs range (mean ± SD)]; [0.365-488 (69.5 ± 117)] µg L -1 than Ogun State groundwater [sum REEs range (mean ± SD)]; [1.14-232 (22.6 ± 41.1)] µg L -1 . Boreholes are more enriched with REEs than wells. Significant (P < 0.05) positive correlation (R = Pearson) was recorded in Lagos State groundwater between sum REEs and Fe (R = 0.55). However, there were no significant correlations between sum REEs, pH (R = 0.073) and HCO 3 2- (R = 0.157) in Ogun State groundwater. Chondrite-normalized plot shows that Lagos groundwater exhibits positive Ce anomaly, while Ogun State groundwater does not. The source of REE in Lagos State may be from the ocean and leaching from wastes dumpsites, while the source in Ogun State groundwater may be from the rocks.

Recovery of rare earth elements (REEs) from uranium containing solutions using biosorption

NASA Astrophysics Data System (ADS)

Botalov, Maxim; Bunkov, Grigory; Rychkov, Vladimir; Kirillov, Evgeny; Kirillov, Sergey; Kuchta, Kerstin; Kücüker, Mehmet Ali; Atamaniuk, Iryna

2017-09-01

Batch testing and determination of appropriate biosorbent and experimental procedures for recovery of REEs from artificial solution as well as the efficiency of the process for recovery of REEs from artificial solution via biosorption are given in present research work.

Rare earth elements minimal harvest year variation facilitates robust geographical origin discrimination: The case of PDO "Fava Santorinis".

PubMed

Drivelos, Spiros A; Danezis, Georgios P; Haroutounian, Serkos A; Georgiou, Constantinos A

2016-12-15

This study examines the trace and rare earth elemental (REE) fingerprint variations of PDO (Protected Designation of Origin) "Fava Santorinis" over three consecutive harvesting years (2011-2013). Classification of samples in harvesting years was studied by performing discriminant analysis (DA), k nearest neighbours (κ-NN), partial least squares (PLS) analysis and probabilistic neural networks (PNN) using rare earth elements and trace metals determined using ICP-MS. DA performed better than κ-NN, producing 100% discrimination using trace elements and 79% using REEs. PLS was found to be superior to PNN, achieving 99% and 90% classification for trace and REEs, respectively, while PNN achieved 96% and 71% classification for trace and REEs, respectively. The information obtained using REEs did not enhance classification, indicating that REEs vary minimally per harvesting year, providing robust geographical origin discrimination. The results show that seasonal patterns can occur in the elemental composition of "Fava Santorinis", probably reflecting seasonality of climate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rare-earth leaching from Florida phosphate rock in wet-process phosphoric acid production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Haijun; Zhang, Patrick; Jin, Zhen

Phosphorite, or phosphate rock, is the most significant secondary rare-earth resource. It contains high amounts of phosphate-bearing minerals along with low contents of rare earth elements (REEs). In Florida, about 19 Mt of phosphate rock are mined annually and most are used to manufacture fertilizers using a wet process, in which sulfuric acid reacts with phosphates to produce phosphoric acid and phosphogypsum. In the wet process, REEs are also leached out into solution and eventually get lost in the leaching residue and phosphate fertilizer. Recovering REEs from Florida phosphate rock in the wet process will be beneficial to broadening rare-earthmore » availability, improving the quality of phosphoric acid product and protecting the environment. Here, this study focuses on the influences of wet-process operating conditions on REE leaching efficiency. The results indicate that REE leaching efficiency increases with phosphoric acid addition in the initial pulp. At a temperature of 75 °C, a stoichiometric ratio of sulfuric acid (H2 SO4 ) to calcium oxide (CaO) of 1.05 and a weight ratio of liquid to solid of 3.5, REE leaching efficiency reached a relatively high value of 52.82 percent. The trends of REE leaching efficiency were similar to those for phosphoric acid (P2O5 ). Extensive tests on the leaching residue showed that during leaching, about 90 percent of the REEs were released from the phosphate rock but only 52.82 percent ended up in the leaching solution. This phenomenon can be attributed to two factors: (1) the effect of phosphate ions (PO43-) in the solution, which caused REE ions to form REE phosphates and be precipitated into the leaching residue, and (2) the influence of large amounts of anions such as sulfate (SO42-), dihydrogen phosphate (H2 PO4-) and hydrogen phosphate (HPO42-) anions as well as the polar molecule H3 PO4 , which surrounded the REE cations and formed an ion atmosphere that prevented the PO43- from contacting and combining with REE

Rare-earth leaching from Florida phosphate rock in wet-process phosphoric acid production

DOE PAGES

Liang, Haijun; Zhang, Patrick; Jin, Zhen; ...

2017-08-01

Phosphorite, or phosphate rock, is the most significant secondary rare-earth resource. It contains high amounts of phosphate-bearing minerals along with low contents of rare earth elements (REEs). In Florida, about 19 Mt of phosphate rock are mined annually and most are used to manufacture fertilizers using a wet process, in which sulfuric acid reacts with phosphates to produce phosphoric acid and phosphogypsum. In the wet process, REEs are also leached out into solution and eventually get lost in the leaching residue and phosphate fertilizer. Recovering REEs from Florida phosphate rock in the wet process will be beneficial to broadening rare-earthmore » availability, improving the quality of phosphoric acid product and protecting the environment. Here, this study focuses on the influences of wet-process operating conditions on REE leaching efficiency. The results indicate that REE leaching efficiency increases with phosphoric acid addition in the initial pulp. At a temperature of 75 °C, a stoichiometric ratio of sulfuric acid (H2 SO4 ) to calcium oxide (CaO) of 1.05 and a weight ratio of liquid to solid of 3.5, REE leaching efficiency reached a relatively high value of 52.82 percent. The trends of REE leaching efficiency were similar to those for phosphoric acid (P2O5 ). Extensive tests on the leaching residue showed that during leaching, about 90 percent of the REEs were released from the phosphate rock but only 52.82 percent ended up in the leaching solution. This phenomenon can be attributed to two factors: (1) the effect of phosphate ions (PO43-) in the solution, which caused REE ions to form REE phosphates and be precipitated into the leaching residue, and (2) the influence of large amounts of anions such as sulfate (SO42-), dihydrogen phosphate (H2 PO4-) and hydrogen phosphate (HPO42-) anions as well as the polar molecule H3 PO4 , which surrounded the REE cations and formed an ion atmosphere that prevented the PO43- from contacting and combining with REE

Characterization of Rare Earth Elements in in Clay Deposits Associated with Central Appalachian Coal Seams

NASA Astrophysics Data System (ADS)

Scott, M.; Verba, C.; Falcon, A.; Poston, J.; McKoy, M.

2017-12-01

Because of their multiple uses in clean energy technologies, rare earth elements (REE) are critical for national economic and energy security. With no current domestic source, supply remains a major concern for domestic security. Underclay - specifically the layer of stratum beneath a coal bed - is a potentially rich source of REE. This study focuses on the characterization and ion exchange recovery of REE from underclay samples from the Lower Freeport, Middle Kittanning, and Pittsburgh coal seams in West Virginia. Multimodal techniques provided quantitative assessments of REE-bearing mineral phases in select underclays and the influence of organic acid rock treatment on the recovery of REE from both exchangeable and crystalline mineral phases present. All samples are from extensively weathered horizons that contain abundant kaolinite and illite. Total REE concentrations range from 250-450 ppm and all samples have a HREE/LEEE ratio >20%. Rare earth element bearing minerals identified in the clay are monazite, xenotime, florencite, and crandallite. Our selective recovery approach is designed to isolate and recover REE through partial dissolution of the clay matrix and ion exchange rather than dissolution/recovery of phosphate or aluminosilicate bound REE. These results provide a better understanding of coal seam underclay, the affinity of REEs for specific ligands and colloids, and how the rock and ligands respond to different chemical treatments. These processes are important to the development and commercialization of efficient and cost effective methods to extract REE from domestic geologic deposits and recover into salable forms.

Geophysical Framework of a Rare Earth Element Enriched Terrane, Mountain Pass, California

NASA Astrophysics Data System (ADS)

Denton, K. M.; Ponce, D. A.; Peacock, J.; Miller, D. M.; Miller, J. S.

2016-12-01

Carbonatite ore deposits continue to be the primary source for rare earth elements (REEs), however large viable REE ore deposits are uncommon. The Mountain Pass carbonatite deposit, located in the eastern Mojave Desert of California, is the largest economic deposit of light REEs in North America. A 1.417 Ga ultrapotassic suite (shonkinite, syenite, and granite) and a 1.375 Ga barite-bastnasite-rich carbonatite (sovite) ore deposit comprise the enclave of REE-enriched outcrops and dikes that occupy a narrow ( 3 km) zone of 1.7 Ga gneiss extending at least 10-km to the southeast from southern Clark Mountain. Modeling of gravity, magnetic, and magnetotelluric (MT) data reveals subsurface features that form the structural framework of the REE terrane. The carbonatite and ultrapotassic mafic suite is associated with a local gravity high that is superimposed on a 4 km-wide gravity terrace, likely related to less dense granitic gneiss basement. Although physical property data indicate that the intrusive suite and carbonatite are essentially and nonmagnetic, aeromagnetic data indicate that these rocks occur along the eastern edge of a prominent north-northwest trending aeromagnetic high. This relationship suggests that they may have been preferentially emplaced along a zone of weakness or fault. The source of the magnetic high is 2-3 km below the surface and coincides with a relatively electrically conductive (3 orders of magnitude higher than surrounding rock) feature. MT data indicate that the western edge of the magnetic feature could be connected to a deeper ( 8 km) conductive feature related to possible intrusions and/or hydrothermal systems. The lack of a magnetic signature of the REE terrane can be explained by alteration of magnetite, given that the terrane lies within a broader alteration zone and observed magnetic low. If so, such an alteration event, capable of remobilizing rare earth elements, likely occurred during or after emplacement of the intrusive suite

Distribution characteristics of rare earth elements in children's scalp hair from a rare earths mining area in southern China.

PubMed

Tong, Shi-Lu; Zhu, Wang-Zhao; Gao, Zhao-Hua; Meng, Yu-Xiu; Peng, Rui-Ling; Lu, Guo-Cheng

2004-01-01

In order to demonstrate the validity of using scalp hair rare earth elements (REEs) content as a biomarker of human REEs exposure, data were collected on REEs exposure levels from children aged 11-15 years old and living in an ion-adsorptive type light REEs (LREEs) mining and surrounding areas in southern China. Sixty scalp hair samples were analyzed by ICP-MS for 16 REEs (La Lu, Y and Sc). Sixteen REEs contents in the samples from the mining area (e.g., range: La: 0.14-6.93 microg/g; Nd: 0.09-5.27 microg/g; Gd: 12.2-645.6ng/g; Lu: 0.2-13.3 ng/g; Y: 0.03-1.27 microg/g; Sc: 0.05-0.30 microg/g) were significantly higher than those from the reference area (range: La: 0.04-0.40 microg/g; Nd: 0.04-0.32 microg/g; Gd: 8.3-64.6 ng/g; Lu: 0.4-3.3ng/g; Y: 0.03-0.29 microg/g; Sc: 0.11-0.36 microg/g) and even much higher than those published in the literature. The distribution pattern of REEs in scalp hair from the mining area was very similar to that of REEs in the mine and the atmosphere shrouding that area. In conclusion, the scalp hair REEs contents may indicate not only quantitatively but also qualitatively (distribution pattern) the absorption of REEs from environmental exposure into human body. The children living in this mining area should be regarded as a high-risk group with REEs (especially LREEs) exposure, and their health status should be examined from a REEs health risk assessment perspective.

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

NASA Astrophysics Data System (ADS)

Van Pelt, R.; Zobeck, T. M.; Barnes, M. A.; Baddock, M.; D'Odorico, P.

2011-12-01

Plant communities in desert environments are spatially anisotropic. Nutrient islands develop below shrub canopies and in the bases of bunch grasses that enhance plant growth and reinforce the spatial anisotropy. Catastrophic disturbance that removes the vegetation such as fire or drought can result in the release of the trapped sediment which becomes redistributed over the landscape by wind and water. We applied Rare Earth Element (REE) tracers to different landscape positions of an anisotropic Northern Chihuahua Desert ecosystem at the Sevilleta National Wildlife Refuge in central New Mexico in an effort to study this process. We delineated three 0.5 m by 6 m plots of desert grassland and three plots of desert grassland-shrubland ecotone. Nitric acid was used to dissolve the REE oxides (Eu2O3, Dy2O3, and Pr6O11) which were then diluted in distilled water to a target concentration of 1 g REE l-1 and applied to the surface at a rate of 4 l m-2. From laboratory column studies using soil collected at the site, we estimated that this would penetrate the surface to a depth of 2.5 cm resulting in a sediment REE concentration of approximately 100 mg kg-1. Eu was applied to bare surfaces between vegetation characterized as sand with a surface covering of gravel, Pr was applied under grass clumps, and Dy was applied under Creosote Bush (Larrea tridentata (DC.). Two replicate 0.25 m2 areas of each surface type were also tagged to obtain a sample of tagged surface sediment for analysis. The area containing the plots was burned by U.S. Fish and Wildlife personnel on April 14, 2010. During the next two days, two grassland plots and two grassland-shrubland ecotone plots were tested by placing a portable boundary layer field wind tunnel over the plots and blowing them with 12 m s-1 wind for 10 minutes during which time a paired set of entrained sediment samples were captured at the outlet of the wind tunnel. This period was followed by a 30 minute test in which clean quartz sand

Rare earth elements in parasol mushroom Macrolepiota procera.

PubMed

Falandysz, Jerzy; Sapkota, Atindra; Mędyk, Małgorzata; Feng, Xinbin

2017-04-15

This study aimed to investigate occurrence and distribution of 16 rare earth elements (REEs) in edible saprobic mushroom Macrolepiota procera, and to estimate possible intake and risk to human consumer. Mushrooms samples were collected from sixteen geographically diverse sites in the northern regions of Poland. The results showed that for Ce as the most abundant among the RREs in edible caps, the mean concentration was at 0.18±0.29mgkg -1 dry biomass. The mean concentration for Σ16 REEs determined in caps of fungus was 0.50mgkg -1 dry biomass and in whole fruiting bodies was 0.75mgkg -1 dry biomass. From a point of view by consumer, the amounts of REEs contained in edible caps of M. procera could be considered small. Hence, eating a tasty caps of this fungus would not result in a health risk for consumer because of exposure to the REEs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of recovery and recycling of rare earth elements from waste fluorescent lamp phosphors

NASA Astrophysics Data System (ADS)

Eduafo, Patrick Max

Characterization techniques and experimental measurements were used to evaluate a process for recycling rare earth elements (REEs) from spent fluorescent lamp phosphors. QEMSCAN analysis revealed that over 60% of the rare earth bearing minerals was less than 10 microm. A representative sample of the as-received feed contained 14.59 wt% total rare earth elements (TREE) and upon sieving to below 75 microm, the grade increased to 19.60 wt% REE with 98.75% recovery. Based on experimental work, a new process for extracting the chief REEs from end of life fluorescent lamps has been developed. The proposed flowsheet employs a three-stage leaching and precipitation process for selective extraction and recovery of the REEs. Hydrochloric acid was used as lixiviant in batch leach experiments on the phosphor powder. The maximum extraction obtained was 100% for both yttrium and europium under the following leaching conditions: 2.5 M HCl, 70°C, 1 hour, 180 g/L and 600 rpm. However, the solubility of cerium, lanthanum and terbium remained low at these conditions. Kinetic data of the leaching of yttrium and europium showed best fit to the logarithmic rate expression of the empirical model of leaching. Activation energy was calculated to be 77.49 kJ/mol for Y and 72.75 kJ/mol for Eu in the temperature range of 298 to 343 K. Precipitation tests demonstrate that at least 50% excess the stoichiometric amount of oxalic acid is needed to recover yttrium and europium efficiently to produce a pure (Y, Eu) mixed oxide. Total recovery of the REEs was achieved even at very low pH or without any base added. Over 99% pure mixed rare earth oxide at 99% recovery has been attained. An economic assessment of the developed process using operating and capital cost have be undertaken and based on the analysis of the three economic scenarios, two are economic and one is non-economic.

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 μm) REE record of a sediment core MD05-2925 (9°20.61'S, 151°27.61'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 δ18O 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.

Rare earth elements in human and animal health: State of art and research priorities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagano, Giovanni, E-mail: gbpagano@tin.it; Aliberti, Francesco; Guida, Marco

Background: A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. Methods: A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. Results: Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures havemore » been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. Conclusion: The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments. - Highlights: • An extensive number of activities have been developed utilizing rare earth elements (REE). • The literature of REE-associated health effects in humans, and on animal studies is reviewed. • The main literature gaps are discussed, in epidemiological and in animal studies. • Prospects studies are suggested, aimed at evaluating long-term effects of REE

MICROBIALLY MEDIATED LEACHING OF RARE EARTH ELEMENTS FROM RECYCLABLE MATERIALS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, D. W.; Fujita, Y.; Daubaras, D. L.

2016-09-01

Bioleaching offers a potential approach for recovery of rare earth elements (REE) from recyclable materials, such as fluorescent lamp phosphors or degraded industrial catalysts. Microorganisms were enriched from REE-containing ores and recyclable materials with the goal of identifying strains capable of extracting REE from solid materials. Over 100 heterotrophic microorganisms were isolated and screened for their ability to produce organic acids capable of leaching REE. The ten most promising isolates were most closely related to Pseudomonas, Acinetobacter and Talaromyces. Of the acids produced, gluconic acid appeared to be the most effective at leaching REE (yttrium, lanthanum, cerium, europium, and terbium)more » from retorted phosphor powders (RPP), fluidized cracking catalyst (FCC), and europium-doped yttrium oxide (YOEu). We found that an Acinetobacter isolates, BH1, was the most capable strain and able to leach 33% of the total REE content from the FCC material. These results support the continuing evaluation of gluconic acid-producing microbes for large-scale REE recovery from recyclable materials.« less

Behaviour of Rare Earth Elements during the Earth's core formation

NASA Astrophysics Data System (ADS)

Faure, Pierre; Bouhifd, Mohamed Ali; Boyet, Maud; Hammouda, Tahar; Manthilake, Geeth

2017-04-01

Rare Earth Elements (REE) are classified in the refractory group, which means that they have a high temperature condensation and their volatility-controlled fractionation is limited to high-temperature processes. Anomalies have been measured for Eu, Yb and Sm, which are the REE with the lowest condensation temperatures in CAIs and chondrules (e.g. [1]). REE are particularly abundant in the sulfides of enstatite chondrites, 100 to 1000 times the CI value [e.g. 2,3], proving that these elements are not strictly lithophile under extremely reducing conditions. However by investigating experimentally the impact of Earth's core formation on the behavior of Sm and Nd, we have shown the absence of fractionation between Sm and Nd during the segregation of the metallic phase [4]. Recently, Wohlers and Wood [5] proposed that Nd and Sm could be fractionated in presence of a S-rich alloy phase. However, their results were obtained at pressure and temperature conditions below the plausible conditions of the Earth's core formation. Clearly, large pressure range needs to be covered before well-constrained model can be expected. Furthermore, our preliminary metal-silicate partitioning results show that Ce and Eu have higher metal/silicate partition coefficients than their neighboring elements, and that the presence of sulphur enhances the relative difference between partition coefficients. In this presentation, we will present and discuss new metal-silicate partition coefficients of all REE at a deep magma ocean at pressures ranging from those of the uppermost upper mantle ( 5 GPa) to a maximum pressure expected in the range of 20 GPa, temperatures ranging from 2500 to about 3000 K, and oxygen fugacities within IW-1 to IW-5 (1 to 5 orders of magnitude lower than the iron-wüstite buffer). We will discuss the effect of S, as well as the effect of H2O on the behaviour of REE during the Earth's core formation: recent models suggest that contrary to currently accepted beliefs, the

The rare-earth elements: Vital to modern technologies and lifestyles

USGS Publications Warehouse

Van Gosen, Bradley S.; Verplanck, Philip L.; Long, Keith R.; Gambogi, Joseph; Seal, Robert R.

2014-01-01

Until recently, the rare-earth elements (REEs) were familiar to a relatively small number of people, such as chemists, geologists, specialized materials scientists, and engineers. In the 21st century, the REEs have gained visibility through many media outlets because of (1) the public has recognized the critical, specialized properties that REEs contribute to modern technology, as well as (2) China's dominance in production and supply of the REEs and (3) international dependence on China for the majority of the world's REE supply.Since the late 1990s, China has provided 85–95 percent of the world’s REEs. In 2010, China announced their intention to reduce REE exports. During this timeframe, REE use increased substantially. REEs are used as components in high technology devices, including smart phones, digital cameras, computer hard disks, fluorescent and light-emitting-diode (LED) lights, flat screen televisions, computer monitors, and electronic displays. Large quantities of some REEs are used in clean energy and defense technologies. Because of the many important uses of REEs, nations dependent on new technologies, such as Japan, the United States, and members of the European Union, reacted with great concern to China’s intent to reduce its REE exports. Consequently, exploration activities intent on discovering economic deposits of REEs and bringing them into production have increased.

Sustainability of rare earth elements chain: from production to food - a review.

PubMed

Turra, Christian

2018-02-01

Rare earth elements (REE) are a group of chemical elements that include lanthanoids (lanthanum to lutetium), scandium and yttrium. In the last decades, the REE demand in the industry and other areas has increased significantly. In general, REE have shown low concentrations in soils, plants, water and atmosphere, but they may accumulate in such environments due to anthropogenic inputs. In areas where there is REE contamination, the slow accumulation of these elements in the environment could become problematic. Many studies have shown environmental areas contaminated with REE and their toxic effects. Thus, it is important to review, in order to improve the current understanding of these elements in the environment, showing the effects of REE exposure in mining, soil, water, plants and food. Besides, there are few suppliers and a limited quantity of these elements in the world. This paper suggests options to improve the sustainability management of REE chain.

Rare earth elements in fine-grained sediments of major rivers from the high-standing island of Taiwan

NASA Astrophysics Data System (ADS)

Li, Chuan-Shun; Shi, Xue-Fa; Kao, Shuh-Ji; Liu, Yan-Guang; Lyu, Hua-Hua; Zou, Jian-Jun; Liu, Sheng-Fa; Qiao, Shu-Qing

2013-06-01

Thirty-eight sediment samples from 15 primary rivers on Taiwan were retrieved to characterize the rare earth element (REE) signature of fluvial fine sediment sources. Compared to the three large rivers on the Chinese mainland, distinct differences were observed in the REE contents, upper continental crust normalized patterns and fractionation factors of the sediment samples. The average REE concentrations of the Taiwanese river sediments are higher than those of the Changjiang and Huanghe, but lower than the Zhujiang. Light rare earth elements (LREEs) are enriched relative to heavy rare earth elements (HREEs) with ratios from 7.48 to 13.03. We found that the variations in (La/Lu)UCC-(Gd/Lu)UCC and (La/Yb)UCC-(Gd/Yb)UCC are good proxies for tracing the source sediments of Taiwanese and Chinese rivers due to their distinguishable values. Our analyses indicate that the REE compositions of Taiwanese river sediments were primarily determined by the properties of the bedrock, and the intensity of chemical weathering in the drainage areas. The relatively high relief and heavy rainfall also have caused the REEs in the fluvial sediments from Taiwan to be transported to the estuaries down rivers from the mountains, and in turn delivered nearly coincidently to the adjacent seas by currents and waves. Our studies suggest that the REE patterns of the river sediments from Taiwan are distinguishable from those from the other sources of sediments transported into the adjacent seas, and therefore are useful proxies for tracing the provenances and dispersal patterns of sediments, as well as paleoenvironmental changes in the marginal seas.

The adsorption of rare earth ions using carbonized polydopamine nano shells

DOE PAGES

Sun, Xiaoqi; Luo, Huimin; Mahurin, Shannon Mark; ...

2016-01-07

Herein we report the structure effects of nano carbon shells prepared by carbonized polydopamine for rare earth elements (REEs) adsorption for the first time. The solid carbon sphere, 60 nm carbon shell and 500 nm carbon shell were prepared and investigated for adsorption and desorption of REEs. The adsorption of carbon shells for REEs was found to be better than the solid carbon sphere. The effect of acidities on the adsorption and desorption properties was discussed in this study. The good adsorption performance of carbon shells can be attributed to their porous structure, large specific surface area, amine group andmore » carbonyl group of dopamine.« less

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 (ΣREE) 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rare earth element deposits in China

USGS Publications Warehouse

Xie, Yu-Ling; Hou, Zeng-qian; Goldfarb, Richard J.; Guo, Xiang; Wang, Lei

2016-01-01

China is the world’s leading rare earth element (REE) producer and hosts a variety of deposit types. Carbonatite- related REE deposits, the most significant deposit type, include two giant deposits presently being mined in China, Bayan Obo and Maoniuping, the first and third largest deposits of this type in the world, respectively. The carbonatite-related deposits host the majority of China’s REE resource and are the primary supplier of the world’s light REE. The REE-bearing clay deposits, or ion adsorption-type deposits, are second in importance and are the main source in China for heavy REE resources. Other REE resources include those within monazite or xenotime placers, beach placers, alkaline granites, pegmatites, and hydrothermal veins, as well as some additional deposit types in which REE are recovered as by-products. Carbonatite-related REE deposits in China occur along craton margins, both in rifts (e.g., Bayan Obo) and in reactivated transpressional margins (e.g., Maoniuping). They comprise those along the northern, eastern, and southern margins of the North China block, and along the western margin of the Yangtze block. Major structural features along the craton margins provide first-order controls for REE-related Proterozoic to Cenozoic carbonatite alkaline complexes; these are emplaced in continental margin rifts or strike-slip faults. The ion adsorption-type REE deposits, mainly situated in the South China block, are genetically linked to the weathering of granite and, less commonly, volcanic rocks and lamprophyres. Indosinian (early Mesozoic) and Yanshanian (late Mesozoic) granites are the most important parent rocks for these REE deposits, although Caledonian (early Paleozoic) granites are also of local importance. The primary REE enrichment is hosted in various mineral phases in the igneous rocks and, during the weathering process, the REE are released and adsorbed by clay minerals in the weathering profile. Currently, these REE-rich clays are

Rare earth elements in Hamersley BIF minerals

NASA Astrophysics Data System (ADS)

Alibert, Chantal

2016-07-01

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

Rare earth element transfer from soil to navel orange pulp (Citrus sinensis Osbeck cv. Newhall) and the effects on internal fruit quality.

PubMed

Cheng, Jinjin; Ding, Changfeng; Li, Xiaogang; Zhang, Taolin; Wang, Xingxiang

2015-01-01

The effects of soil rare earth element (REE) on navel orange quality and safety in rare earth ore areas have gained great attention. This study investigated the transfer characteristics of REE from soil to navel orange pulp (Citrus sinensis Osbeck cv. Newhall) and examined the effects of soil REE on internal fruit quality in Xinfeng County, Jiangxi province, China. Path analysis showed that soil REE, pH, cation exchange capacity (CEC), and Fe oxide (Feox) significantly affected pulp REE concentrations. A Freundlich-type prediction model for pulp REE was established: log[REEpulp] = -1.036 + 0.272 log[REEsoil] - 0.056 pH - 0.360 log[CEC] + 0.370 log[Feox] (n = 114, R2 = 0.60). From the prediction model, it was inferred that even when soil REE and Feox were as high as 1038 mg kg-1 and 96.4 g kg-1, respectively, and pH and CEC were as low as 3.75 and 5.08 cmol kg-1, respectively, pulp REE concentrations were much lower than the food limit standard. Additionally, soil REE levels were significantly correlated with selected fruit quality indicators, including titratable acidity (r = 0.52, P < 0.01), total soluble solids (r = 0.48, P < 0.01) and vitamin C (r = 0.56, P < 0.01). Generally, under routine methods of water and fertilization management, the cultivation of navel oranges in rare earth ore areas of south China with soil REE ranging from 38.6 to 546 mg kg-1 had improved in internal fruit quality.

Rare Earth Element Transfer from Soil to Navel Orange Pulp (Citrus sinensis Osbeck cv. Newhall) and the Effects on Internal Fruit Quality

PubMed Central

Cheng, Jinjin; Ding, Changfeng; Li, Xiaogang; Zhang, Taolin; Wang, Xingxiang

2015-01-01

The effects of soil rare earth element (REE) on navel orange quality and safety in rare earth ore areas have gained great attention. This study investigated the transfer characteristics of REE from soil to navel orange pulp (Citrus sinensis Osbeck cv. Newhall) and examined the effects of soil REE on internal fruit quality in Xinfeng County, Jiangxi province, China. Path analysis showed that soil REE, pH, cation exchange capacity (CEC), and Fe oxide (Feox) significantly affected pulp REE concentrations. A Freundlich-type prediction model for pulp REE was established: log[REEpulp] = -1.036 + 0.272 log[REEsoil] - 0.056 pH - 0.360 log[CEC] + 0.370 log[Feox] (n = 114, R2 = 0.60). From the prediction model, it was inferred that even when soil REE and Feox were as high as 1038 mg kg-1 and 96.4 g kg-1, respectively, and pH and CEC were as low as 3.75 and 5.08 cmol kg-1, respectively, pulp REE concentrations were much lower than the food limit standard. Additionally, soil REE levels were significantly correlated with selected fruit quality indicators, including titratable acidity (r = 0.52, P < 0.01), total soluble solids (r = 0.48, P < 0.01) and vitamin C (r = 0.56, P < 0.01). Generally, under routine methods of water and fertilization management, the cultivation of navel oranges in rare earth ore areas of south China with soil REE ranging from 38.6 to 546 mg kg-1 had improved in internal fruit quality. PMID:25806821

Sorption of the Rare Earth Elements and Yttrium (REE-Y) in calcite: the mechanism of a new effective tool in identifying paleoearthquakes on carbonate faults

NASA Astrophysics Data System (ADS)

Moraetis, Daniel; Mouslopoulou, Vasiliki; Pratikakis, Alexandros

2015-04-01

A new tool for identifying paleoearthquakes on carbonate faults has been successfully tested on two carbonate faults in southern Europe (the Magnola Fault in Italy and the Spili Fault in Greece): the Rare Earth Element and Yttrium (REE-Y) method (Manighetti et al., 2010; Mouslopoulou et al., 2011). The method is based on the property of the calcite in limestone scarps to absorb the REE and Y from the soil during its residence beneath the ground surface (e.g. before its exhumation due to earthquakes). Although the method is established, the details of the enrichment mechanism are poorly investigated. Here we use published data together with new information from pot-experiments to shed light on the sorption mechanism and the time effectiveness of the REE-Y method. Data from the Magnola and Spili faults show that the average chemical enrichment is ~45%, in REE-Y while the denudation rate of the enriched zones is ~1% higher every 400 years due to exposure of the fault scarp in weathering. They also show that the chemical enrichment is significant even for short periods of residence time (e.g., ~100 years). To better understand the enrichment mechanism, we performed a series of pot experiments, where carbonate tiles extracted from the Spili Fault were buried into soil collected from the hanging-wall of the same fault. We irrigated the pots with artificial rain that equals 5 years of rainfall in Crete and at temperatures of 15oC and 25oC. Following, we performed sorption isotherm, kinetic and pH-edge tests for the europium (Eu), the cerium (Ce) and the ytterbium (Yt) that occur in the calcite minerals. The processes of adsorption and precipitation in the batch experiments are simulated by the Mineql software. The pot experiments indicate incorporation of the REE and Y into the surface of the carbonate tile which is in contact with the soil. The pH of the leached solution during the rain application range from 7.6 to 8.3. Nutrient release like Ca is higher in the leached

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.

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. 

Rare earth element mobility in vesicular lava during low-grade metamorphism

NASA Astrophysics Data System (ADS)

Nyström, Jan Olov

1984-12-01

A geochemical comparison of basaltic relicts and spilitic domains from two burial metamorphosed flows in central Chile, of similar original composition and rich and poor in amygdules, respectively, demonstrates a relationship between initial vesicularity and rare earth element (REE) mobility. During spilitization the REE were partly leached from permeable parts of the flows and precipitated in voids, now amygdules and veinlets. The REE (excluding Eu) moved coherently in the highly amygdaloidal flow: spilitic domains and amygdules inherited the basaltic REE pattern. Besides being characterized by a positive Eu anomaly, epidotes separated from amygdules have a REE distribution which mimics that of the basalt; the absolute contents range widely, suggesting local and/or temporal REE variations in the metamorphic fluids. Pumpellyite differs by being strongly enriched in heavy REE. Similar ratios of Th, Hf and Ta in samples as contrasting as relict basalt and a geode are consistent with coherent leaching. Coherent mobility, when established for a rock system, can be used to elucidate, for example, whether minerals in cross-cutting veins were formed by local redistribution or from introduced material.

Rare-earth elements in human colostrum milk.

PubMed

Poniedziałek, Barbara; Rzymski, Paweł; Pięt, Małgorzata; Niedzielski, Przemysław; Mleczek, Mirosław; Wilczak, Maciej; Rzymski, Piotr

2017-11-01

Rare-earth elements (REEs) are used in a growing number of applications, and their release to environment has increased over the decades. Knowledge of REEs in human milk and factors that could possibly influence their concentration is scarce. This study evaluated the concentrations of 16 REEs (Ce, Eu, Er, Gd, La, Nd, Pr, Sc, Sm, Dy, Ho, Lu, Tb, Tm, Y, and Yb) in human colostrum milk collected from Polish women (n = 100) with the ICP-OES technique. The concentrations (mean ± SD) of Pr (41.9 ± 13.2 μg L -1 ), Nd (11.0 ± 4.0 μg L -1 ), La (7.1 ± 5.2 μg L -1 ), and Er (2.2 ± 0.8 μg L -1 ) were found above detection limits. The total mean ± SD concentration of detected REEs was 60.9 ± 17.8 μg L -1 . Current smokers displayed significantly increased Nd concentrations compared to women who had never smoked. No other associations between REEs in colostrum milk and age, diet in pregnancy (food supplement use and frequency of fish, meat, and vegetable consumption) or place of living (urban/rural) were found. This study adds to general understanding of the occurrence and turnover of REEs in women and human fluids.

Rare earths in the Leadville Limestone and its marble derivates

USGS Publications Warehouse

Jarvis, J.C.; Wildeman, T.R.; Banks, N.G.

1975-01-01

Samples of unaltered and metamorphosed Leadville Limestone (Mississippian, Colorado) were analyzed by neutron activation for ten rare-earth elements (REE). The total abundance of the REE in the least-altered limestone is 4-12 ppm, and their distribution patterns are believed to be dominated by the carbonate minerals. The abundances of the REE in the marbles and their sedimentary precursors are comparable, but the distribution patterns are not. Eu is enriched over the other REE in the marbles, and stratigraphically upward in the formation (samples located progressively further from the heat source), the light REE become less enriched relative to the heavy REE. The Eu anomaly is attributed to its ability, unique among the REE, to change from the 3+ to 2+ oxidation state. Whether this results in preferential mobilization of the other REE or whether this reflects the composition of the pore fluid during metamorphism is unknown. Stratigraphically selective depletion of the heavy REE may be attributed to more competition for the REE between fluid and carbonate minerals in the lower strata relative to the upper strata. This competition could have been caused by changes in the temperature of the pore fluid or to the greater resistance to solution of the dolomite in the lower parts of the formation than the calcite in the upper parts. ?? 1975.

The behavior of rare earth elements in naturally and anthropogenically acidified waters

USGS Publications Warehouse

Wood, Scott A.; Gammons, Christopher H.; Parker, Stephen R.

2006-01-01

In this paper, the behavior of rare earth elements (REE) in a watershed impacted by acid-mine drainage (Fisher Creek, Montana) is compared to that in a volcanically acidified watershed (Rio Agrio and Lake Caviahue, Argentina). The REE behave conservatively in acidic waters with pH values less than approximately 5.5. However, above pH 5.5, REE concentrations are controlled by adsorption onto or co-precipitation with a variety of Fe or Al oxyhydroxides. The heavy REE partition to a greater extent into the solid phase than the light REE as pH rises above 6. Concentrations of REE exhibit diel (24-h) cycling in waters that were initially acidic, but have become neutralized downstream. In Fisher Creek, at the most downstream sampling station investigated (pH 6.8), concentrations of dissolved REE were 190–840% higher in the early morning versus the late afternoon. This cycling can be related to temperature-dependent, cyclic adsorption–desorption of REE onto hydrous ferric or aluminum oxide or both. Similar but gentler diel cycling of the REE was found at Rio Agrio. The existence of such cycling has important ramifications for the study of REE in natural waters.

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pagano, Giovanni, E-mail: gbpagano@tin.it; Guida, Marco; Siciliano, Antonietta

Background: Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. Methods: Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. Results: REEs affectedmore » P. lividus larvae with concentration-related increase in developmental defects, 10{sup −6} to 10{sup −4} M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10{sup −5} to 10{sup −4} M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. Conclusion: REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies. - Highlights: • Seven rare earth elements exerted different effects on sea urchin early life stages. • Embryo-, spermio- and mitotoxicity, and oxidative/ nitrosative stress were found. • Nominal vs. analytical REE concentrations were checked. • Comparative toxicities were evaluated for the different REE.« less

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.

Rare earth elements in German soils - A review.

PubMed

Mihajlovic, Julia; Rinklebe, Jörg

2018-08-01

Rare earth elements (REEs) are increasingly used in high-tech industry, agriculture, and healthcare technologies what leads to their release into soils and waters, and to the transfer into plants what may have negative impacts on human health and the environment. The toxicity and potential mobilization of REEs in soils can be assessed by their content and geochemical behavior along with soil properties. However, those interactions are so far not reviewed in German soils although such a review is important for a better understanding and prediction of the potential mobilization and toxicity. Therefore, this review summarizes the recent knowledge about REE contents and potential mobilization in different soil profiles in Germany. We found that the REE content tends to decrease in dependence on the parent material in the following order: Carbonatite > basalt > orthogneiss > clay slate > loess > sandstone > Pleistocene and Holocene sediments > organic material. Also, we used data of earlier studies, summarized and newly evaluated those data aiming to quantify the factors influencing the total REE content in German soil profiles. The contents of REEs in soil profiles of different parent material showed significant relations with content of clay, carbonate, organic matter, aluminium, iron, and manganese. Geochemical fractionation results suggest that the bioavailability of REEs is relatively low while the residual fraction is relatively high in German soils. In soils, where water fluctuations are important, the redox potential is a key factor controlling the mobilization of REEs also via related changes of pH. Copyright © 2018 Elsevier Ltd. All rights reserved.

Leaching behavior of rare earth elements in fort union lignite coals of North America

DOE PAGES

Laudal, Daniel A.; Benson, Steven A.; Addleman, Raymond Shane; ...

2018-03-30

Fort Union lignite coal samples were subjected to a series of aqueous leaching experiments to understand the extraction behavior of the rare earth elements (REE). This testing was aimed at understanding the modes of occurrence of the REE in the lignite coals, as well as to provide foundational data for development of rare earth extraction processes. In a first series of tests, a sequential leaching process was used to investigate modes of occurrence of the REE of select lignite coals. The tests involved sequential exposure to solvents consisting of water, ammonium acetate and dilute hydrochloric acid (HCl). The results indicatedmore » that water and ammonium acetate extracted very little of the REE, indicating the REE are not present as water soluble or ion-exchangeable forms. However, the data shows that a large percentage of the REE were extracted with the hydrochloric acid (80–95 wt%), suggesting presence in HCl-soluble mineral forms such as carbonates, and/or presence as organic complexes. A second series of tests was performed involving single-step leaching with dilute acids and various operating parameters, including acid type, acid concentration, acid/coal contact time and coal particle size. For select samples, additional tests were performed to understand the results of leaching, including float-sink density separations and humic acid extraction. The results have shown that the majority of REE in Fort Union lignites appear to be associated weakly with the organic matrix of the coals, most likely as coordination complexes of carboxylic acid groups. The light REE and heavy REE exhibit different behaviors, however. The extractable light REE appear to have association both in acid-soluble mineral forms and as organic complexes, whereas the extractable heavy REE appear to be almost solely associated with the organics. In conclusion, scandium behavior was notably different than yttrium and the lanthanides, and the data suggests the extractable content is

Leaching behavior of rare earth elements in fort union lignite coals of North America

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laudal, Daniel A.; Benson, Steven A.; Addleman, Raymond Shane

Fort Union lignite coal samples were subjected to a series of aqueous leaching experiments to understand the extraction behavior of the rare earth elements (REE). This testing was aimed at understanding the modes of occurrence of the REE in the lignite coals, as well as to provide foundational data for development of rare earth extraction processes. In a first series of tests, a sequential leaching process was used to investigate modes of occurrence of the REE of select lignite coals. The tests involved sequential exposure to solvents consisting of water, ammonium acetate and dilute hydrochloric acid (HCl). The results indicatedmore » that water and ammonium acetate extracted very little of the REE, indicating the REE are not present as water soluble or ion-exchangeable forms. However, the data shows that a large percentage of the REE were extracted with the hydrochloric acid (80–95 wt%), suggesting presence in HCl-soluble mineral forms such as carbonates, and/or presence as organic complexes. A second series of tests was performed involving single-step leaching with dilute acids and various operating parameters, including acid type, acid concentration, acid/coal contact time and coal particle size. For select samples, additional tests were performed to understand the results of leaching, including float-sink density separations and humic acid extraction. The results have shown that the majority of REE in Fort Union lignites appear to be associated weakly with the organic matrix of the coals, most likely as coordination complexes of carboxylic acid groups. The light REE and heavy REE exhibit different behaviors, however. The extractable light REE appear to have association both in acid-soluble mineral forms and as organic complexes, whereas the extractable heavy REE appear to be almost solely associated with the organics. In conclusion, scandium behavior was notably different than yttrium and the lanthanides, and the data suggests the extractable content is

Mobility of rare earth element in hydrothermal process and weathering product: a review

NASA Astrophysics Data System (ADS)

Lintjewas, L.; Setiawan, I.

2018-02-01

The Rare Earth Element (REE), consists of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Lu, Ho, Er, Tm, Yb, are important elements to be used as raw materials of advanced technology such as semiconductors, magnets, and lasers. The research of REE in Indonesia has not been done. Several researches were conducted on granitic rocks and weathering product such as Bangka, Sibolga, West Kalimantan, West Sulawesi and Papua. REE can be formed by hydrothermal processes such as Bayan Obo, South China. The REE study on active hydrothermal system (geothermal) in this case also has the potential to produce mineral deposits. The purpose of this review paper is to know the mobility of REE on hydrothermal process and weathering products. Mobility of REE in the hydrothermal process can change the distribution patterns and REE content such as Ce, Eu, La, Lu, Nd, Sm, and Y. Another process besides the hydrothermal is weathering process. REE mobility is influenced by weathering products, where the REE will experience residual and secondary enrichment processes in heavier minerals.

African Dust Transport Captured by Rare Earth Elemental Concentrations in Coral Microatolls

NASA Astrophysics Data System (ADS)

Ouellette, G., Jr.; DeLong, K.; Herrmann, A.; Huang, C. Y.; Shen, C. C.

2017-12-01

Winds are integral components of the climate system; unfortunately, windsare also among the climate variables that are most difficult to study prior to the instrumentalrecord. Paleoclimatologists use sedimentary dust records (e.g., lake and ocean cores) tounderstand past wind circulation conditions; however, these types of records typically are notamenable to sub-annual interpretation due to their limited temporal resolution. Here wedeveloped a coral-based dust-wind proxy to overcome these temporal limitations by usingtrace (nmol/mol) rare earth elemental concentrations recorded in the skeletons of coralmicroatolls. The rare earth elements (REE; the lanthanides as well as scandium and yttrium)behave similarly in geologic and geochemical systems, and have served as useful proxies ofgeological processes in both deep and shallow time. Corals incorporate REE as they deposittheir exoskeletons that extend incrementally with time forming annual density band couplets.Coral microatolls grow at or near the sea surface, where coral REE concentrations are mostsensitive to dust deposition. Our study site off the west coast of Haiti is down stream of light-REE depleted bedrock whereas REE in African dust, transported by the easterly trade winds,reflect average crustal abundances. This unique "upstream" source signature allows forterrestrial contamination of the dust-wind signal to be ruled out. Light REE concentrations (esp.Nd and Pr) demonstrate an order of magnitude increase within coral aragonite coincident withmajor African dust plume events throughout the past decade, with Nd/Ca and Pr/Ca increasingfrom an average of 27 nmol/mol to an average 144 nmol/mol and an average of 5 nmol/mol toan average of 37 nmol/mol, respectively, during major African dust plume events. Monthly-resolved REE analysis shows these REE peaks coincide with the summer dust season rather thanHaiti's two wet seasons in spring and autumn. Regression of our coral REE dust proxy tosatellite records of

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Hydrothermal transport and deposition of the rare earth elements by fluorine-bearing aqueous liquids

NASA Astrophysics Data System (ADS)

Migdisov, Art A.; Williams-Jones, A. E.

2014-12-01

New technologies, particularly those designed to address environmental concerns, have created a great demand for the rare earth elements (REE), and focused considerable attention on the processes by which they are concentrated to economically exploitable levels in the Earth's crust. There is widespread agreement that hydrothermal fluids played an important role in the formation of the world's largest economic REE deposit, i.e. Bayan Obo, China. Until recently, many researchers have assumed that hydrothermal transport of the REE in fluorine-bearing ore-forming systems occurs mainly due to the formation of REE-fluoride complexes. Consequently, hydrothermal models for REE concentration have commonly involved depositional mechanisms based on saturation of the fluid with REE minerals due to destabilization of REE-fluoride complexes. Here, we demonstrate that these complexes are insignificant in REE transport, and that the above models are therefore flawed. The strong association of H+ and F- as HF° and low solubility of REE-F solids greatly limit transport of the REE as fluoride complexes. However, this limitation does not apply to REE-chloride complexes. Because of this, the high concentration of Cl- in the ore fluids, and the relatively high stability of REE-chloride complexes, the latter can transport appreciable concentrations of REE at low pH. The limitation also does not apply to sulphate complexes and in some fluids, the concentration of sulphate may be sufficient to transport significant concentrations of REE as sulphate complexes, particularly at weakly acidic pH. This article proposes new models for hydrothermal REE deposition based on the transport of the REE as chloride and sulphate complexes.

Trade Group Rules Against China in Rare Earths Dispute

NASA Astrophysics Data System (ADS)

Showstack, Randy

2014-04-01

The World Trade Organization (WTO) has ruled against China in a trade dispute over rare earth elements (REE) as well as tungsten and molybdenum, the group announced on 26 March. The European Union, Japan, and the United States brought trade cases against China in March 2012 concerning alleged unfair export restraints on the materials (see Eos, 93(13), 134-135, doi:10.1029/2012EO130002).

Preliminary estimates of the quantities of rare-earth elements contained in selected products and in imports of semimanufactured products to the United States, 2010

USGS Publications Warehouse

Bleiwas, Donald I.; Gambogi, Joseph

2013-01-01

Rare-earth elements (REEs) are contained in a wide range of products of economic and strategic importance to the Nation. The REEs may or may not represent a significant component of that product by mass, value, or volume; however, in many cases, the embedded REEs are critical for the device’s function. Domestic sources of primary supply and the manufacturing facilities to produce products are inadequate to meet U.S. requirements; therefore, a significant percentage of the supply of REEs and the products that contain them are imported to the United States. In 2011, mines in China produced roughly 97 percent of the world’s supply of REEs, and the country’s production of these elements will likely dominate global supply until at least 2020. Preliminary estimates of the types and amount of rare-earth elements, reported as oxides, in semimanufactured form and the amounts used for electric vehicle batteries, catalytic converters, computers, and other applications were developed to provide a perspective on the Nation’s use of these elements. The amount of rare-earth metals recovered from recycling, remanufacturing, and reuse is negligible when the tonnage of products that contain REEs deposited in landfills and retained in storage is considered. Under favorable market conditions, the recovery of REEs from obsolete products could potentially displace a portion of the supply from primary sources.

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

Analysis of low levels of rare earths by radiochemical neutron activation analysis

USGS Publications Warehouse

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

1985-01-01

A procedure for the radiochemical neutron-activation analysis for the rare earth elements (REE) involves the separation of the REE as a group by rapid ion-exchange methods and determination of yields by reactivation or by energy dispersive X-ray fluorescence (EDXRF) spectrometry. The U. S. Geological Survey (USGS) standard rocks, BCR-1 and AGV-1, were analyzed to determine the precision and accuracy of the method. We found that the precision was ??5-10% on the basis of replicate analysis and that, in general the accuracy was within ??5% of accepted values for most REE. Data for USGS standard rocks BIR-1 (Icelandic basalt) and DNC-1 (North Carolina diabase) are also presented. ?? 1985 Akade??miai Kiado??.

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...

Direct dating and characterization of the Pope's Hill REE Deposit, Labrador

NASA Astrophysics Data System (ADS)

Chafe, A. N.; Hanchar, J. M.; Fisher, C.; Piccoli, P. M.; Crowley, J. L.; Dimmell, P. M.

2012-12-01

The Pope's Hill rare earth element (REE) trend (PHT) is located approximately 100 km southwest of Happy Valley-Goose Bay, along the Trans Labrador Highway, in central Labrador. Whole-rock geochemical analyses of the main REE-bearing unit indicate total rare earth element contents ranging from 1 to 22 weight percent (wt%) REE3+. The REE-enriched unit is hosted within a hydrothermally altered syenite, trending northeast and traceable for approximately 2.8km. Samples of ore, host rock, and country rock, were collected from throughout the trend in order to: 1) quantify which phases concentrate the REE and their abundances and distribution in the ore; and 2) use in situ LA-ICPMS and ID-TIMS U-Pb geochronology and in situ Sm-Nd isotopes using LA-MC-ICPMS in monazite from the ore and host rock to constrain the timing of mineralization and determine the source of the REE. These data will help develop predictive models for this type of mineral deposit elsewhere. The PHT is defined as the host syenite and REE-enriched segregations; two contrasting lithologies. The rare earth element minerals (REE) occur in millimeter- to centimeter-scale pods that are locally discontinuous. The REE are hosted in a variety of silicate, phosphate, carbonate, and niobate phases; with a majority hosted in allanite(-Ce), titanite(-Ce), monazite(-Ce), britholite(-Ce); and a minor percentage in REE-carbonates and fergusonite(-Nd). Both apatite and titanite occur in two different compositional forms that range in chemistry from end-member stoichiometric apatite and titanite to highly REE-enriched - apatite-britholite and titanite(-Ce), where chemical substitutions, such as Si4+ + REE3+ substitute for Ca2+ + P5+ in apatite and REE3+ + Fe3+ substitute for Ca2+ + Ti4+ in titanite in order to incorporate up to ~40 wt% REE2O3 in both minerals. The U-Pb geochronology indicate that allanite, titanite(-Ce), monazite and fergusonite crystallized from ~1060 to ~940 Ma, a period spanning ~120 Ma. Sm-Nd tracer

An impact of moss sample cleaning on uncertainty of analytical measurement and pattern profiles of rare earth elements.

PubMed

Dołęgowska, Sabina; Gałuszka, Agnieszka; Migaszewski, Zdzisław M

2017-12-01

The main source of rare earth elements (REE) in mosses is atmospheric deposition of particles. Sample treatment operations including shaking, rinsing or washing, which are made in a standard way on moss samples prior to chemical analysis, may lead to removing particles adsorbed onto their tissues. This in turn causes differences in REE concentrations in treated and untreated samples. For the present study, 27 combined moss samples were collected within three wooded areas and prepared for REE determinations by ICP-MS using both manual cleaning by shaking and triple rinsing with deionized water. Higher concentrations of REE were found in manually cleaned samples. The comparison of REE signatures and shale-normalized REE concentration patterns showed that the treatment procedure did not lead to fractionation of REE. All the samples were enriched in medium rare earth elements, and the δMREE factor remained practically unchanged after rinsing. Positive anomalies of Nd, Sm, Eu, Gd, Er and Yb were observed in both, manually cleaned and rinsed samples. For all the elements examined, analytical uncertainty was below 3.0% whereas sample preparation uncertainty computed with ANOVA, RANOVA, modified RANOVA and range statistics methods varied from 3.5 to 29.7%. In most cases the lowest s rprep values were obtained with the modified RANOVA method. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rare earth elements (REE) as natural and applied tracers in the catchment area of Gessental valley, former uranium mining area of Eastern Thuringia, Germany

NASA Astrophysics Data System (ADS)

Buechel, G.; Merten, D.; Geletneky, J. W.; Kothe, E.

2003-04-01

Between 1947 and 1990 about 113.000 t of uranium were excavated at the former uranium mining site of Ronneburg (Eastern Thuringia, Germany). The legacy consists of more than 200 million m^3 of metasedimentary rocks rich in organic matter, sulfides and heavy metals originally deposited in mining heaps at the surface. The metasedimentary rocks formed under anoxic conditions about a 400 Mio. years ago are now exposed to oxic conditions. The oxidation of markasite and pyrite results in the formation of H_2SO_4. The formation of acid mine drainage (AMD) leads to high concentrations of uranium, rare earth elements (REE) and other heavy metals in surface water, seepage water and groundwater. This mobilization is due to alteration enhanced by high microbial activity and low pH. The tolerance mechanisms towards heavy metal pollution of soil substrate and surface/groundwater has allowed the selection of microbes which have, e.g. specific transporter genes and which are associated to plants in symbiotic interactions like mycorrhiza. In order to follow the processes linking alteration of metasedimentary rocks to biological systems the use of tracers is needed. One group of such tracers occuring in high concentrations in the water phase at the Ronneburg mining site are the REE (La-Lu) which are featured by very similar chemical behaviour. They show smooth but continuous variations of their chemical behaviour as a function of atomic number. For seepage water of the waste rock dump Nordhalde - sampled over a period of two years - the shale normalized REE patterns show enrichment of heavy REE and only minor variations, although the concentration differs. At sampling points in the surface water and in groundwater rather similar REE patterns were observed. Thus, REE can be used as tracers to identify diffuse inflow of REE-rich acid mine drainage of the dumps into the creek and the sediments. The absolute concentrations of REE in the creek and in ground water are up to 1000 times

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

DOE PAGES

Kim, Daejin; Powell, Lawrence E.; Delmau, Lætitia H.; ...

2015-06-24

In this paper, 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 acidmore » 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. Finally, 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.« less

Adsorption of Rare Earths(Ⅲ) Using an Efficient Sodium Alginate Hydrogel Cross-Linked with Poly-γ-Glutamate

PubMed Central

Xu, Shuxia; Wang, Zhiwei; Gao, Yuqian; Zhang, Shimin; Wu, Kun

2015-01-01

With the exploitation of rare earth ore, more and more REEs came into groundwater. This was a waste of resources and could be harmful to the organisms. This study aimed to find an efficient adsorption material to mitigate the above issue. Through doping sodium alginate (SA) with poly-γ-glutamate (PGA), an immobilized gel particle material was produced. The composite exhibited excellent capacity for adsorbing rare earth elements (REEs). The amount of La3+ adsorbed on the SA-PGA gel particles reached approximately 163.93 mg/g compared to the 81.97 mg/g adsorbed on SA alone. The factors that potentially affected the adsorption efficiency of the SA-PGA composite, including the initial concentration of REEs, the adsorbent dosage, and the pH of the solution, were investigated. 15 types of REEs in single and mixed aqueous solutions were used to explore the selective adsorption of REEs on gel particles. Scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy analyses of the SA and SA-PGA gel beads suggested that the carboxyl groups in the composite might play a key role in the adsorption process and the morphology of SA-PGA changed from the compact structure of SA to a porous structure after doping PGA. The kinetics and thermodynamics of the adsorption of REEs were well fit with the pseudo-second-order equation and the Langmuir adsorption isotherm model, respectively. It appears that SA-PGA is useful for recycling REEs from wastewater. PMID:25996388

Revisit of rare earth element fractionation during chemical weathering and river sediment transport

NASA Astrophysics Data System (ADS)

Su, Ni; Yang, Shouye; Guo, Yulong; Yue, Wei; Wang, Xiaodan; Yin, Ping; Huang, Xiangtong

2017-03-01

Although rare earth element (REE) has been widely applied for provenance study and paleoenvironmental reconstruction, its mobility and fractionation during earth surface processes from weathering to sediment deposition remain more clarification. We investigated the REE fractionations during chemical weathering and river sediment transport based on the systematic observations from a granodiorite-weathering profile and Mulanxi River sediments in southeast China. Two chemical phases (leachates and residues) were separated by 1 N HCl leaching and the leachates account for 20-70% of the bulk REE concentration. REEs in the weathering profile have been mobilized and fractionated to different extents during chemical weathering and pedogenesis. Remarkable cerium anomalies (Ce/Ce* = 0.1-10.6) occur during weathering as a result of coprecipitation with Mn (hydro)oxides in the profile, while poor or no Ce anomalies in the river sediments were observed. This contrasting feature sheds new light on the indication of Ce anomaly for redox change. The hydraulic sorting-induced mineral redistribution can further homogenize the weathering and pedogenic alterations and thus weaken the REE fractionations in river sediments. The mineral assemblage is the ultimate control on REE composition, and the Mn-Fe (hydro)oxides and secondary phosphate minerals are the main hosts of acid-leachable REEs while the clay minerals could be important reservoirs for residual REEs. We thus suggest that the widely used REE proxies such as (LREE/HREE)UCC ratio in the residues is reliable for the indication of sediment provenance, while the ratio in the leachates can indicate the total weathering process to some extent.

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.

Geochemistry of some rare earth elements in groundwater, Vierlingsbeek, The Netherlands.

PubMed

Janssen, René P T; Verweij, Wilko

2003-03-01

Groundwater samples were taken from seven bore holes at depths ranging from 2 to 41m nearby drinking water pumping station Vierlingsbeek, The Netherlands and analysed for Y, La, Ce, Pr, Nd, Sm and Eu. Shale-normalized patterns were generally flat and showed that the observed rare earth elements (REE) were probably of natural origin. In the shallow groundwaters the REEs were light REE (LREE) enriched, probably caused by binding of LREEs to colloids. To improve understanding of the behaviour of the REE, two approaches were used: calculations of the speciation and a statistical approach. For the speciation calculations, complexation and precipitation reactions including inorganic and dissolved organic carbon (DOC) compounds, were taken into account. The REE speciation showed REE(3+), REE(SO(4))(+), REE(CO(3))(+) and REE(DOC) being the major species. Dissolution of pure REE precipitates and REE-enriched solid phases did not account for the observed REEs in groundwater. Regulation of REE concentrations by adsorption-desorption processes to Fe(III)(OH)(3) and Al(OH)(3) minerals, which were calculated to be present in nearly all groundwaters, is a probable explanation. The statistical approach (multiple linear regression) showed that pH is by far the most significant groundwater characteristic which contributes to the variation in REE concentrations. Also DOC, SO(4), Fe and Al contributed significantly, although to a much lesser extent, to the variation in REE concentrations. This is in line with the calculated REE-species in solution and REE-adsorption to iron and aluminium (hydr)oxides. Regression equations including only pH, were derived to predict REE concentrations in groundwater. External validation showed that these regression equations were reasonably successful to predict REE concentrations of groundwater of another drinking water pumping station in quite different region of The Netherlands.

Determination of Rare Earth Elements in Geological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS).

PubMed

Bhatt, Chet R; Jain, Jinesh C; Goueguel, Christian L; McIntyre, Dustin L; Singh, Jagdish P

2018-01-01

Laser-induced breakdown spectroscopy (LIBS) was used to detect rare earth elements (REEs) in natural geological samples. Low and high intensity emission lines of Ce, La, Nd, Y, Pr, Sm, Eu, Gd, and Dy were identified in the spectra recorded from the samples to claim the presence of these REEs. Multivariate analysis was executed by developing partial least squares regression (PLS-R) models for the quantification of Ce, La, and Nd. Analysis of unknown samples indicated that the prediction results of these samples were found comparable to those obtained by inductively coupled plasma mass spectrometry analysis. Data support that LIBS has potential to quantify REEs in geological minerals/ores.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John

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

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

DOE PAGES

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John; ...

2015-06-26

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

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.

A simple enrichment correction factor for improving erosion estimation by rare earth oxide tracers

USDA-ARS?s Scientific Manuscript database

Spatially distributed soil erosion data are needed to better understanding soil erosion processes and validating distributed erosion models. Rare earth element (REE) oxides were used to generate spatial erosion data. However, a general concern on the accuracy of the technique arose due to selective ...

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...

Interactions of phosphate solubilising microorganisms with natural rare-earth phosphate minerals: a study utilizing Western Australian monazite.

PubMed

Corbett, Melissa K; Eksteen, Jacques J; Niu, Xi-Zhi; Croue, Jean-Philippe; Watkin, Elizabeth L J

2017-06-01

Many microbial species are capable of solubilising insoluble forms of phosphate and are used in agriculture to improve plant growth. In this study, we apply the use of known phosphate solubilising microbes (PSM) to the release of rare-earth elements (REE) from the rare-earth phosphate mineral, monazite. Two sources of monazite were used, a weathered monazite and mineral sand monazite, both from Western Australia. When incubated with PSM, the REE were preferentially released into the leachate. Penicillum sp. released a total concentration of 12.32 mg L -1 rare-earth elements (Ce, La, Nd, and Pr) from the weathered monazite after 192 h with little release of thorium and iron into solution. However, cultivation on the mineral sands monazite resulted in the preferential release of Fe and Th. Analysis of the leachate detected the production of numerous low-molecular weight organic acids. Gluconic acid was produced by all microorganisms; however, other organic acids produced differed between microbes and the monazite source provided. Abiotic leaching with equivalent combinations of organic acids resulted in the lower release of REE implying that other microbial processes are playing a role in solubilisation of the monazite ore. This study demonstrates that microbial solubilisation of monazite is promising; however, the extent of the reaction is highly dependent on the monazite matrix structure and elemental composition.

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

NASA Astrophysics Data System (ADS)

Tang, Jianwu; Johannesson, Karen H.

2010-12-01

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

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.

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

COST-EFFECTIVE RARE EARTH ELEMENT RECYCLING PROCESS FROM INDUSTRIAL SCRAP AND DISCARDED ELECTRONIC PRODUCTS TO VALUABLE MAGNETIC ALLOYS AND PERMANENT MAGNETS - PHASE II

EPA Science Inventory

Rare earth element (REE) based Nd-Fe-B and Sm-Co permanent magnets have been widely used because of their excellent magnetic properties. The applications of Nd-Fe-B and Sm-Co rare earth permanent magnets include hybrid electric vehicles (HEVs), power generators for wind tur...

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

NASA Astrophysics Data System (ADS)

Wiche, Oliver

2016-04-01

Germanium (Ge) and rare earth elements (REEs) are economically valuable raw materials that have become an integral part of our modern high tech society. While most of these elements are not actually rare in terms of general amounts in the earth's crust, they are rarely found in sufficient abundances in single locations for their mining to be economically viable. The average concentration of Ge in soils is estimated at 1.6 μg g-1. The REEs comprise a group of 16 elements including La, the group of lanthanides and Y that are abundant in the earth crust with concentrations varying from 35 μg g-1 (La), 40 μg g-1 (Nd), 6 μg g-1 (Gd) and 3.5 μg g-1 (Er) to 0.5 μg g-1 in Tm. Thus, a promising chance to improve supply of these elements could be phytomining. Unfortunately, bioavailability of Ge and REEs in soils appears to be low, in particular in neutral or alkaline soils. A sequential dissolution analysis of 120 soil samples taken from the A-horizons of soils in the area of Freiberg (Saxony, Germany) revealed that only 0.2% of total Ge and about 0.5% of La, Nd, Gd and Er of bulk concentrations were easily accessible by leaching with NH4-acetate (pH 7). Most of the investigated elements were bound to Fe-/Mn-oxides and silicates and were therefore only poorly available for plant uptake. Here we report an environmentally friendly approach for enhanced phytoextraction of Ge and REEs from soils using mixed cultures of plant species with efficient mechanisms for the acquisition of nutrients in the rhizosphere. The rhizosphere is characterized as the zone in soil sourrounding a plant root that consists of a gradient in chemical, physical and biological soil properties driven by rhizodeposits like carboxylates and protons. Some species like white lupin (Lupinus albus) are able to excrete large amounts of organic acid anions(predominantly citrate and malate) and show a particularly high potential for the acidification of the rhizosphere. In our experiments, mixed cultures

Rare earth element geochemistry characteristics of seawater and porewater from deep sea in western Pacific.

PubMed

Deng, Yinan; Ren, Jiangbo; Guo, Qingjun; Cao, Jun; Wang, Haifeng; Liu, Chenhui

2017-11-28

Deep-sea sediments contain high concentrations of rare earth element (REE) which have been regarded as a huge potential resource. Understanding the marine REE cycle is important to reveal the mechanism of REE enrichment. In order to determine the geochemistry characteristics and migration processes of REE, seawater, porewater and sediment samples were systematically collected from the western Pacific for REE analysis. The results show a relatively flat REE pattern and the HREE (Heavy REE) enrichment in surface and deep seawater respectively. The HREE enrichment distribution patterns, low concentrations of Mn and Fe and negative Ce anomaly occur in the porewater, and high Mn/Al ratios and low U concentrations were observed in sediment, indicating oxic condition. LREE (Light REE) and MREE (Middle REE) enrichment in upper layer and depletion of MREE in deeper layer were shown in porewater profile. This study suggests that porewater flux in the western Pacific basin is a minor source of REEs to seawater, and abundant REEs are enriched in sediments, which is mainly caused by the extensive oxic condition, low sedimentation rate and strong adsorption capacity of sediments. Hence, the removal of REEs of porewater may result in widespread REE-rich sediments in the western Pacific basin.

Fate and transport of trace metals and rare earth elements in the Snake River, an AMD/ARD-impacted watershed. Montezuma, Colorado USA.

NASA Astrophysics Data System (ADS)

McKnight, D. M.; Rue, G.

2017-12-01

Recent research in Snake River Watershed, located near the historic boomtown of Montezuma and adjacent the Continental Divide in the Colorado Rocky Mountains, has revealed the distinctive occurrence of rare earth elements (REE) at high concentrations. Here the weathering of the mineralized lithology naturally generates acid rock drainage (ARD) in addition to drainage recieved from abandoned mine adits throughout the area, results in aqueous REE concentrations three orders of magnitude higher than in most major rivers. The dominant mechanism responsible for this enrichment; their dissolution from secondary and accessory mineral stocks, abundant in REEs, promoted by the low pH waters generated from geochemical weathering of disseminated sulfide minerals. While REEs behave conservatively in acidic conditions, as well as in the presence of stabilizing ligands such as sulfate, downstream circumneutral inputs from pristine streams and a rising pH are resulting in observed fractional losses of heavy rare earth elements as well as partitioning towards colloidal and solid phases. These finding in combination with the established role of dissolved organic matter (DOM) in binding with both trace metals and REEs, suggest that competitive interactions, complexation, and scavenging are likely contributing to these proportional losses. However, outstanding questions yet remain regarding the effects of an increasing flux of trace metals as well as REEs from the Snake River Watershed into Dillon Reservoir, a major drinking water supply for the City of Denver, in part due to hydroclimatological drivers that are enhancing geochemical weathering and reducing groundwater recharge in alpine areas across the Colorado Rockies. Based on these findings also we seek to broaden this body of work to further investigate the behavior of rare earth elements (REE) in other aquatic environment as well the influence of trace metals, DOM, and pH in altering their reactivity and subsequent watershed

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.

Advanced Characterization of Rare Earth Elements in Coal Utilization Byproducts

NASA Astrophysics Data System (ADS)

Verba, C.; Scott, M.; Dieterich, M.; Poston, J.; Collins, K.

2016-12-01

Rare earth elements (REE) in various forms (e.g., crystalline mineral phases; adsorbed/absorbed state on and into organic macerals, neoformed glass from flyash or bottom ash) from domestic feedstocks such as coal deposits to coal utilization byproducts (CUB) have the potential to reduce foreign REE dependence and increase domestic resource security. Characterization is critical for understanding environmental risks related to their fate and transport as well as determining the most practical and economical techniques for concentrating the REE and converting them into chemical stocks for manufacturing. Several complementary electron microscopy (SEM-EDS, EPMA-WDS, FIB-SEM, cathodoluminescence, and XRD) and post image processing techniques were used to understand REE transition from coal to CUB. Sites of interest were identified and imaged and respective elemental x-ray maps acquired and montaged. Pixel classification of SEM imagers was completed using image analysis techniques to quantify the distribution of REE associated features. Quantitative elemental analysis of phases were completed using EMPA-WDS followed by FIB-SEM. The FIB-SEM results were reconstructed into 3D volumes and features of interest (e.g. monazite) were analyzed to determine the structure and volumetric estimation of REEs and thus predict detrital REE phases to ICP-MS results. Trace minerals were identified as pyrite, zircon, REE-phosphates' (monazite, xenotime), and barite within the coal tailings. In CUB, amorphous aluminosilicates, iron oxide cenospheres, and calcium oxides were present; monazite appear to be unaltered and unaffected by the combustion process in these samples. Thermal decomposition may have occurred due to presence of detrital zircon and xenotime and subsequent thin Ca-oxide coating enriched in trace REEs.

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

USDA-ARS?s Scientific Manuscript database

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...

Levels of rare earth elements, heavy metals and uranium in a population living in Baiyun Obo, Inner Mongolia, China: a pilot study.

PubMed

Hao, Zhe; Li, Yonghua; Li, Hairong; Wei, Binggan; Liao, Xiaoyong; Liang, Tao; Yu, Jiangping

2015-06-01

The Baiyun Obo deposit is the world's largest rare earth elements (REE) deposit. We aimed to investigate levels of REE, heavy metals (HMs) and uranium (U) based on morning urine samples in a population in Baiyun Obo and to assess the possible influence of rare earth mining processes on human exposure. In the mining area, elevated levels were found for the sum of the concentrations of light REE (LREE) and heavy REE (HREE) with mean values at 3.453 and 1.151 μg g(-1) creatinine, which were significantly higher than those in the control area. Concentrations of HMs and U in the population increased concomitantly with increasing REE levels. The results revealed that besides REE, HMs and U were produced with REE exploitation. Gender, age, educational level, alcohol and smoking habit were major factors contributing to inter-individual variation. Males were more exposed to these metals than females. Concentrations in people in the senior age group and those with only primary education were low. Drinking and smoking were associated with the levels of LREE, Cr, Cu, Cd and Pb in morning urine. Hence this study provides basic and useful information when addressing public and environmental health challenges in the areas where REE are mined and processed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of Rare Earth Element Minerals in Coal Utilization Byproducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montross, Scott N.; Verba, Circe A.; Collins, Keith

The United States currently produces over 100 million tons of coal utilization byproducts (CUB) per year in the form of fly ash, bottom ash, slag, and flue gas (American Coal Ash Association (ACCA), 2015). But this “waste material” also contains potentially useful levels of rare earth elements (REE). Rare earth elements are crucial for many existing and emerging technologies, but the U.S. lacks a domestic, sustainable REE source. Our project explored the possibility of developing a supply of REEs for U.S. technologies by extracting REEs from CUBs. This work offers the potential to reduce our dependence on other countries formore » supply of these critical elements (NETL, REE 2016 Project Portfolio). Geologic and diagenetic history, industrial preparation methods, and the specific combustion process all play major roles in the composition of CUB. During combustion, inorganic mineral phases of coal particles are fluidized at temperatures higher than 1400oC, so inorganic mineral materials are oxidized, fused, disintegrated, or agglomerated into larger spherical and amorphous (non-crystalline) particles. The original mineralogy of the coal-containing rock and heating/cooling of the material significantly affects the composition and morphology of the particles in the combustion byproduct (Kutchko and Kim, 2006). Thus, different types of coal/refuse/ash must be characterized to better understand mineral evolution during the combustion process. Our research focused on developing a working model to address how REE minerals behave during the combustion process: this research should help determine the most effective engineering methods for extracting REEs from CUBs. We used multimodal imaging and image processing techniques to characterize six rock and ash samples from different coal power plants with respect to morphology, grain size, presence of mineral phases, and elemental composition. The results of these characterization activities provided thresholds for

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

NASA Astrophysics Data System (ADS)

Elderfield, H.; Hawkesworth, C. J.; Greaves, M. J.; Calvert, S. E.

1981-04-01

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. 143Nd /144Nd ratios in the nodules (˜0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mineralogical controls on mobility of rare earth elements in acid mine drainage environments.

PubMed

Soyol-Erdene, T O; Valente, T; Grande, J A; de la Torre, M L

2018-08-01

Rare earth elements (REE) were analyzed in river waters, acid mine waters, and extracts of secondary precipitates collected in the Iberian Pyrite Belt. The obtained concentrations of the REE in river water and mine waters (acid mine drainage - AMD) were in the range of 0.57 μg/L (Lu) and 2579 μg/L (Ce), which is higher than previously reported in surface waters from the Iberian Pyrite Belt, but are comparable with previous findings from AMD worldwide. Total REE concentrations in river waters were ranged between 297 μg/L (Cobica River) and 7032 μg/L (Trimpancho River) with an average of 2468 μg/L. NASC (North American Shale Composite) normalized REE patterns for river and acid mine waters show clear convex curvatures in middle-REE (MREE) with respect to light- and heavy-REE. During the dissolution experiments of AMD-precipitates, heavy-REE and middle-REE generate the most enriched patterns in the solution. A small number of precipitates did not display MREE enrichment (an index Gd n /Lu n  < 1.0) in NASC normalized pattern and produced relatively lower REE concentrations in extracts. Additionally, very few samples, which mainly contained aluminum sulfates, e.g., pickeringite and alunogen, displayed light-REE enrichment relative to heavy-REE (HREE). In general, the highest retention of REE occurs in samples enriched in magnesium (epsomite or hexahydrite) and aluminum sulfates, mainly pickeringite. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Automated Quantitative Rare Earth Elements Mineralogy by Scanning Electron Microscopy

NASA Astrophysics Data System (ADS)

Sindern, Sven; Meyer, F. Michael

2016-09-01

Increasing industrial demand of rare earth elements (REEs) stems from the central role they play for advanced technologies and the accelerating move away from carbon-based fuels. However, REE production is often hampered by the chemical, mineralogical as well as textural complexity of the ores with a need for better understanding of their salient properties. This is not only essential for in-depth genetic interpretations but also for a robust assessment of ore quality and economic viability. The design of energy and cost-efficient processing of REE ores depends heavily on information about REE element deportment that can be made available employing automated quantitative process mineralogy. Quantitative mineralogy assigns numeric values to compositional and textural properties of mineral matter. Scanning electron microscopy (SEM) combined with a suitable software package for acquisition of backscatter electron and X-ray signals, phase assignment and image analysis is one of the most efficient tools for quantitative mineralogy. The four different SEM-based automated quantitative mineralogy systems, i.e. FEI QEMSCAN and MLA, Tescan TIMA and Zeiss Mineralogic Mining, which are commercially available, are briefly characterized. Using examples of quantitative REE mineralogy, this chapter illustrates capabilities and limitations of automated SEM-based systems. Chemical variability of REE minerals and analytical uncertainty can reduce performance of phase assignment. This is shown for the REE phases parisite and synchysite. In another example from a monazite REE deposit, the quantitative mineralogical parameters surface roughness and mineral association derived from image analysis are applied for automated discrimination of apatite formed in a breakdown reaction of monazite and apatite formed by metamorphism prior to monazite breakdown. SEM-based automated mineralogy fulfils all requirements for characterization of complex unconventional REE ores that will become

Effects of Simulated Rare Earth Recycling Wastewaters on Biological Nitrification.

PubMed

Fujita, Yoshiko; Barnes, Joni; Eslamimanesh, Ali; Lencka, Malgorzata M; Anderko, Andrzej; Riman, Richard E; Navrotsky, Alexandra

2015-08-18

Increasing rare earth element (REE) supplies by recycling and expanded ore processing will result in generation of new wastewaters. In some cases, disposal to a sewage treatment plant may be favored, but plant performance must be maintained. To assess the potential effects of such wastewaters on biological treatment, model nitrifying organisms Nitrosomonas europaea and Nitrobacter winogradskyi were exposed to simulated wastewaters containing varying levels of yttrium or europium (10, 50, and 100 ppm), and the extractant tributyl phosphate (TBP, at 0.1 g/L). Y and Eu additions at 50 and 100 ppm inhibited N. europaea, even when virtually all of the REE was insoluble. Provision of TBP with Eu increased N. europaea inhibition, although TBP alone did not substantially alter activity. For N. winogradskyi cultures, Eu or Y additions at all tested levels induced significant inhibition, and nitrification shut down completely with TBP addition. REE solubility was calculated using the previously developed MSE (Mixed-Solvent Electrolyte) thermodynamic model. The model calculations reveal a strong pH dependence of solubility, typically controlled by the precipitation of REE hydroxides but also likely affected by the formation of unknown phosphate phases, which determined aqueous concentrations experienced by the microorganisms.

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.

Partition coefficients for REE between garnets and liquids - Implications of non-Henry's Law behaviour for models of basalt origin and evolution

NASA Technical Reports Server (NTRS)

Harrison, W. J.

1981-01-01

An experimental investigation of Ce, Sm and Tm rare earth element (REE) partition coefficients between coexisting garnets (both natural and synthetic) and hydrous liquids shows that Henry's Law may not be obeyed over a range of REE concentrations of geological relevance. Systematic differences between the three REE and the two garnet compositions may be explained in terms of the differences between REE ionic radii and those of the dodecahedral site into which they substitute, substantiating the Harrison and Wood (1980) model of altervalent substitution. Model calculations demonstrate that significant variation can occur in the rare earth contents of melts produced from a garnet lherzolite, if Henry's Law partition coefficients do not apply for the garnet phase.

Distribution and source of rare earth elements in PM2.5 in Xiamen, China.

PubMed

Wang, Shanshan; Yu, Ruilian; Hu, Gongren; Hu, Qichao; Zheng, Quan

2017-12-01

Particulate matter with diameter ≤2.5 µm (PM 2.5 ) is a serious atmospheric pollutant. Composition and source analyses are essential for controlling PM 2.5 . Rare earth elements (REEs) have received little attention as a component of PM 2.5 . In the present study, PM 2.5 samples were collected in urban and suburban areas in Xiamen and analyzed for REEs. The concentration range of total REEs (∑REE) is 12.07 to 98.45 mg/kg, with a mean of 38.53 mg/kg, in urban PM 2.5 and 16.44 to 160.62 mg/kg, with a mean of 42.94 mg/kg, in suburban PM 2.5 . Light REE concentrations are higher in suburban PM 2.5 , whereas heavy REE concentrations are higher in urban PM 2.5 , implying distinct sources of REEs in urban and suburban PM 2.5 . The scatter plots of δEu-∑REE and La-Ce-Sm suggest that REEs in urban PM 2.5 originate from gasoline- and diesel-vehicle exhaust, whereas those in suburban PM 2.5 are mainly influenced by gasoline-vehicle exhaust. Environ Toxicol Chem 2017;36:3217-3222. © 2017 SETAC. © 2017 SETAC.

Standard reference water samples for rare earth element determinations

USGS Publications Warehouse

Verplanck, P.L.; Antweiler, Ronald C.; Nordstrom, D. Kirk; Taylor, Howard 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.

N- and O- ligand doped mesoporous silica-chitosan hybrid beads for the efficient, sustainable and selective recovery of rare earth elements (REE) from acid mine drainage (AMD): Understanding the significance of physical modification and conditioning of the polymer.

PubMed

Ramasamy, Deepika Lakshmi; Puhakka, Ville; Iftekhar, Sidra; Wojtuś, Anna; Repo, Eveliina; Ben Hammouda, Samia; Iakovleva, Evgenia; Sillanpää, Mika

2018-04-15

Silica-chitosan hybrid beads were synthesized via three different methods to investigate the selective recovery of REE from AMD. The influence of amino/non-amino silanes, high molecular weight/high viscous chitosan and N-/O- based ligands were studied and their effects on REE removal efficiencies were analyzed. The adsorption efficiencies of three various groups of modified beads were inspected with respect to feed pH, in a single and a multi-component system, and their affinities towards the light and heavy rare earth elements (LREE/ HREEs) were interpreted to understand the intra-series REE separation behavior. The focus of the study was mainly directed towards utilizing these fabricated beads for the recovery of valuable REEs from the real AMD obtained at three different sampling depths which was found rich in iron, sulfur and aluminum. Moreover, the selectivity of the beads towards REEs improved with silanized and ligand immobilized gels and their impacts on REE recovery in the presence of competing ions were successfully presented in this paper. Also, the synthesized beads showed rapid REE adsorption and recovery within a process time of 5 min. Group II adsorbents, synthesized by forming silica-chitosan hybrid beads followed by PAN/acac modifications, showed superiority over the other groups of adsorbents. Copyright © 2018 Elsevier B.V. All rights reserved.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements.

PubMed

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-14

A synthetic Cu-Al-SO₄ layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu 1-x Al x (SO₄) x/2 (OH)₂·nH₂O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO₄ LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO₄ LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.

Fate and Trophic Transfer of Rare Earth Elements in Temperate Lake Food Webs.

PubMed

Amyot, Marc; Clayden, Meredith G; MacMillan, Gwyneth A; Perron, Tania; Arscott-Gauvin, Alexandre

2017-06-06

Many mining projects targeting rare earth elements (REE) are in development in North America, but the background concentrations and trophic transfer of these elements in natural environments have not been well characterized. We sampled abiotic and food web components in 14 Canadian temperate lakes unaffected by mines to assess the natural ecosystem fate of REE. Individual REE and total REE concentrations (sum of individual element concentrations, ΣREE) were strongly related with each other throughout different components of lake food webs. Dissolved organic carbon and dissolved oxygen in the water column, as well as ΣREE in sediments, were identified as potential drivers of aqueous ΣREE. Log 10 of median bioaccumulation factors ranged from 1.3, 3.7, 4.0, and 4.4 L/kg (wet weight) for fish muscle, zooplankton, predatory invertebrates, and nonpredatory invertebrates, respectively. [ΣREE] in fish, benthic macroinvertebrates, and zooplankton declined as a function of their trophic position, as determined by functional feeding groups and isotopic signatures of nitrogen (δ 15 N), indicating that REE were subject to trophic dilution. Low concentrations of REE in freshwater fish muscle compared to their potential invertebrate prey suggest that fish fillet consumption is unlikely to be a significant source of REE to humans in areas unperturbed by mining activities. However, other fish predators (e.g., piscivorous birds and mammals) may accumulate REE from whole fish as they are more concentrated than muscle. Overall, this study provides key information on the baseline concentrations and trophic patterns for REE in freshwater temperate lakes in Quebec, Canada.

Effects of simulated rare earth recycling wastewaters on biological nitrification

DOE PAGES

Fujita, Yoshiko; Barnes, Joni; Eslamimanesh, Ali; ...

2015-07-16

Current efforts to increase domestic availability of rare-earth element (REE) supplies by recycling and expanded ore processing efforts will result in increased generation of associated wastewaters. In some cases disposal to a sewage treatment plant may be favored but plant performance must be maintained. To assess the potential effects of such wastewaters on biological wastewater treatment, model nitrifying organisms Nitrosomonas europaea and Nitrobacter winogradskyi were exposed to simulated wastewaters containing varying levels of yttrium or europium (10, 50 and 100 ppm), and the REE extractant tributyl phosphate (TBP, at 0.1 g/L). Y and Eu additions above 10 ppm inhibited N.more » europaea activity, even when initially virtually all of the REE was insoluble. The provision of TBP together with Eu increased inhibition of nitrite production by the N. europaea, although TBP alone did not substantially alter nitrifying activity N. winogradskyi was more sensitive to the stimulated wastewaters, with even 10 ppm Eu or Y inducing significant inhibition, and a complete shutdown of nitrifying activity occurred in the presence of the TBP. To analyze the availability of REEs in aqueous solutions, REE solubility has been calculated using the previously developed MSE (Mixed-Solvent Electrolyte) thermodynamic model. The model calculations reveal a strong pH dependence of solubility, which is typically controlled by the precipitation of REE hydroxides but may also be influenced by the formation of a phosphate phase.« less

Effects of simulated rare earth recycling wastewaters on biological nitrification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujita, Yoshiko; Barnes, Joni; Eslamimanesh, Ali

Current efforts to increase domestic availability of rare-earth element (REE) supplies by recycling and expanded ore processing efforts will result in increased generation of associated wastewaters. In some cases disposal to a sewage treatment plant may be favored but plant performance must be maintained. To assess the potential effects of such wastewaters on biological wastewater treatment, model nitrifying organisms Nitrosomonas europaea and Nitrobacter winogradskyi were exposed to simulated wastewaters containing varying levels of yttrium or europium (10, 50 and 100 ppm), and the REE extractant tributyl phosphate (TBP, at 0.1 g/L). Y and Eu additions above 10 ppm inhibited N.more » europaea activity, even when initially virtually all of the REE was insoluble. The provision of TBP together with Eu increased inhibition of nitrite production by the N. europaea, although TBP alone did not substantially alter nitrifying activity N. winogradskyi was more sensitive to the stimulated wastewaters, with even 10 ppm Eu or Y inducing significant inhibition, and a complete shutdown of nitrifying activity occurred in the presence of the TBP. To analyze the availability of REEs in aqueous solutions, REE solubility has been calculated using the previously developed MSE (Mixed-Solvent Electrolyte) thermodynamic model. The model calculations reveal a strong pH dependence of solubility, which is typically controlled by the precipitation of REE hydroxides but may also be influenced by the formation of a phosphate phase.« less

In-situ measurements of rare earth elements in deep sea sediments using nuclear methods.

PubMed

Obhođaš, Jasmina; Sudac, Davorin; Meric, Ilker; Pettersen, Helge E S; Uroić, Milivoj; Nađ, Karlo; Valković, Vlado

2018-03-21

The prospecting activities for finding new rare earth elements (REE) sources have increased greatly in recent years. One of the main discoveries was announced in 2011 by Japanese researchers who found large quantities of REE on the ocean seafloor at the sea depths greater than 4,000 m. The classic approach to investigate REE in deep sea sediments is to obtain sediment samples by drilling that is followed by laborious laboratory analysis. This is very expensive, time consuming and not appropriate for exploring vast areas. In order to efficiently explore the ocean floor for REE deposits, the further development of affordable sensors is needed. Here, we propose two nuclear techniques for exploring REE in surface deep sea sediments: i) Passive measurement of lutetium-176 radioactivity, appropriate if long-term in-situ measurements are possible, and ii) The use of the neutron sensor attached to a remotely operated vehicle for rapid in-situ measurement of gadolinium by thermal neutron-capture. Since concentrations of lutetium and gadolinium show strong linear correlation to the total REE concentrations in deep sea sediments, it is possible to deduce the total REE content by measuring Lu or Gd concentrations only.

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

PubMed

Wang, Lingqing; Liang, Tao

2016-06-01

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

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.

Concomitant Leaching and Electrochemical Extraction of Rare Earth Elements from Monazite.

PubMed

Maes, Synthia; Zhuang, Wei-Qin; Rabaey, Korneel; Alvarez-Cohen, Lisa; Hennebel, Tom

2017-02-07

Rare earth elements (REEs) have become increasingly important in modern day technologies. Unfortunately, their recycling is currently limited, and the conventional technologies for their extraction and purification are exceedingly energy and chemical intensive. New sustainable technologies for REE extraction from both primary and secondary resources would be extremely beneficial. This research investigated a two-stage recovery strategy focused on the recovery of neodymium (Nd) and lanthanum (La) from monazite ore that combines microbially based leaching (using citric acid and spent fungal supernatant) with electrochemical extraction. Pretreating the phosphate-based monazite rock (via roasting) dramatically increased the microbial REE leaching efficiency. Batch experiments demonstrated the effective and continued leaching of REEs by recycled citric acid, with up to 392 mg of Nd L -1 and 281 mg of La L -1 leached during seven consecutive 24 h cycles. Neodymium was further extracted in the catholyte of a three-compartment electrochemical system, with up to 880 mg of Nd L -1 achieved within 4 days (at 40 A m -2 ). Meanwhile, the radioactive element thorium and counterions phosphate and citrate were separated effectively from the REEs in the anolyte, favoring REE extraction and allowing sustainable reuse of the leaching agent. This study shows a promising technology that is suitable for primary ores and can further be optimized for secondary resources.

Experimental mineral/liquid partition coefficients of the rare earth elements /REE/, Sc and Sr for perovskite, spinel and melilite

NASA Technical Reports Server (NTRS)

Nagasawa, H.; Schreiber, H. D.; Morris, R. V.

1980-01-01

Experimental determinations of the mineral/liquid partition coefficients of REE (La, Sm, Eu, Gd, Tb, Yb and Lu), Sc and Sr are reported for the minerals perovskite, spinel and melilite in synthetic systems. Perovskite concentrates light REE with respect to the residual liquid but shows no preference for heavy REE. Spinel greatly discriminates against the incorporation of REE, especially light REE, into its crystal structure. The partition of REE into melilite from a silicate liquid is quite dependent upon both the bulk melt and melilite solid-solution (gehlenite and akermanite components) compositions. As such, melilite can be enriched in REE or will reject REE with corresponding strong negative or strong positive Eu anomalies, respectively.

Responses of plant calmodulin to endocytosis induced by rare earth elements.

PubMed

Wang, Lihong; Cheng, Mengzhu; Chu, Yunxia; Li, Xiaodong; Chen, David D Y; Huang, Xiaohua; Zhou, Qing

2016-07-01

The wide application of rare earth elements (REEs) have led to their diffusion and accumulation in the environment. The activation of endocytosis is the primary response of plant cells to REEs. Calmodulin (CaM), as an important substance in calcium (Ca) signaling systems, regulating almost all of the physiological activities in plants, such as cellular metabolism, cell growth and division. However, the response of CaM to endocytosis activated by REEs remains unknown. By using immunofluorescence labeling and a confocal laser scanning microscope, we found that trivalent lanthanum [La(III)], an REE ion, affected the expression of CaM in endocytosis. Using circular dichroism, X-ray photoelectron spectroscopy and computer simulations, we demonstrated that a low concentration of La(III) could interact with extracellular CaM by electrostatic attraction and was then bound to two Ca-binding sites of CaM, making the molecular structure more compact and orderly, whereas a high concentration of La(III) could be coordinated with cytoplasmic CaM or bound to other Ca-binding sites, making the molecular structure more loose and disorderly. Our results provide a reference for revealing the action mechanisms of REEs in plant cells. Copyright © 2016 Elsevier Ltd. All rights reserved.

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

DOE PAGES

Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

2017-10-26

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

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. Copyright 2009 John Wiley & Sons, Ltd.

Aqueous Rare Earth Element Patterns and Concentration in Thermal Brines Associated With Oil and Gas Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nye, Charles; Quillinan, Scott Austin; Neupane, Ghanashyam

This study is part of a joint effort by the University of Wyoming (UW) School of Energy Resources (SER), the UW Engineering Department, Idaho National Laboratories (INL), and the United States Geological Survey (USGS) to describe rare earth element concentrations in oil and gas produced waters and in coal-fired power station ash ponds. In this work we present rare earth element (REE) and trace metal behavior in produced water from four Wyoming oil and gas fields and surface ash pond water from two coal-fired power stations. The concentration of REEs in oil and gas produced waters is largely unknown. Formore » example, of the 150,000 entries in the USGS National Produced Waters Geochemical Database less than 5 include data for REEs. Part of the reason for this scarcity is the analytical challenge of measuring REEs in high salinity, hydrocarbon-bearing waters. The industry standard for water analysis struggles to detect REEs in natural waters under ideal conditions. The detection of REEs in oil and gas field samples becomes all but impossible with the background noise and interferences caused by high concentrations of non-REE ions and residual hydrocarbons. The INL team members have overcome many of these challenges (e.g. McLing, 2014), and continue to develop their methods. Using the methods of the INL team members we measured REEs in high salinity oil and gas produced waters. Our results show that REEs exist as a dissolved species in all waters measured for this project, typically within the parts per trillion range. The samples may be grouped into two broad categories analytically, and these categories match their genesis: Wyoming oil and gas brines contain elevated levels of Europium, and Wyoming industrial pond waters show elevation in heavy REEs (HREEs). While broadly true, important variations exist within both groups. In the same field Europium can vary by more than an order of magnitude, and likewise HREEs in industrial ponds at the same site can vary by

Rare earth element abundances in presolar SiC

NASA Astrophysics Data System (ADS)

Ireland, T. R.; Ávila, J. N.; Lugaro, M.; Cristallo, S.; Holden, P.; Lanc, P.; Nittler, L.; Alexander, C. M. O'D.; Gyngard, F.; Amari, S.

2018-01-01

Individual isotope abundances of Ba, lanthanides of the rare earth element (REE) group, and Hf have been determined in bulk samples of fine-grained silicon carbide (SiC) from the Murchison CM2 chondrite. The analytical protocol involved secondary ion mass spectrometry with combined high mass resolution and energy filtering to exclude REE oxide isobars and Si-C-O clusters from the peaks of interest. Relative sensitivity factors were determined through analysis of NIST SRM reference glasses (610 and 612) as well as a trace-element enriched SiC ceramic. When normalised to chondrite abundances, the presolar SiC REE pattern shows significant deficits at Eu and Yb, which are the most volatile of the REE. The pattern is very similar to that observed for Group III refractory inclusions. The SiC abundances were also normalised to s-process model predictions for the envelope compositions of low-mass (1.5-3 M⊙) AGB stars with close-to-solar metallicities (Z = 0.014 and 0.02). The overall trace element abundances (excluding Eu and Yb) appear consistent with the predicted s-process patterns. The depletions of Eu and Yb suggest that these elements remained in the gas phase during the condensation of SiC. The lack of depletion in some other moderately refractory elements (like Ba), and the presence of volatile elements (e.g. Xe) indicates that these elements were incorporated into SiC by other mechanisms, most likely ion implantation.

Rare earth elements in freshwater, marine, and terrestrial ecosystems in the eastern Canadian Arctic.

PubMed

MacMillan, Gwyneth Anne; Chételat, John; Heath, Joel P; Mickpegak, Raymond; Amyot, Marc

2017-10-18

Few ecotoxicological studies exist for rare earth elements (REEs), particularly field-based studies on their bioaccumulation and food web dynamics. REE mining has led to significant environmental impacts in several countries (China, Brazil, U.S.), yet little is known about the fate and transport of these contaminants of emerging concern. Northern ecosystems are potentially vulnerable to REE enrichment from prospective mining projects at high latitudes. To understand how REEs behave in remote northern food webs, we measured REE concentrations and carbon and nitrogen stable isotope ratios (∂ 15 N, ∂ 13 C) in biota from marine, freshwater, and terrestrial ecosystems of the eastern Canadian Arctic (N = 339). Wildlife harvesting and tissue sampling was partly conducted by local hunters through a community-based monitoring project. Results show that REEs generally follow a coherent bioaccumulation pattern for sample tissues, with some anomalies for redox-sensitive elements (Ce, Eu). Highest REE concentrations were found at low trophic levels, especially in vegetation and aquatic invertebrates. Terrestrial herbivores, ringed seal, and fish had low total REE levels in muscle tissue (∑REE for 15 elements <0.1 nmol g -1 ), yet accumulation was an order of magnitude higher in liver tissues. Age- and length-dependent REE accumulation also suggest that REE uptake is faster than elimination for some species. Overall, REE bioaccumulation patterns appear to be species- and tissue-specific, with limited potential for biomagnification. This study provides novel data on the behaviour of REEs in ecosystems and will be useful for environmental impact assessment of REE enrichment in northern regions.

Rare earth elements in human and animal health: State of art and research priorities.

PubMed

Pagano, Giovanni; Aliberti, Francesco; Guida, Marco; Oral, Rahime; Siciliano, Antonietta; Trifuoggi, Marco; Tommasi, Franca

2015-10-01

A number of applications have been developed using rare earth elements (REE), implying several human exposures and raising unsolved questions as to REE-associated health effects. A MedLine survey was retrieved from early reports (1980s) up to June 2015, focused on human and animal exposures to REE. Literature from animal models was selected focusing on REE-associated health effects. Some REE occupational exposures, in jobs such as glass polishers, photoengravers and movie projectionists showed a few case reports on health effects affecting the respiratory system. No case-control or cohort studies of occupational REE exposures were retrieved. Environmental exposures have been biomonitored in populations residing in REE mining areas, showing REE accumulation. The case for a iatrogenic REE exposure was raised by the use of gadolinium-based contrast agents for nuclear magnetic resonance. Animal toxicity studies have shown REE toxicity, affecting a number of endpoints in liver, lungs and blood. On the other hand, the use of REE as feed additives in livestock is referred as a safe and promising device in zootechnical activities, possibly suggesting a hormetic effect both known for REE and for other xenobiotics. Thus, investigations on long-term exposures and observations are warranted. The state of art provides a limited definition of the health effects in occupationally or environmentally REE-exposed human populations. Research priorities should be addressed to case-control or cohort studies of REE-exposed humans and to life-long animal experiments. Copyright © 2015 Elsevier Inc. All rights reserved.

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

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. Copyright © 2015 Elsevier Inc. All rights reserved.

Correlation of nasopharyngeal carcinoma with rare earth elements and the Epstein-Barr virus

PubMed Central

Zhang, Xiangmin; Zeng, Xiangfu; Liu, Lianbin; Lan, Xiaolin; Huang, Jing; Zeng, Hongxue; Li, Rong; Luo, Keqing; Wu, Wei; Zhou, Maohua; Li, Shaojin

2018-01-01

The concentration and distribution of rare earth elements (REE) in nasopharyngeal carcinoma (NPC) were measured to investigate connections with tumor size, lymph node metastasis, clinical stages, and Epstein-Barr virus (EBV) infection. There were 30 patients with NPC who met the criteria for inclusion in the present study. The EBV copy number, as well as the concentration and distribution of REE, was analyzed. EBV was detected using reverse transcription-polymerase chain reaction, with the concentrations of REE in NPC tissues measured using inductively coupled plasma-tandem mass spectrometry. The mean values were used when comparing concentrations of REE in NPC tissues as the standard deviation of this parameter was the lowest. Light REE had the highest concentrations, followed by medium, and then heavy REE. The concentrations of REE decreased with increasing tumor size and with the presence of lymph node metastasis. The concentrations of REE gradually increased between stage II and IVa, but markedly decreased thereafter. The elements that exhibited the greatest decreases were terbium, holmium and ytterbium. Furthermore, the concentrations of REE in NPC were not associated with sex (r=0.301, P=0.106) or age (r=−0.011, P=0.955), and were negatively associated with EBV (r=−0.744, P<0.001). By contrast, the EBV copy number increased alongside advancements in clinical stage. Changes in the concentrations of REE in NPC were more prominent for medium and heavy elements. Additionally, alterations in the concentrations of heavy REE may affect the occurrence and development of NPC. PMID:29541176

Correlation of nasopharyngeal carcinoma with rare earth elements and the Epstein-Barr virus.

PubMed

Zhang, Xiangmin; Zeng, Xiangfu; Liu, Lianbin; Lan, Xiaolin; Huang, Jing; Zeng, Hongxue; Li, Rong; Luo, Keqing; Wu, Wei; Zhou, Maohua; Li, Shaojin

2018-04-01

The concentration and distribution of rare earth elements (REE) in nasopharyngeal carcinoma (NPC) were measured to investigate connections with tumor size, lymph node metastasis, clinical stages, and Epstein-Barr virus (EBV) infection. There were 30 patients with NPC who met the criteria for inclusion in the present study. The EBV copy number, as well as the concentration and distribution of REE, was analyzed. EBV was detected using reverse transcription-polymerase chain reaction, with the concentrations of REE in NPC tissues measured using inductively coupled plasma-tandem mass spectrometry. The mean values were used when comparing concentrations of REE in NPC tissues as the standard deviation of this parameter was the lowest. Light REE had the highest concentrations, followed by medium, and then heavy REE. The concentrations of REE decreased with increasing tumor size and with the presence of lymph node metastasis. The concentrations of REE gradually increased between stage II and IVa, but markedly decreased thereafter. The elements that exhibited the greatest decreases were terbium, holmium and ytterbium. Furthermore, the concentrations of REE in NPC were not associated with sex (r=0.301, P=0.106) or age (r=-0.011, P=0.955), and were negatively associated with EBV (r=-0.744, P<0.001). By contrast, the EBV copy number increased alongside advancements in clinical stage. Changes in the concentrations of REE in NPC were more prominent for medium and heavy elements. Additionally, alterations in the concentrations of heavy REE may affect the occurrence and development of NPC.

Bio- and mineral acid leaching of rare earth elements from synthetic phosphogypsum

NASA Astrophysics Data System (ADS)

Hu, Z.; Antonick, P.; Fujita, Y.; Reed, D. W.; Riman, R.; Eslamimanesh, A.; Das, G.; Anderko, A.; Wu, L.; Shivaramaiah, R.; Navrotsky, A.

2017-12-01

Rare earth elements (REE) are critical to many clean energy technologies. However, the lack of U.S. domestic production and the reliance on imported REE put U.S. energy security at risk. Consequently development of new sources is of strategic interest. Global phosphate deposits contain 27 million tons of REE and 38% of these REE end up in phosphogypsum (PG) waste during phosphate fertilizer production. Recovering REE from PG is a first step toward a trash-to-treasure transformation. We studied the leaching of REE from synthetic PG samples containing Y, Nd, or Eu using a suite of lixiviants including spent medium from the growth of the bacterium Gluconobacter oxydans ("biolixiviant"), gluconic acid, common mineral acids (phosphoric and sulfuric), and water. Synthetic PG was used to facilitate the comparison of the different lixiviants; real PG waste is extremely heterogeneous. Gluconic acid was the predominant identified organic acid in the biolixiviant. The leaching efficiency of the acidic lixiviants at the same pH (2.1) or molar concentration as gluconic acid in the biolixiviant (220 mM) were compared and rationalized by thermodynamic simulation using the mixed-solvent electrolyte model. Initial results indicate that the biolixiviant was more effective at leaching the REE than the mineral acids at pH 2.1. At 220 mM acid concentrations, sulfuric acid was the most effective, followed by the biolixiviant. Interestingly, for a given lixiviant, the leaching behavior of the REE differed. This study provides insight into the definition of an efficient lixiviant for leaching REE from phosphate fertilizer production waste.

Formation of carbonatite-related giant rare-earth-element deposits by the recycling of marine sediments

PubMed Central

Hou, Zengqian; Liu, Yan; Tian, Shihong; Yang, Zhiming; Xie, Yuling

2015-01-01

Carbonatite-associated rare-earth-element (REE) deposits are the most significant source of the world’s REEs; however, their genesis remains unclear. Here, we present new Sr-Nd-Pb and C-O isotopic data for Cenozoic carbonatite-hosted giant REE deposits in southwest China. These REE deposits are located along the western margin of the Yangtze Craton that experienced Proterozoic lithospheric accretion, and controlled by Cenozoic strike-slip faults related to Indo-Asian continental collision. The Cenozoic carbonatites were emplaced as stocks or dykes with associated syenites, and tend to be extremely enriched in Ba, Sr, and REEs and have high 87Sr/86Sr ratios (>0.7055). These carbonatites were likely formed by melting of the sub-continental lithospheric mantle (SCLM), which had been previously metasomatized by high-flux REE- and CO2-rich fluids derived from subducted marine sediments. The fertility of these carbonatites depends on the release of REEs from recycled marine sediments and on the intensity of metasomatic REE refertilization of the SCLM. We suggest that cratonic edges, particularly along ancient convergent margins, possess the optimal configuration for generating giant REE deposits; therefore, areas of metamorphic basement bounded or cut by translithospheric faults along cratonic edges have a high potential for such deposits. PMID:26035414

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements

PubMed Central

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-01

A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1−xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5–8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis. PMID:29342887

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 10 pg g(-1), as well as measurement repeatability below 15%. Overall, the Na2O2/ICP-MS/MS method proved to be a suitable lab-based method to quickly and accurately screen rock samples originating from quartz-rich geological areas for rare earth element content; particularly useful if checking commercial viability. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparative Analysis of Processes for Recovery of Rare Earths from Bauxite Residue

NASA Astrophysics Data System (ADS)

Borra, Chenna Rao; Blanpain, Bart; Pontikes, Yiannis; Binnemans, Koen; Van Gerven, Tom

2016-11-01

Environmental concerns and lack of space suggest that the management of bauxite residue needs to be re-adressed. The utilization of the residue has thus become a topic high on the agenda for both academia and industry, yet, up to date, it is only rarely used. Nonetheless, recovery of rare earth elements (REEs) with or without other metals from bauxite residue, and utilization of the left-over residue in other applications like building materials may be a viable alternative to storage. Hence, different processes developed by the authors for recovery of REEs and other metals from bauxite residue were compared. In this study, preliminary energy and cost analyses were carried out to assess the feasibility of the processes. These analyses show that the combination of alkali roasting-smelting-quenching-leaching is a promising process for the treatment of bauxite residue and that it is justified to study this process at a pilot scale.

An assessment of exposure to rare earth elements among patients receiving long-term parenteral nutrition.

PubMed

Galusha, Aubrey L; Kruger, Pamela C; Howard, Lyn J; Parsons, Patrick J

2018-05-01

Patients receiving long-term parenteral nutrition (PN) are exposed to potentially toxic elements, which may accumulate in bone. Bone samples collected from seven PN patients (average = 14 years) and eighteen hip/knee samples were analyzed for Al as part of a previous investigation. Yttrium was serendipitously detected in the PN bone samples, leading to the present investigation of rare earth elements (REEs). A method for quantitating fifteen REEs in digested bone was developed based on tandem ICP-MS (ICP-MS/MS) to resolve spectral interferences. The method was validated against nine biological reference materials (RMs) for which assigned values were available for most REEs. Values found in two NIST bone SRMs (1400 Bone Ash and 1486 Bone Meal) compared favorably to those reported elsewhere. Method detection limits ranged from 0.9 ng g -1 (Tm) to 5.8 ng g -1 (Y). Median REE values in the PN patient group were at least fifteen times higher than the "control" group, and exceeded all previously reported data for eleven REEs in human bones. REE content in PN bones normalized to the Earth's upper crust revealed anomalies for Gd in two patients, likely from exposure to Gd-containing contrast agents used in MRI studies. A retrospective review of the medical record for one patient revealed an almost certain case of nephrogenic systemic fibrosis, associated with Gd exposure. Analysis of two current PN formulations showed traces of REEs with relative abundances similar to those found in the PN bones, providing convincing evidence that PN solutions were the primary source of REEs in this population. Copyright © 2018 Elsevier GmbH. All rights reserved.

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

DOE Data Explorer

Dean Stull

2016-05-24

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

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.

Recovery and separation of rare earth elements using columns loaded with DNA-filter hybrid.

PubMed

Takahashi, Yoshio; Kondo, Kazuhiro; Miyaji, Asami; Umeo, Miyuki; Honma, Tetsuo; Asaoka, Satoshi

2012-01-01

Given that the supply of several rare earth elements (REEs) is sometimes limited, recycling REEs used in various advanced materials, such as Nd magnets, is important for realizing efficient use of REE resources. In the present work, the feasibility of using DNA for REE recovery and separation was examined, along with the identification of the binding site of REEs in DNA. In particular, a DNA-cellulose filter paper hybrid was prepared so that DNA-based materials can be used for the separation of REEs using columns loaded with DNA. N,N'-Disuccinimidyl was used as a cross-linker reagent for the fixation of DNA onto a fibrous cellulose filter. The results showed that (i) the DNA-filter hybrid has a sufficiently high affinity to adsorb REEs; (ii) the adsorption capacity was 0.182 mg/g for Nd; and (iii) the affinity of REEs for DNA was stronger for REEs with larger atomic numbers. The difference of the affinity among REEs in the third result was compared with the adsorption patterns of REEs discussed in the literature. The comparison suggests that phosphate in the DNA-filter paper hybrid was responsible for REE adsorption onto the hybrid. The results were supported by the Nd, Dy, and Lu L(III)-edge EXAFS; the REE-P shell was identified for the second neighboring atom, showing the importance of the phosphate site as REE binding sites. The difference in the affinity among REEs suggest that group separation of REEs (such as La, Ce, (Pr and Nd), (Ho, Dy, and Er), (Tb and Gd), (Sm, Eu), Tm, Yb, and Lu) is possible, although complete isolation of each REE from a solution containing all REEs may be difficult. For practical applications, Nd and Fe(III) were successfully separated from a synthetic solution of Nd magnet waste using columns loaded with the DNA-filter hybrid.

Rare earth elements and select actinoids in the Canadian House Dust Study.

PubMed

Rasmussen, P E; Levesque, C; Chénier, M; Gardner, H D

2017-09-01

Nationally representative baseline data are presented for rare earth elements (REE), thorium (Th) and uranium (U) in house dust sampled from 1025 urban homes, in units of concentrations (μg g -1 ), loadings (μg m -2 ), and loading rates (ng m -2  d -1 ). Spearman rank correlations indicate that, in addition to outdoor sources, consumer products and building materials can influence indoor dust concentrations of REE, Th, and U. Correlations (P<.01) with numbers of occupants, dogs, and cats suggest soil track-in. Correlations (P<.01) with hardwood floors suggest release of REE additives used in pigments and coatings during daily wear and tear. Concentrations of light REE are elevated in smokers' homes compared to non-smokers' homes (P<.001), suggesting that a key source is "mischmetal," the REE alloy used in cigarette-lighter flints. Indoor sources include geological impurities in raw materials used in consumer products, such as U and Th impurities in bentonite clay used in cat litter, and REE impurities in phosphates used for a variety of applications including dog food and building materials. Median gastric bioaccessibility (pH 1.5) of most REE in dust ranges from about 20% to 29%. Household vacuum samples correlate with fresh dust samples from the same homes (P<.001 for all investigated elements). © 2017 Her Majesty the Queen in Right of Canada Indoor Air © 2017 John Wiley & Sons Ltd.

Phytoextraction of rare earth elements in herbaceous plant species growing close to roads.

PubMed

Mikołajczak, Patrycja; Borowiak, Klaudia; Niedzielski, Przemysław

2017-06-01

The aim of study was to determine the phytoextraction of rare earth elements (REEs) to roots, stems and leaves of five herbaceous plant species (Achillea millefolium L., Artemisia vulgaris L., Papaver rhoeas L., Taraxacum officinale AND Tripleurospermum inodorum), growing in four areas located in close proximity to a road with varied traffic intensity. Additionally, the relationship between road traffic intensity, REE concentration in soil and the content of these elements in plant organs was estimated. A. vulgaris and P. rhoeas were able to effectively transport REEs in their leaves, independently of area collection. The highest content of REEs was observed in P. rhoeas leaves and T. inodorum roots. Generally, HREEs were accumulated in P. rhoeas roots and leaves and also in the stems of T. inodorum and T. officinale, whereas LREEs were accumulated in T. inodorum roots and T. officinale stems. It is worth underlining that there was a clear relationship between road traffic intensity and REE, HREE and LREE concentration in soil. No positive correlation was found between the concentration of these elements in soil and their content in plants, with the exception of T. officinale. An effective transport of REEs from the root system to leaves was observed, what points to the possible ability of some of the tested plant species to remove REEs from soils near roads.

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.

A supported liquid membrane system for the selective recovery of rare earth elements from neodymium-based permanent magnets

DOE PAGES

Kim, Daejin; Powell, Lawrence; Delmau, Lætitia H.; ...

2016-04-04

We present that the rare earth elements (REEs) play a vital role in the development of green energy and high-tech industries. In order to meet the fast-growing demand and to ensure sufficient supply of the REEs, it is essential to develop an efficient REE recovery process from post-consumer REE-containing products. In this research effort, we have developed a supported liquid membrane system utilizing polymeric hollow fiber modules to extract REEs from neodymium-based magnets with neutral extractants such as tetraoctyl digylcol amide (TODGA). The effect of process variables such as REE concentration, molar concentration of acid, and membrane area on REEmore » recovery was investigated. We have demonstrated the selective extraction and recovery of REEs such as Nd, Pr, and Dy without co-extraction of non-REEs from permanent NdFeB magnets through the supported liquid membrane system. The extracted REEs were then recovered by precipitation followed by the annealing step to obtain crystalline REE powders in nearly pure form. Finally, the recovered REE oxides were characterized by X-ray diffraction, scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, and inductively coupled plasma–optical emission spectroscopy.« less

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

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Taylor, Howard 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.

Geochemical characteristics of rare earth elements in different types of soil: A chemometric approach.

PubMed

Khan, Aysha Masood; Behkami, Shima; Yusoff, Ismail; Md Zain, Sharifuddin Bin; Bakar, Nor Kartini Abu; Bakar, Ahmad Farid Abu; Alias, Yatimah

2017-10-01

Rare earth elements (REEs) are becoming significant due to their huge applications in many industries, large-scale mining and refining activities. Increasing usage of such metals pose negative environmental impacts. In this research ICP-MS has been used to analyze soil samples collected from former ex-mining areas in the depths of 0-20 cm, 21-40 cm, and 41-60 cm of residential, mining, natural, and industrial areas of Perak. Principal component analysis (PCA) revealed that soil samples taken from different mining, industrial, residential, and natural areas are separated into four clusters. It was observed that REEs were abundant in most of the samples from mining areas. Concentration of the rare elements decrease in general as we move from surface soil to deeper soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Environmental Characteristics of Carbonatite and Alkaline Intrusion-related Rare Earth Element (REE) Deposits

NASA Astrophysics Data System (ADS)

Seal, R. R., II; Piatak, N. M.

2017-12-01

Carbonatites and alkaline intrusions are important sources of REEs. Environmental risks related to these deposit types have been assessed through literature review and evaluation of the geochemical properties of representative samples of mill tailings and their leachates. The main ore mineral in carbonatite deposits is bastnasite [(Ce,La)(CO3)F], which is found with dolomite and calcite ( 65 %), barite (20 - 25 %), plus a number of minor accessory minerals including sulfides such as galena and pyrite. Generally, alkaline intrusion-related REE deposits either occur in layered complexes or with dikes and veins cutting alkaline intrusions. Such intrusions have a more diverse group of REE ore minerals that include fluorcarbonates, oxides, silicates, and phosphates. Ore also can include minor calcite and iron (Fe), lead (Pb), and zinc (Zn) sulfides. The acid-generating potential of both deposit types is low because of a predominance of carbonate minerals in the carbonatite deposits, the presence of feldspars and minor calcite in alkaline intrusion-related deposits, and to only minor to trace occurrence of potentially acid-generating sulfide minerals. Both deposit types, however, are produced by igneous and hydrothermal processes that enrich high-field strength, incompatible elements, which typically are excluded from common rock-forming minerals. Elements such as yttrium (Y), niobium Nb), zirconium (Zr), hafnium (Hf), tungsten (W), titanium (Ti), tantalum (Ta), scandium (Sc), thorium (Th), and uranium (U) can be characteristic of these deposits and may be of environmental concern. Most of these elements, including the REEs, but with the exception of U, have low solubilities in water at the near-neutral pH values expected around these deposits. Mill tailings from carbonatite deposits can exceed residential soil and sediment criteria for Pb, and leachates from mill tailings can exceed drinking water guidelines for Pb. The greatest environmental challenges, however, are

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

Rare earth element geochemistry of feldspars: examples from Fe-oxide Cu-Au systems in the Olympic Cu-Au Province, South Australia

NASA Astrophysics Data System (ADS)

Kontonikas-Charos, Alkis; Ciobanu, Cristiana L.; Cook, Nigel J.; Ehrig, Kathy; Krneta, Sasha; Kamenetsky, Vadim S.

2018-04-01

Rare earth element (REE) fractionation trends in feldspars are reported from Olympic Dam (including Wirrda Well and Phillip's Ridge) and Cape Donington (Port Lincoln), for comparison with two other igneous-hydrothermal terranes within the eastern Gawler Craton: Moonta-Wallaroo and Hillside. The case studies were selected as they represent 1590 Ma Hiltaba Suite and/or 1845 - 1810 Ma Donington Suite granites, and, aside from Cape Donington, are associated with Mesoproterozoic iron-oxide copper gold (IOCG)-type mineralization. Both plagioclase and alkali feldspar were analyzed within selected samples with the purpose of constraining and linking changes in REE concentrations and fractionation trends in feldspars to local and whole-rock textures and geochemistry. Two unique, reproducible fractionation trends were obtained for igneous plagioclase and alkali feldspars, distinguished from one another by light rare earth element enrichment, Eu-anomalies and degrees of fractionation (e.g. La/Lu slopes). Results for hydrothermal albite and K-feldspar indicate that REE concentrations and fractionation trends are generally inherited from igneous predecessors, however in some instances, significant amounts of REE appear to have been lost to the fluid. These results may have critical implications for the formation of world-class IOCG systems, in which widespread alkali metasomatism plays a key role by altering the physical and chemical properties of the host rocks during early stages of IOCG formation, as well as trapping trace elements (including REE).

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

Battery related cobalt and REE flows in WEEE treatment.

PubMed

Sommer, P; Rotter, V S; Ueberschaar, M

2015-11-01

In batteries associated with waste electrical and electronic equipment (WEEE), battery systems can be found with a higher content of valuable and critical raw materials like cobalt and rare earth elements (REE) relative to the general mix of portable batteries. Based on a material flow model, this study estimates the flows of REE and cobalt associated to WEEE and the fate of these metals in the end-of-life systems. In 2011, approximately 40 Mg REE and 325 Mg cobalt were disposed of with WEEE-batteries. The end-of-life recycling rate for cobalt was 14%, for REE 0%. The volume of waste batteries can be expected to grow, but variation in the battery composition makes it difficult to forecast the future secondary raw material potential. Nevertheless, product specific treatment strategies ought to be implemented throughout the stages of the value chain. Copyright © 2015 Elsevier Ltd. All rights reserved.

Distribution of rare earth elements in soil and grape berries of Vitis vinifera cv. "Glera".

PubMed

Pepi, Salvatore; Sansone, Luigi; Chicca, Milvia; Marrocchino, Elena; Vaccaro, Carmela

2016-08-01

The renowned Vitis vinifera L. cultivar "Glera" (Magnoliopsida Vitaceae) has been grown for hundreds of years in the Italian regions of Veneto and Friuli to produce the sparkling Prosecco wine, with controlled designation of origin (DOC). We evaluated the relationship among the concentrations of rare earth elements (REE) in soil and in "Glera" grape berries in vineyards belonging to five different localities in the Veneto alluvial plain, all included in the DOC area of Prosecco. The concentration of REE in samples of soil and juice or solid residues of grape berries was determined by inductively coupled plasma mass spectrometry (ICP-MS), and the index of bioaccumulation was calculated to define the specific assimilation of these elements from soil to grape berries. The concentration of REE in soil samples allowed an identification of each locality examined, and REE were mostly detected in solid grape berry residues in comparison to juice. These data may be useful to associate REE distribution in soil and grape berries to a specific geographical origin, in order to prevent fraudulent use of wine denomination labels.

Using rare earth elements to constrain particulate organic carbon flux in the East China Sea.

PubMed

Hung, Chin-Chang; Chen, Ya-Feng; Hsu, Shih-Chieh; Wang, Kui; Chen, Jianfang; Burdige, David J

2016-09-27

Fluxes of particulate organic carbon (POC) in the East China Sea (ECS) have been reported to decrease from the inner continental shelf towards the outer continental shelf. Recent research has shown that POC fluxes in the ECS may be overestimated due to active sediment resuspension. To better characterize the effect of sediment resuspension on particle fluxes in the ECS, rare earth elements (REEs) and organic carbon (OC) were used in separate two-member mixing models to evaluate trap-collected POC fluxes. The ratio of resuspended particles from sediments to total trap-collected particles in the ECS ranged from 82-94% using the OC mixing model, and 30-80% using the REEs mixing model, respectively. These results suggest that REEs may be better proxies for sediment resuspension than OC in high turbidity marginal seas because REEs do not appear to undergo degradation during particle sinking as compared to organic carbon. Our results suggest that REEs can be used as tracers to provide quantitative estimates of POC fluxes in marginal seas.

Using rare earth elements to constrain particulate organic carbon flux in the East China Sea

PubMed Central

Hung, Chin-Chang; Chen, Ya-Feng; Hsu, Shih-Chieh; Wang, Kui; Chen, Jian Feng; Burdige, David J.

2016-01-01

Fluxes of particulate organic carbon (POC) in the East China Sea (ECS) have been reported to decrease from the inner continental shelf towards the outer continental shelf. Recent research has shown that POC fluxes in the ECS may be overestimated due to active sediment resuspension. To better characterize the effect of sediment resuspension on particle fluxes in the ECS, rare earth elements (REEs) and organic carbon (OC) were used in separate two-member mixing models to evaluate trap-collected POC fluxes. The ratio of resuspended particles from sediments to total trap-collected particles in the ECS ranged from 82–94% using the OC mixing model, and 30–80% using the REEs mixing model, respectively. These results suggest that REEs may be better proxies for sediment resuspension than OC in high turbidity marginal seas because REEs do not appear to undergo degradation during particle sinking as compared to organic carbon. Our results suggest that REEs can be used as tracers to provide quantitative estimates of POC fluxes in marginal seas. PMID:27670426

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.

Crystal-chemistry and partitioning of REE in whitlockite

NASA Technical Reports Server (NTRS)

Colson, R. O.; Jolliff, B. L.

1993-01-01

Partitioning of Rare Earth Elements (REE) in whitlockite is complicated by the fact that two or more charge-balancing substitutions are involved and by the fact that concentrations of REE in natural whitlockites are sufficiently high such that simple partition coefficients are not expected to be constant even if mixing in the system is completely ideal. The present study combines preexisting REE partitioning data in whitlockites with new experiments in the same compositional system and at the same temperature (approximately 1030 C) to place additional constraints on the complex variations of REE partition coefficients and to test theoretical models for how REE partitioning should vary with REE concentration and other compositional variables. With this data set, and by combining crystallographic and thermochemical constraints with a SAS simultaneous-equation best-fitting routine, it is possible to infer answers to the following questions: what is the speciation on the individual sites Ca(B), Mg, and Ca(IIA) (where the ideal structural formula is Ca(B)18 Mg2Ca(IIA)2P14O56); how are REE's charge-balanced in the crystal; and is mixing of REE in whitlockite ideal or non-ideal. This understanding is necessary in order to extrapolate derived partition coefficients to other compositional systems and provides a broadened understanding of the crystal chemistry of whitlockite.

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. Copyright © 2014 Elsevier Inc. All rights reserved.

Systematic Investigation of REE Mobility and Fractionation During Continental Shale Weathering Along a Climate Gradient

NASA Astrophysics Data System (ADS)

Jin, L.; Ma, L.; Dere, A. L. D.; White, T.; Brantley, S. L.

2014-12-01

Rare earth elements (REE) have been identified as strategic natural resources and their demand in the United States is increasing rapidly. REE are relatively abundant in the Earth's crust, but REE deposits with minable concentrations are uncommon. One recent study has pointed to the deep-sea REE-rich muds in the Pacific Ocean as a new potential resource, related to adsorption and concentration of REE from seawater by hydrothermal iron-oxyhydroxides and phillipsite (Kato et al., 2010). Finding new REE deposits will be facilitated by understanding global REE cycles: during the transformation of bedrock into soils, REEs are leached into natural waters and transported to oceans. At present, the mechanisms and factors controlling release, transport, and deposition of REE - the sources and sinks - at Earth's surface remain unclear. Here, we systematically studied soil profiles and bedrock in seven watersheds developed on shale bedrock along a climate transect in the eastern USA, Puerto Rico and Wales to constrain the mobility and fractionation of REE during chemical weathering processes. In addition, one site on black shale (Marcellus) bedrock was included to compare behaviors of REEs in organic-rich vs. organic-poor shale end members under the same environmental conditions. Our investigation focused on: 1) the concentration of REEs in gray and black shales and the release rates of REE during shale weathering, 2) the biogeochemical and hydrological conditions (such as redox, dissolved organic carbon, and pH) that dictate the mobility and fractionation of REEs in surface and subsurface environments, and 3) the retention of dissolved REEs on soils, especially onto secondary Fe/Al oxyhydroxides and phosphate mineral phases. This systematic study sheds light on the geochemical behaviors and environmental pathways of REEs during shale weathering along a climosequence.

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

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

PubMed

Tan, Quanyin; Deng, Chao; Li, Jinhui

2016-01-28

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.

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.

Rare earths recovery and gypsum upgrade from Florida phosphogypsum

DOE PAGES

Liang, Haijun; Zhang, Patrick; Jin, Zhen; ...

2017-11-01

Phosphogypsum is a byproduct created during the production of industrial wet-process phosphoric acid. This study focused on recovering rare earth elements (REEs) from a Florida phosphogypsum sample and investigated the effects of removing detrimental impurities such as phosphorus pentoxide (P 2O 5), uranium (U) and fluorine (F) during the leaching process. Experimental results indicated that REE leaching efficiency increased rapidly, reached a maximum and then began to decrease with sulfuric acid concentrations ranging from 0 to 10 percent and temperatures ranging from 20 to 70 °C. At a sulfuric acid concentration of 5 percent and leaching temperature of 50 °C,more » REE leaching efficiency obtained a maximum value of approximately 43 percent. Increasing the leaching time or liquid/solid ratio increased the leaching efficiency. The leaching efficiencies of P 2O 5, U and F consistently increased with sulfuric acid concentration, temperature, leaching time and liquid/solid ratio within the testing ranges. A fine-grain gypsum concentrate, sized smaller than 40 μm, was separated from leached phosphogypsum through elutriation, in which the P 2O 5, U and F content levels were reduced by 99, 70 and 83 percent, respectively, from their content levels in fresh phosphogypsum.« less

Rare earths recovery and gypsum upgrade from Florida phosphogypsum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Haijun; Zhang, Patrick; Jin, Zhen

Phosphogypsum is a byproduct created during the production of industrial wet-process phosphoric acid. This study focused on recovering rare earth elements (REEs) from a Florida phosphogypsum sample and investigated the effects of removing detrimental impurities such as phosphorus pentoxide (P 2O 5), uranium (U) and fluorine (F) during the leaching process. Experimental results indicated that REE leaching efficiency increased rapidly, reached a maximum and then began to decrease with sulfuric acid concentrations ranging from 0 to 10 percent and temperatures ranging from 20 to 70 °C. At a sulfuric acid concentration of 5 percent and leaching temperature of 50 °C,more » REE leaching efficiency obtained a maximum value of approximately 43 percent. Increasing the leaching time or liquid/solid ratio increased the leaching efficiency. The leaching efficiencies of P 2O 5, U and F consistently increased with sulfuric acid concentration, temperature, leaching time and liquid/solid ratio within the testing ranges. A fine-grain gypsum concentrate, sized smaller than 40 μm, was separated from leached phosphogypsum through elutriation, in which the P 2O 5, U and F content levels were reduced by 99, 70 and 83 percent, respectively, from their content levels in fresh phosphogypsum.« less

Behavioral deficits and neural damage of Caenorhabditis elegans induced by three rare earth elements.

PubMed

Xu, Tiantian; Zhang, Manke; Hu, Jiani; Li, Zihan; Wu, Taipu; Bao, Jianing; Wu, Siyu; Lei, Lili; He, Defu

2017-08-01

Rare earth elements (REEs) are widely used in industry, agriculture, medicine and daily life in recent years. However, environmental and health risks of REEs are still poorly understood. In this study, neurotoxicity of trichloride neodymium, praseodymium and scandium were evaluated using nematode Caenorhabditis elegans as the assay system. Median lethal concentrations (48 h) were 99.9, 157.2 and 106.4 mg/L for NdCl 3 , PrCl 3 and ScCl 3 , respectively. Sublethal dose (10-30 mg/L) of these trichloride salts significantly inhibited body length of nematodes. Three REEs resulted in significant declines in locomotor frequency of body bending, head thrashing and pharyngeal pumping. In addition, mean speed and wavelength of crawling movement were significantly reduced after chronic exposure. Using transgenic nematodes, we found NdCl 3 , PrCl 3 and ScCl 3 resulted in loss of dendrite and soma of neurons, and induced down-expression of dat-1::GFP and unc-47::GFP. It indicates that REEs can lead to damage of dopaminergic and GABAergic neurons. Our data suggest that exposure to REEs may cause neurotoxicity of inducing behavioral deficits and neural damage. These findings provide useful information for understanding health risk of REE materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Obtaining of Nano Oxide Systems SiO2-REE with Alkoxide Technology

NASA Astrophysics Data System (ADS)

Amelina, Anna; Grinberg, Evgenii

A lot of oxides systems with REE as dopants are used in catalytic processes in organic synthesis. They are very perspectives as thermostable coating in aerospace technics. These systems are usually based on silicon or aluminium oxides and doped with rare-earth elements. This systems can be produced by different methods. One of the most perspective of them is “sol-gel”-method with silicium, aluminium and rare-earth alkoxides as a precursor of doped silica and alumina, or their derivatives. Thus the obtaining of composite SiO _{2} - REE oxide materials by the hydrolysis doped with rare-earth elements was suggested. Some of alcoholate derivatives such as El(OR)n were used in this processes. The SiO _{2}- REE oxides were precipitated during the sol-gel process, where tetraethoxysilane (TEOS) as used as SiO _{2} sources. Also it is known that alkoxides of alkali metals, including lithium alkoxides, are widely used in industry and synthetic chemistry, as well as a source of lithium in various mixed oxide compositions, such as lithium niobate, lithium tantalate or lithium silicate. Therefore, we attempted to obtain the lithium silicate, which is also doped with rare-earth elements. Lithium silicate was obtained by alkaline hydrolysis of tetraethoxysilane with lithium alkoxide. Lithium alkoxide were synthesized by dissolving at metal in the corresponding alcohol are examined. The dependence of the rate of dissolving of the metal on the method of mixing of the reaction mixture and the degree of metal dispersion was investigated. The mathematical model of the process was composed and also optimization of process was carried out. Some oxide SiO _{2}, Al _{2}O _{3} and rare-earth nanostructured systems were obtained by sol-gel-method. The size of particle was determined by electron and X-ray spectroscopy and was in the range of 5 - 15 nm. Purity of this oxide examples for contaminating of heavy metals consists n.(1E-4...1E-5) wt%. Sols obtained by this method may be used

Determination and distribution of rare earth elements in beach rock samples using instrumental neutron activation analysis (INAA)

NASA Astrophysics Data System (ADS)

Ravisankar, R.; Manikandan, E.; Dheenathayalu, M.; Rao, Brahmaji; Seshadreesan, N. P.; Nair, K. G. M.

2006-10-01

Beach rocks are a peculiar type of formation when compared to other types of rocks. Rare earth element (REE) concentrations in beach rock samples collected from the South East Coast of Tamilnadu, India, have been measured using the instrumental neutron activation analysis (INAA) single comparator K0 method. The irradiations were carried out using a thermal neutron flux of ˜10 11 n cm -2 s -1 at 20 kW power using the Kalpakkam mini reactor (KAMINI), IGCAR, Kalpakkam, Tamilnadu. Accuracy and precision were evaluated by assaying irradiated standard reference material (SRM 1646a estuarine sediment). The results being found to be in good agreement with certified values. REE elements have been determined from 15 samples using high-resolution gamma spectrometry. The geochemical behavior of REE in beach rock, in particular REE (chondrite-normalized) pattern has been studied.

Inductively Coupled Plasma Optical Emission Spectrometry for Rare Earth Elements Analysis

NASA Astrophysics Data System (ADS)

He, Man; Hu, Bin; Chen, Beibei; Jiang, Zucheng

2017-01-01

Inductively coupled plasma optical emission spectrometry (ICP-OES) merits multielements capability, high sensitivity, good reproducibility, low matrix effect and wide dynamic linear range for rare earth elements (REEs) analysis. But the spectral interference in trace REEs analysis by ICP-OES is a serious problem due to the complicated emission spectra of REEs, which demands some correction technology including interference factor method, derivative spectrum, Kalman filtering algorithm and partial least-squares (PLS) method. Matrix-matching calibration, internal standard, correction factor and sample dilution are usually employed to overcome or decrease the matrix effect. Coupled with various sample introduction techniques, the analytical performance of ICP-OES for REEs analysis would be improved. Compared with conventional pneumatic nebulization (PN), acid effect and matrix effect are decreased to some extent in flow injection ICP-OES, with higher tolerable matrix concentration and better reproducibility. By using electrothermal vaporization as sample introduction system, direct analysis of solid samples by ICP-OES is achieved and the vaporization behavior of refractory REEs with high boiling point, which can easily form involatile carbides in the graphite tube, could be improved by using chemical modifier, such as polytetrafluoroethylene and 1-phenyl-3-methyl-4-benzoyl-5-pyrazone. Laser ablation-ICP-OES is suitable for the analysis of both conductive and nonconductive solid samples, with the absolute detection limit of ng-pg level and extremely low sample consumption (0.2 % of that in conventional PN introduction). ICP-OES has been extensively employed for trace REEs analysis in high-purity materials, and environmental and biological samples.

Accumulation of rare earth elements in human bone within the lifespan.

PubMed

Zaichick, Sofia; Zaichick, Vladimir; Karandashev, Vasilii; Nosenko, Sergey

2011-02-01

For the first time, the contents of rare earth elements (REEs) in a rib bone of a healthy human were determined. The mean value of the contents of Ce, Dy, Er, Gd, La, Nd, Pr, Sm, Tb, and Yb (10 elements out of 17 total REEs), as well as the upper limit of means for Ho, Lu, Tm, and Y (4 elements) were measured in the rib bone tissue of 38 females and 42 males (15 to 55 years old) using inductively coupled plasma mass spectrometry (ICP-MS). We found age-related accumulation of REEs in the bone tissue of healthy individuals who lived in a non-industrial region. It was calculated that during a lifespan the content of REEs in a skeleton of non-industrial region residents may increase by one to two orders of magnitude. Using our results as indicative normal values and published data we estimated relative Gd accumulation in the bone tissue of patients according to magnetic resonance imaging with contrast agent and La accumulation in the bone tissue of patients receiving hemodialysis after treatment with lanthanum carbonate as a phosphate binder. It was shown that after such procedures contents of Gd and La in the bone tissue of patients are two to three orders of magnitude higher than normal levels. In our opinion, REEs incorporation may affect bone quality and health similar to other potentially toxic trace metals. The impact of elevated REEs content on bone physiology, biochemistry and morphology requires further investigation.

Rare earth element concentrations in geological and synthetic samples using synchrotron X-ray fluorescence analysis

USGS Publications Warehouse

Chen, J.R.; Chao, E.C.T.; Back, J.M.; Minkin, J.A.; Rivers, M.L.; Sutton, S.R.; Cygan, G.L.; Grossman, J.N.; Reed, M.J.

1993-01-01

The concentrations of rare earth elements (REEs) in specific mineral grains from the Bayan Obo ore deposit and synthetic high-silica glass samples have been measured by synchrotron X-ray fluorescence (SXRF) analysis using excitation of the REE K lines between 33 and 63 keV. Because SXRF, a nondestructive analytical technique, has much lower minimum detection limits (MDLs) for REEs, it is an important device that extends the in situ analytical capability of electron probe microanalysis (EPMA). The distribution of trace amounts of REEs in common rock-forming minerals, as well as in REE minerals and minerals having minor quantities of REEs, can be analyzed with SXRF. Synchrotron radiation from a bending magnet and a wiggler source at the National Synchrotron Light Source, Brookhaven National Laboratory, was used to excite the REEs. MDLs of 6 ppm (La) to 26 ppm (Lu) for 3600 s in 60-??m-thick standard samples were obtained with a 25-??m diameter wiggler beam. The MDLs for the light REEs were a factor of 10-20 lower than the MDLs obtained with a bending magnet beam. The SXRF REE concentrations in mineral grains greater than 25 ??m compared favorably with measurements using EPMA. Because EPMA offered REE MDLs as low as several hundred ppm, the comparison was limited to the abundant light REEs (La, Ce, Pr, Nd). For trace values of medium and heavy REEs, the SXRF concentrations were in good agreement with measurements using instrumental neutron activation analysis (INAA), a bulk analysis technique. ?? 1993.

Recovery of Rare Earth Elements from Coal and Coal Byproducts via a Closed Loop Leaching Process: Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterson, Richard; Heinrichs, Michael; Argumedo, Darwin

Objectives: Through this grant, Battelle proposes to address Area of Interest (AOI) 1 to develop a bench-scale technology to economically separate, extract, and concentrate mixed REEs from coal ash. U.S. coal and coal byproducts provide the opportunity for a domestic source of REEs. The DOE’s National Energy Technology Laboratory (NETL) has characterized various coal and coal byproducts samples and has found varying concentrations of REE ranging up to 1,000 parts per million by weight. The primary project objective is to validate the economic viability of recovering REEs from the coal byproduct coal ash using Battelle’s patented closed-loop Acid Digestion Processmore » (ADP). This will be accomplished by selecting coal sources with the potential to provide REE concentrations above 300 parts per million by weight, collecting characterization data for coal ash samples generated via three different methods, and performing a Techno-Economic Analysis (TEA) for the proposed process. The regional availability of REE-laden coal ash, the regional market for rare earth concentrates, and the system capital and operating costs for rare earth recovery using the ADP technology will be accounted for in the TEA. Limited laboratory testing will be conducted to generate the parameters needed for the design of a bench scale system for REE recovery. The ultimate project outcome will be the design for an optimized, closed loop process to economically recovery REEs such that the process may be demonstrated at the bench scale in a Phase 2 project. Project Description: The project will encompass evaluation of the ADP technology for the economic recovery of REEs from coal and coal ash. The ADP was originally designed and demonstrated for the U.S. Army to facilitate demilitarization of cast-cured munitions via acid digestion in a closed-loop process. Proof of concept testing has been conducted on a sample of Ohio-based Middle Kittanning coal and has demonstrated the feasibility of

Unraveling Recrystallization Mechanisms Governing Texture Development from Rare-Earth Element Additions to Magnesium

NASA Astrophysics Data System (ADS)

Imandoust, Aidin; Barrett, Christopher D.; Al-Samman, Talal; Tschopp, Mark A.; Essadiqi, Elhachmi; Hort, Norbert; El Kadiri, Haitham

2018-03-01

The origin of texture components often associated with rare-earth element (REE) additions in wrought magnesium alloys is a long-standing problem in magnesium technology. While their influence on the texture is unquestionable, it is not yet clear why certain texture components, such as < 11\\bar{2}1 > ||{extrusion}{direction}, are favored over other components typically observed in traditional magnesium alloys. The objective of this research is to identify the mechanisms accountable for these RE textures during early stages of recrystallization. Electron backscattered diffraction and transmission electron microscopy analyses reveal that REEs in zinc-containing magnesium alloys corroborate discontinuous dynamic recrystallization. REEs promote isotropic growth for all nuclei generated through the bulging mechanism. During nucleation, the effect of REEs on orientation selection was explained by the diversified activity of both < 10\\bar{1}0 > and [0001] Taylor axes in the same grain with a marked preference for [0001] rotations to occur first. During nuclei growth, no growth preference was observed when sufficient REEs are added in the zinc-containing magnesium alloys, instead isotropic nuclei growth across all grain orientations occurs. This phenomenon is attributed to REEs segregating to grain boundaries (GBs), in agreement with prior computational and theoretical results (Barrett et al., Scripta Mater 146:46-50, 2018) that show a more isotropic GB energy and mobility after segregation.

Rare Earth Element Recovery from Low-Grade Feedstocks Using Engineered E. coli

NASA Astrophysics Data System (ADS)

Brewer, A. W.; Park, D.; Jiao, Y.

2017-12-01

Rare earth elements (REEs) are critical materials for emerging science and technology industries, especially in the field of clean energy. However, their supply is potentially at risk due to political and economic concerns. The exploitation of new, low-grade REE sources in the United States, such as geothermal brines and mine tailings, may help to mitigate that supply risk. To purify and concentrate REEs from these sources, we have developed a biosorption approach using engineered E. coli cells that express a lanthanide binding tag on the cell surface. This tag has a high selectivity for REEs that enhances the native cell wall adsorption properties; the terbium adsorption capacity was increased approximately 2-fold, and the REE surface affinity was increased compared to all non-REE metals except copper. This biosorption method offers advantages over conventional REE extraction methods as it is inexpensive, environmentally friendly, and effective with low-grade feedstocks. In order to expand this method to an industrial scale, the cells must be contained in a durable material that permits the cell surfaces to function in a variety of bioreactor systems and to be reused through multiple adsorption and desorption cycles. Polyethylene glycol diacrylate (PEGDA) beads, with diameters from 200-400 um, can be impregnated with high concentrations of cells, and show promise in the selective adsorption of REEs from solution. In the future, the application of the adsorptive qualities of these engineered cells may be expanded to include other valuable metals, such as indium and gallium, to further develop the economic potential of this approach. Prepared by LLNL under Contract DE-AC52-07NA27344. LLNL-ABS-736022.

Direct quantification of rare earth doped titania nanoparticles in individual human cells

NASA Astrophysics Data System (ADS)

Jeynes, J. C. G.; Jeynes, C.; Palitsin, V.; Townley, H. E.

2016-07-01

There are many possible biomedical applications for titania nanoparticles (NPs) doped with rare earth elements (REEs), from dose enhancement and diagnostic imaging in radiotherapy, to biosensing. However, there are concerns that the NPs could disintegrate in the body thus releasing toxic REE ions to undesired locations. As a first step, we investigate how accurately the Ti/REE ratio from the NPs can be measured inside human cells. A quantitative analysis of whole, unsectioned, individual human cells was performed using proton microprobe elemental microscopy. This method is unique in being able to quantitatively analyse all the elements in an unsectioned individual cell with micron resolution, while also scanning large fields of view. We compared the Ti/REE signal inside cells to NPs that were outside the cells, non-specifically absorbed onto the polypropylene substrate. We show that the REE signal in individual cells co-localises with the titanium signal, indicating that the NPs have remained intact. Within the uncertainty of the measurement, there is no difference between the Ti/REE ratio inside and outside the cells. Interestingly, we also show that there is considerable variation in the uptake of the NPs from cell-to-cell, by a factor of more than 10. We conclude that the NPs enter the cells and remain intact. The large heterogeneity in NP concentrations from cell-to-cell should be considered if they are to be used therapeutically.

The impact of transport processes on rare earth element patterns in marine authigenic and biogenic phosphates

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2017-04-01

Rare earth elements (REEs) are commonly used proxies to reconstruct water chemistry and oxygen saturation during the formation of authigenic and biogenic phosphates in marine environments. In the modern ocean REEs exhibit a distinct pattern with enrichment of heavy REEs and strong depletion in cerium (Ce). The wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry has been very different in the Earth's past. However, both early and late diagenesis are known to affect REE signatures in phosphates altering primary marine signals. Herein we present a dataset of REE signatures in 38 grain specific LA-ICP-MS measurements of isolated phosphate and carbonate grains in three discrete rock samples. The phosphates mainly consist of authigenic phosphates and phosphatized microfossils that formed in a microbially mediated micro-milieu. In addition, isolated biogenic and reworked phosphatic grains are also present. The phosphates are emplaced in bioclastic grain- to packstones deposited on a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene Monterey event. The results reveal markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Grain shape and REE patterns together indicate that authigenic, biogenic and reworked phosphates have distinct REE patterns irrespective of the sample. Our study shows that while REE patterns in phosphates do reflect water chemistry during authigenesis, they are often already heavily altered during reworking, a process, which can occur in geologically negligible timespans. REE patterns are therefore more likely to reflect complex enrichment processes after their formation. Similarities in the REE patterns of reworked and biogenic phosphate further suggest that the

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.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis

NASA Astrophysics Data System (ADS)

Zaharescu, Dragos G.; Burghelea, Carmen I.; Dontsova, Katerina; Presler, Jennifer K.; Maier, Raina M.; Huxman, Travis; Domanik, Kenneth J.; Hunt, Edward A.; Amistadi, Mary K.; Gaddis, Emily E.; Palacios-Menendez, Maria A.; Vaquera-Ibarra, Maria O.; Chorover, Jon

2017-02-01

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake.

Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis

PubMed Central

Zaharescu, Dragos G.; Burghelea, Carmen I.; Dontsova, Katerina; Presler, Jennifer K.; Maier, Raina M.; Huxman, Travis; Domanik, Kenneth J.; Hunt, Edward A.; Amistadi, Mary K.; Gaddis, Emily E.; Palacios-Menendez, Maria A.; Vaquera-Ibarra, Maria O.; Chorover, Jon

2017-01-01

The rare earth elements (REE) are increasingly important in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. However, REE distribution in early rock-microbe-plant systems has remained elusive. We tested the hypothesis that REE mass-partitioning during incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, vascular plants (Buffalo grass), and arbuscular mycorrhiza. Pore-water element abundances revealed a rapid transition from abiotic to biotic signatures of weathering, the latter associated with smaller aqueous loss and larger plant uptake. Abiotic dissolution was 39% of total denudation in plant-microbes-mycorrhiza treatment. Microbes incremented denudation, particularly in rhyolite, and this resulted in decreased bioavailable solid pools in this rock. Total mobilization (aqueous + uptake) was ten times greater in planted compared to abiotic treatments, REE masses in plant generally exceeding those in water. Larger plants increased bioavailable solid pools, consistent with enhanced soil genesis. Mycorrhiza generally had a positive effect on total mobilization. The main mechanism behind incipient REE weathering was carbonation enhanced by biotic respiration, the denudation patterns being largely dictated by mineralogy. A consistent biotic signature was observed in La:phosphate and mobilization: solid pool ratios, and in the pattern of denudation and uptake. PMID:28230202

Effect of low doses of dietary rare earth elements on growth performance of broilers.

PubMed

He, M L; Wehr, U; Rambeck, W A

2010-02-01

The present study was designed to investigate effect of dietary rare earth elements (REE), including both organic and inorganic compounds, on growth performance of broilers. In experiment 1, a total of 180 male Ross broiler chicks were allocated to 72 pens with different assignment: four chicks per pen or individually. The following three treatment diets were applied: control, REE-chlorides at a dose of 40 mg/kg and REE-citrate at a dose of 70 mg/kg. Each treatment group had 24 pens containing both assignments (12 pens each). In experiment 2, a total of 72 male 3-day-old Ross broiler chicks were separated to four groups: control, REE-chlorides at a dose of 70 mg/kg and REE-citrate at doses of 70 mg/kg and 100 mg/kg. In experiment 1, dietary REE-citrate improved body weight gain during the overall period by 5.0% (p < 0.05) while the increase with REE-chloride was not significant. In experiment 2, growth effects (p < 0.05) were only found in the period from day 21 to slaughter with all REE forms, and feed conversion ratio was improved by 3.4% (p < 0.05) with REE-citrate. No significant effects of REE were found on chill weight, percentages of breast meat, thigh weight, drumstick weight and wing weight. Concentrations of La and Ce in the liver and muscles were very low, accounting for 0.11-0.76 and 0.02-0.30 mg/kg respectively. There was weak tendency for a dose-response relationship especially in the groups supplemented with REE-chlorides. The main blood serum biochemical parameters were not significantly affected by REE in the diets. The results suggest that dietary supplementation of low doses of REE-citrates might improve growth performance of broilers without affecting carcass composition and health of the broilers.

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

The surface sediment types and their rare earth element characteristics from the continental shelf of the northern south China sea

NASA Astrophysics Data System (ADS)

Wang, Shuhong; Zhang, Nan; Chen, Han; Li, Liang; Yan, Wen

2014-10-01

The grain size as well as some major and trace elements, including rare earth element (REE), for 273 surface sediment samples collected from the continental shelf of the northern South China Sea were analyzed in this study. The sediment types are mainly sandy silt and silt, making up 60% of the whole samples, and secondly are mud, sandy mud, muddy sand and silty sand, making up 28% of the whole samples, based on grain-size in which the Folk's classification was used. The total REE content (ΣREE) show a wide variation from 21 ppm to 244 ppm with an average value of 155 ppm, which similar to the average ΣREE of the China loess, but much different from that in deep-sea clay, showing a significant terrigenous succession. The REE contents in different sediment types vary greatly, mainly enriching in silt, sandy silt, mud and sandy mud. The REE distribution contours parallel to the coastal, presenting like strips and their contents gradually reduce with increasing distance from the coast. The high content of the western Pearl River Mouth, Shang/Xiachuan Islands and Hailing Bay might be regarded to the coastal current developed from the east to the west along to the Pearl River Mouth in the northern South China Sea. But the chondrite-normalized REE patterns in various sediment types have no difference, basically same as those of coastal rivers and upper crust. They all show relative enrichments in light rare earth element (LREE), noticeable negative Eu anomaly and no Ce anomaly, indicating that those sediments are terrigenous sediments and from the same source region. Further analysis suggest that the sedimentary environment in the study area is relatively stable and granite widely distributed in the South China mainland is the main source of REE, which are transported mainly by the Pearl River. The late diagenesis has little effect on the REE.

The fractionation and geochemical characteristics of rare earth elements measured in ambient size-resolved PM in an integrated iron and steelmaking industry zone.

PubMed

Dai, Qili; Li, Liwei; Yang, Jiamei; Liu, Baoshuang; Bi, Xiaohui; Wu, Jianhui; Zhang, YuFen; Yao, Lin; Feng, Yinchang

2016-09-01

Improved understanding of the fractionation and geochemical characteristic of rare earth elements (REEs) from steel plant emissions is important due to the unclear atmospheric signature of these elements and their adverse impact on human health and the environment. In this study, ambient particulate matter of different sizes was collected from one site in an integrated iron and steelmaking industrial zone (HG) and one urban background site with no direct industrial emissions (ZWY) during a 1-year sampling campaign in China. The total concentrations of REEs for TSP, PM10, and PM2.5 were 27.248, 14.989, 3.542 ng/m(3) in HG and 6.326, 5.274, 1.731 ng/m(3), respectively, in ZWY, which revealed the local influence of the steelmaking activities to the air quality. With respect to ZWY, the REEs in HG site are obviously fractionated in the coarser fraction, and LREEs account for more than 80 % of the total REE burden in all of the samples. Additionally, the REEs in HG and ZWY show a homogeneous trend with successively increased LREE/HREE ratios from the coarse particles to the fine particles. In our samples, La, Ce, Nd, and Sm are the most enriched rare earth elements, especially in the HG site. Moreover, ternary diagrams of LaCeSm indicate that the REEs in HG are potentially contributed by steelworks, carrier vehicles, coal combustion, and road dust re-suspension.

Interaction of rare earth elements and components of the Horonobe deep groundwater.

PubMed

Kirishima, Akira; Kuno, Atsushi; Amamiya, Hiroshi; Kubota, Takumi; Kimuro, Shingo; Amano, Yuki; Miyakawa, Kazuya; Iwatsuki, Teruki; Mizuno, Takashi; Sasaki, Takayuki; Sato, Nobuaki

2017-02-01

To better understand the migration behavior of minor actinides in deep groundwater, the interactions between doped rare earth elements (REEs) and components of Horonobe deep groundwater were investigated. Approximately 10 ppb of the REEs, i.e. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, and Yb were doped into a groundwater sample collected from a packed section in a borehole drilled at 140 m depth in the experiment drift of Horonobe Underground Research Laboratory in Hokkaido, Japan. The groundwater sample was sequentially filtered with a 0.2 μm pore filter, and 10 kDa, 3 kDa and 1 kDa nominal molecular weight limit (NMWL) ultrafilters with conditions kept inert. Next, the filtrate solutions were analyzed with inductively coupled plasma mass spectrometry (ICP-MS) to determine the concentrations of the REEs retained in solution at each filtration step, while the used filters were analyzed through neutron activation analysis (NAA) and TOF-SIMS element mapping to determine the amounts and chemical species of the trapped fractions of REEs on each filter. A strong relationship between the ratios of REEs retained in the filtrate solutions and the ionic radii of the associated REEs was observed; i.e. smaller REEs occur in larger proportions dissolved in the solution phase under the conditions of the Horonobe groundwater. The NAA and TOF-SIMS analyses revealed that portions of the REEs were trapped by the 0.2 μm pore filter as REE phosphates, which correspond to the species predicted to be predominant by chemical equilibrium calculations for the conditions of the Horonobe groundwater. Additionally, small portions of colloidal REEs were trapped by the 10 kDa and 3 kDa NMWL ultrafilters. These results suggest that phosphate anions play an important role in the chemical behavior of REEs in saline (seawater-based) groundwater, which may be useful for predicting the migration behavior of trivalent actinides released from radioactive waste repositories in the far

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.

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE PAGES

Yang, Jon; Verba, Circe; Torres, Marta; ...

2018-02-01

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jon; Verba, Circe; Torres, Marta

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Typical aqueous rare earth element behavior in co-produced Brines, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nye, Charles; Quillinan, Scott; McLing, Travis

Normalization of Rare Earth Elements (REEs) is important to remove the distracting effects of the Oddo–Harkins rule and provide a meaningful baseline. Normalizations for rocks are well developed and include chondritic meteorites, UCC, PM, PAAS, and NASC. However normalizations for aqueous REEs are limited to oceanic regions such as the North Pacific Deep Water or North Atlantic Surface Water. This leaves water in contact with continental lithologies without a suitable normalization. We present a preliminary continental aqueous REE normalization derived from 38 deep basin hydrocarbon brines in Wyoming. The REEs in these waters are seven orders of magnitude more dilutemore » than NASC but with significant europium enrichment. Gromet 1984 reports NASC Eu/Eu* is 0.2179, whereas in the normalization offered here, Eu/Eu* is 3.868. These waters also are free from the distracting reduction-oxidation cerium behavior found in ocean normalizations. Because these samples exhibit both the uniform behavior of NASC and the absolute concentration of seawater, a normalization based upon them offers a unique combination of the advantages of both. We used single-peak gaussian analysis to quantify the mean values for each REE and estimate the distribution variability. Additional sample collection during the last year revealed that the Powder River Basin (PRB) is atypical relative to the other sampled basins of Wyoming. Those other basins are the Wind River Basin (WRB) Green River Basin (GRB) and Wamsutter Area (WA). A pre-normalization gadolinium anomaly (Gd/Gd*) of between 4 and 23 with a mean of 11.5, defines the PRB samples. Other basins in this study range from 1 to 7 with a mean of 2.8. Finally, we present a preliminary model for ligand-based behavior of REEs in these samples. This model identifies bicarbonate, bromide, and chloride as forming significant complexes with REEs contributing to REE solubility. The ligand model explains observed REEs in the sampled Cretaceous and

Novel Polyethylenimine–Acrylamide/SiO 2 Hybrid Hydrogel Sorbent for Rare-Earth-Element Recycling from Aqueous Sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qiuming; Wilfong, Walter C.; Kail, Brian W.

Recycling rare earth elements (REEs) becomes increasingly important due to their supply vulnerability and increasing demands in industry, agriculture, and national security. Hybrid hydrogel sorbents were outstanding due to their high stability and selectivity. Organic-inorganic hybrid hydrogels were synthesized by thermo-polymerization of acrylamide onto PEI polymer chain with N,N’-methylene bisacrylamide as a crosslinker. The grafted network was evidenced by DRIFTS and XPS. The porous structure was observed by SEM. Crosslink degree, PEI grafting degree, and SiO 2 concentration were studied to optimize the REEs adsorption. The pH value of the medium greatly affected REE adsorption capacity, where the nearly neutralmore » conditions gave the strongest bonding of REEs to active sites. Moreover, kinetic studies showed that the rate-determining step of the adsorption process was chemical sorption, and that REE diffusion within micropores was the control step for, specifically, intraparticle diffusion. The adsorbents showed excellent selectivity and recyclability for REEs through 5 adsorption-desorption cycles in contact with synthetic acid mine drainage solution. A high separation toward REEs over fouling metals was achieved by using a citrate-based buffer eluent solution. This hybrid hydrogel shows promise for the recycling of REEs from aqueous solutions.« less

Novel Polyethylenimine–Acrylamide/SiO 2 Hybrid Hydrogel Sorbent for Rare-Earth-Element Recycling from Aqueous Sources

DOE PAGES

Wang, Qiuming; Wilfong, Walter C.; Kail, Brian W.; ...

2017-09-14

Recycling rare earth elements (REEs) becomes increasingly important due to their supply vulnerability and increasing demands in industry, agriculture, and national security. Hybrid hydrogel sorbents were outstanding due to their high stability and selectivity. Organic-inorganic hybrid hydrogels were synthesized by thermo-polymerization of acrylamide onto PEI polymer chain with N,N’-methylene bisacrylamide as a crosslinker. The grafted network was evidenced by DRIFTS and XPS. The porous structure was observed by SEM. Crosslink degree, PEI grafting degree, and SiO 2 concentration were studied to optimize the REEs adsorption. The pH value of the medium greatly affected REE adsorption capacity, where the nearly neutralmore » conditions gave the strongest bonding of REEs to active sites. Moreover, kinetic studies showed that the rate-determining step of the adsorption process was chemical sorption, and that REE diffusion within micropores was the control step for, specifically, intraparticle diffusion. The adsorbents showed excellent selectivity and recyclability for REEs through 5 adsorption-desorption cycles in contact with synthetic acid mine drainage solution. A high separation toward REEs over fouling metals was achieved by using a citrate-based buffer eluent solution. This hybrid hydrogel shows promise for the recycling of REEs from aqueous solutions.« less

A novel methodology for rapid digestion of rare earth element ores and determination by microwave plasma-atomic emission spectrometry and dynamic reaction cell-inductively coupled plasma-mass spectrometry.

PubMed

Helmeczi, Erick; Wang, Yong; Brindle, Ian D

2016-11-01

Short-wavelength infrared radiation has been successfully applied to accelerate the acid digestion of refractory rare-earth ore samples. Determinations were achieved with microwave plasma-atomic emission spectrometry (MP-AES) and dynamic reaction cell - inductively coupled plasma-mass spectrometry (DRC-ICP-MS). The digestion method developed was able to tackle high iron-oxide and silicate matrices using only phosphoric acid in a time frame of only 8min, and did not require perchloric or hydrofluoric acid. Additionally, excellent recoveries and reproducibilities of the rare earth elements, as well as uranium and thorium, were achieved. Digestions of the certified reference materials OREAS-465 and REE-1, with radically different mineralogies, delivered results that mirror those obtained by fusion processes. For the rare-earth CRM OKA-2, whose REE data are provisional, experimental data for the rare-earth elements were generally higher than the provisional values, often exceeding z-values of +2. Determined values for Th and U in this reference material, for which certified values are available, were in excellent agreement. Copyright © 2016 Elsevier B.V. All rights reserved.

LA-ICP-MS analysis of isolated phosphatic grains indicates selective rare earth element enrichment during reworking and transport processes

NASA Astrophysics Data System (ADS)

Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

2016-04-01

Rare earth elements (REE) are a commonly used proxy to reconstruct water chemistry and oxygen saturation during the formation history of authigenic and biogenic phosphates in marine environments. In the modern ocean REE exhibit a distinct pattern with enrichment of heavy REE and strong depletion in Cerium. Studies of ancient phosphates and carbonates, however, showed that this 'modern' pattern is only rarely present in the geological past. Consequently, the wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry had to have been radically different in the earth's past. A wealth of studies has already shown that both early and late diagenesis can strongly affect REE signatures in phosphates and severely alter primary marine signals. However, no previous research was conducted on how alteration processes occurring prior to final deposition affect marine phosphates. Herein we present a dataset of multiple LA-ICP-MS measurements of REE signatures in isolated phosphate and carbonate grains deposited in a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene "Monterey event". The phosphates are represented by authigenic, biogenic and detrital grains emplaced in bioclastic grain- to packstones dominated by bryozoan and echinoderm fragments, as well as abundant benthic and planktic foraminifers. The results of 39 grain specific LA-ICP-MS measurements in three discrete rock samples reveals four markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Considering grain shape and REE patterns together indicate that authigenic, detrital and biogenic phosphates have distinct REE patterns irrespective of the sample. Our results show that the observed REE patterns in phosphates only broadly reflect

Effects of soil type on leaching and runoff transport of rare earth elements and phosphorous in laboratory experiments.

PubMed

Wang, Lingqing; Liang, Tao; Chong, Zhongyi; Zhang, Chaosheng

2011-01-01

Through leaching experiments and simulated rainfall experiments, characteristics of vertical leaching of exogenous rare earth elements (REEs) and phosphorus (P) and their losses with surface runoff during simulated rainfall in different types of soils (terra nera soil, cinnamon soil, red soil, loess soil, and purple soil) were investigated. Results of the leaching experiments showed that vertical transports of REEs and P were relatively low, with transport depths less than 6 cm. The vertical leaching rates of REEs and P in the different soils followed the order of purple soil > terra nera soil > red soil > cinnamon soil > loess soil. Results of the simulated rainfall experiments (83 mm h⁻¹) revealed that more than 92% of REEs and P transported with soil particles in runoff. The loss rates of REEs and P in surface runoff in the different soil types were in the order of loess soil > terra nera soil > cinnamon soil > red soil > purple soil. The total amounts of losses of REEs and P in runoff were significantly correlated.

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

Rare earth element content of cryptocrystalline magnesites of Konya, Turkey

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zedef, Veysel, E-mail: vzedef@selcuk.edu.tr; Russell, Michael

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

U-Pb, Re-Os, and Ar/Ar geochronology of rare earth element (REE)-rich breccia pipes and associated host rocks from the Mesoproterozoic Pea Ridge Fe-REE-Au deposit, St. Francois Mountains, Missouri

USGS Publications Warehouse

Aleinikoff, John N.; Selby, David; Slack, John F.; Day, Warren C.; Pillers, Renee M.; Cosca, Michael A.; Seeger, Cheryl; Fanning, C. Mark; Samson, Iain

2016-01-01

Rare earth element (REE)-rich breccia pipes (600,000 t @ 12% rare earth oxides) are preserved along the margins of the 136-million metric ton (Mt) Pea Ridge magnetite-apatite deposit, within Mesoproterozoic (~1.47 Ga) volcanic-plutonic rocks of the St. Francois Mountains terrane in southeastern Missouri, United States. The breccia pipes cut the rhyolite-hosted magnetite deposit and contain clasts of nearly all local bedrock and mineralized lithologies.Grains of monazite and xenotime were extracted from breccia pipe samples for SHRIMP U-Pb geochronology; both minerals were also dated in one polished thin section. Monazite forms two morphologies: (1) matrix granular grains composed of numerous small (<50 μm) crystallites intergrown with rare xenotime, thorite, apatite, and magnetite; and (2) coarse euhedral, glassy, bright-yellow grains similar to typical igneous or metamorphic monazite. Trace element abundances (including REE patterns) were determined on selected grains of monazite (both morphologies) and xenotime. Zircon grains from two samples of host rhyolite and two late felsic dikes collected underground at Pea Ridge were also dated. Additional geochronology done on breccia pipe minerals includes Re-Os on fine-grained molybdenite and 40Ar/39Ar on muscovite, biotite, and K-feldspar.Ages (±2σ errors) obtained by SHRIMP U-Pb analysis are as follows: (1) zircon from the two host rhyolite samples have ages of 1473.6 ± 8.0 and 1472.7 ± 5.6 Ma; most zircon in late felsic dikes is interpreted as xenocrystic (age range ca. 1522–1455 Ma); a population of rare spongy zircon is likely of igneous origin and yields an age of 1441 ± 9 Ma; (2) pale-yellow granular monazite—1464.9 ± 3.3 Ma (no dated xenotime); (3) reddish matrix granular monazite—1462.0 ± 3.5 Ma and associated xenotime—1453 ± 11 Ma; (4) coarse glassy-yellow monazite—1464.8 ± 2.1, 1461.7 ± 3.7 Ma, with rims at 1447.2 ± 4.7 Ma; and (5) matrix monazite (in situ)—1464.1 ± 3.6 and 1454

Spatial variability and geochemistry of rare earth elements in soils from the largest uranium-phosphate deposit of Brazil.

PubMed

Cunha, Cleyton Saialy Medeiros; da Silva, Ygor Jacques Agra Bezerra; Escobar, Maria Eugenia Ortiz; do Nascimento, Clístenes Williams Araújo

2018-02-22

The Itataia uranium-phosphate deposit is the largest uranium reserve in Brazil. Rare earth elements (REEs) are commonly associated with phosphate deposits; however, there are no studies on the concentrations of REEs in soils of the Itataia deposit region. Thus, the objective of the research was to evaluate the concentration and spatial variability of REEs in topsoils of Itataia phosphate deposit region. In addition, the influence of soil properties on the geochemistry of REEs was investigated. Results showed that relatively high mean concentrations (mg kg -1 ) of heavy REEs (Gd 6.01; Tb 1.25; Ho 1.15; Er 4.05; Tm 0.64; Yb 4.61; Lu 0.65) were found in surface soils samples. Soil properties showed weak influence on the geochemical behavior of REEs in soils, except for the clay content. On the other hand, parent material characteristics, such as P and U, had strong influence on REEs concentrations. Spatial distribution patterns of REEs in soils are clearly associated with P and U contents. Therefore, geochemical surveys aiming at the delineation of ore-bearing zones in the region can benefit from our data. The results of this work reinforce the perspective for co-mining of P, U and REEs in this important P-U reserve.

Environmentally Friendly Economical Sequestration of Rare Earth Metals from Geothermal Waters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stull, Dean P.

The purpose of this work was to complete a proof of concept study to apply and validate a novel method developed by Tusaar for the capture and recovery of rare earth elements (known as REEs) and other critical and valuable elements from geothermal waters produced from deep within the earth. Geothermal water provides heat for power production at many geothermal power plants in the western United States. The target elements, the REEs, are vital to modern day electronics, batteries, motors, automobiles and many other consumer favorites and necessities. Currently there are no domestic sources of REEs while domestic and internationalmore » demand for the products they are used in continues to rise. Many of the REEs are considered “strategically” important. A secure supply of REEs in the USA would benefit consumers and the country at large. A new method to recover these REEs from geothermal waters used at existing geothermal power plants around the country is a high priority and would benefit consumers and the USA. The result of this project was the successful development and demonstration of an integrated process for removal and recovery of the REEs from synthetic geothermal brines on a small laboratory scale. The work included preparation of model geothermal brines to test, selection of the most effective proprietary sorbent media to capture the REEs and testing of the media under a variety of potential operating conditions. Geothermal brines are generally very high in salt content and contain a wide range of elements and anions associated with the rock layers from which they are produced. Processing the geothermal water is difficult because it is corrosive and the dissolved minerals in the water precipitate easily once the temperature and pressure change. No commercial technologies have been shown to be effective or robust enough under these geothermal brine conditions to be commercially viable for removal of REEs. Technologies including ion exchange

Geochemistry of rare earth elements within waste rocks from the Montviel carbonatite deposit, Québec, Canada.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Pelletier, Mia

2018-04-01

Several rare earth element (REE) mine projects around the world are currently at the feasibility stage. Unfortunately, few studies have evaluated the contamination potential of REE and their effects on the environment. In this project, the waste rocks from the carbonatites within the Montviel proterozoic alkaline intrusion (near Lebel-sur-Quévillon, Quebec, Canada) are assessed in this research. The mineralization is mainly constituted by light REE (LREE) fluorocarbonates (qaqarssukite-Ce, kukharenkoite-Ce), LREE carbonates (burbankite, Sr-Ba-Ca-REE, barytocalcite, strontianite, Ba-REE-carbonates), and phosphates (apatite, monazite). The gangue minerals are biotites, chlorite, albite, ankerite, siderite, and calcite. The SEM-EDS analyses show that (i) the majority of REE are associated with the fine fraction (< 106 μm), (ii) REE are mainly associated with carbonates, (iii) all analyzed minerals preferably contain LREE (La, Ce, Pr, Nd, Sm, Eu), (iv) the sum of LREE in each analyzed mineral varies between ~ 3 and 10 wt%, (v) the heavy REE (HREE) identified are Gd and Yb at < 0.4 wt%, and (vi) three groups of carbonate minerals were observed containing variable concentrations of Ca, Na, and F. Furthermore, the mineralogical composition of REE-bearing minerals, REE mobility, and REE speciation was investigated. The leachability and geochemical behavior of these REE-bearing mine wastes were tested using normalized kinetic testing (humidity cells). Leachate results displayed higher LREE concentrations, with decreasing shale-normalized patterns. Thermodynamical equilibrium calculations suggest that the precipitation of secondary REE minerals may control the REE mobility.

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

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.

Geochemical studies of rare earth elements in the Portuguese pyrite belt, and geologic and geochemical controls on gold distribution

USGS Publications Warehouse

Grimes, David J.; Earhart, Robert L.; de Carvalho, Delfim; Oliveira, Vitor; Oliveira, Jose T.; Castro, Paulo

1998-01-01

This report describes geochemical and geological studies which were conducted by the U.S. Geological Survey (USGS) and the Servicos Geologicos de Portugal (SPG) in the Portuguese pyrite belt (PPB) in southern Portugal. The studies included rare earth element (REE) distributions and geological and geochemical controls on the distribution of gold. Rare earth element distributions were determined in representative samples of the volcanic rocks from five west-trending sub-belts of the PPB in order to test the usefulness of REE as a tool for the correlation of volcanic events, and to determine their mobility and application as hydrothermal tracers. REE distributions in felsic volcanic rocks show increases in the relative abundances of heavy REE and a decrease in La/Yb ratios from north to south in the Portuguese pyrite belt. Anomalous amounts of gold are distributed in and near massive and disseminated sulfide deposits in the PPB. Gold is closely associated with copper in the middle and lower parts of the deposits. Weakly anomalous concentrations of gold were noted in exhalative sedimentary rocks that are stratigraphically above massive sulfide deposits in a distal manganiferous facies, whereas anomalously low concentrations were detected in the barite-rich, proximal-facies exhalites. Altered and pyritic felsic volcanic rocks locally contain highly anomalous concentrations of gold, suggesting that disseminated sulfide deposits and the non-ore parts of massive sulfide deposits should be evaluated for their gold potential.

Leaching of rare earth elements from fluorescent powder using the tea fungus Kombucha.

PubMed

Hopfe, Stefanie; Flemming, Katrin; Lehmann, Falk; Möckel, Robert; Kutschke, Sabine; Pollmann, Katrin

2017-04-01

In most modern technologies such as flat screens, highly effective magnets and lasers, as well as luminescence phosphors, Rare Earth Elements (REE) are used. Unfortunately no environmentally friendly recycling process exists so far. In comparison to other elements the interaction of microorganisms with REE has been studied to a less extent. However, as REE are ubiquitously present in nature it can be assumed that microorganisms play an important role in the biogeochemistry of REE. This study investigates the potential of organic acid-producing microbes for extracting REE from industrial waste. In Germany, 175 tons of fluorescent phosphor (FP) are collected per year as a distinct fraction from the recycling of compact fluorescent lamps. Because the FP contains about 10% of REE-oxides bound in the so-called triband dyes it is a readily accessible secondary resource of REE. Using the symbiotic mixed culture Kombucha, consisting of yeasts and acetic acid bacteria, REE were leached at a significant rate. The highest leaching-rates were observed in shake cultures using the entire Kombucha-consortium or its supernatant as leaching agent compared to experiments using the isolates Zygosaccharomyces lentus and Komagataeibacter hansenii as leaching organisms. During the cultivation, the pH decreased as a result of organic acid production (mainly acetic and gluconic acid). Thus, the underlying mechanism of the triband dye solubilisation is probably linked to the carboxyl-functionality or a proton excess. In accordance with the higher solubility of REE-oxides compared to REE-phosphates and -aluminates, the red dye Y 2 O 3 :Eu 2+ containing relatively expensive REE was shown to be preferentially solubilized. These results show that it is possible to dissolve the REE-compounds of FP with the help of microbial processes. Moreover, they provide the basis for the development of an eco-friendly alternative to the currently applied methods that use strong inorganic acids or toxic

Ultrasound-assisted extraction of rare-earth elements from carbonatite rocks.

PubMed

Diehl, Lisarb O; Gatiboni, Thais L; Mello, Paola A; Muller, Edson I; Duarte, Fabio A; Flores, Erico M M

2018-01-01

In view of the increasing demand for rare-earth elements (REE) in many areas of high technology, alternative methods for the extraction of these elements have been developed. In this work, a process based on the use of ultrasound for the extraction of REE from carbonatite (an igneous rock) is proposed to avoid the use of concentrated reagents, high temperature and excessive extraction time. In this pioneer work for REE extraction from carbonatite rocks in a preliminary investigation, ultrasonic baths, cup horn systems or ultrasound probes operating at different frequencies and power were evaluated. In addition, the power released to the extraction medium and the ultrasound amplitude were also investigated and the temperature and carbonatite mass/volume of extraction solution ratio were optimized to 70°C and 20mg/mL, respectively. Better extraction efficiencies (82%) were obtained employing an ultrasound probe operating at 20kHz for 15min, ultrasound amplitude of 40% (692Wdm -3 ) and using a diluted extraction solution (3% v/v HNO 3 +2% v/v HCl). It is important to mention that high extraction efficiency was obtained even using a diluted acid mixture and relatively low temperature in comparison to conventional extraction methods for REE. A comparison of results with those obtained by mechanical stirring (500rpm) using the same conditions (time, temperature and extraction solution) was carried out, showing that the use of ultrasound increased the extraction efficiency up to 35%. Therefore, the proposed ultrasound-assisted procedure can be considered as a suitable alternative for high efficiency extraction of REE from carbonatite rocks. Copyright © 2017 Elsevier B.V. All rights reserved.

Fast and simultaneously determination of light and heavy rare earth elements in monazite using combination of ultraviolet-visible spectrophotometry and multivariate analysis

NASA Astrophysics Data System (ADS)

Anggraeni, Anni; Arianto, Fernando; Mutalib, Abdul; Pratomo, Uji; Bahti, Husein H.

2017-05-01

Rare Earth Elements (REE) are elements that a lot of function for life, such as metallurgy, optical devices, and manufacture of electronic devices. Sources of REE is present in the mineral, in which each element has similar properties. Currently, to determining the content of REE is used instruments such as ICP-OES, ICP-MS, XRF, and HPLC. But in each instruments, there are still have some weaknesses. Therefore we need an alternative analytical method for the determination of rare earth metal content, one of them is by a combination of UV-Visible spectrophotometry and multivariate analysis, including Principal Component Analysis (PCA), Principal Component Regression (PCR), and Partial Least Square Regression (PLS). The purpose of this experiment is to determine the content of light and medium rare earth elements in the mineral monazite without chemical separation by using a combination of multivariate analysis and UV-Visible spectrophotometric methods. Training set created 22 variations of concentration and absorbance was measured using a UV-Vis spectrophotometer, then the data is processed by PCA, PCR, and PLSR. The results were compared and validated to obtain the mathematical equation with the smallest percent error. From this experiment, mathematical equation used PLS methods was better than PCR after validated, which has RMSE value for La, Ce, Pr, Nd, Gd, Sm, Eu, and Tb respectively 0.095; 0.573; 0.538; 0.440; 3.387; 1.240; 1.870; and 0.639.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 fieldsmore » 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.« less

Comparative toxicities of selected rare earth elements: Sea urchin embryogenesis and fertilization damage with redox and cytogenetic effects.

PubMed

Pagano, Giovanni; Guida, Marco; Siciliano, Antonietta; Oral, Rahime; Koçbaş, Fatma; Palumbo, Anna; Castellano, Immacolata; Migliaccio, Oriana; Thomas, Philippe J; Trifuoggi, Marco

2016-05-01

Broad-ranging adverse effects are known for rare earth elements (REE), yet only a few studies tested the toxicity of several REE, prompting studies focusing on multi-parameter REE toxicity. Trichloride salts of Y, La, Ce, Nd, Sm, Eu and Gd were tested in Paracentrotus lividus sea urchin embryos and sperm for: (1) developmental defects in either REE-exposed larvae or in the offspring of REE-exposed sperm; (2) fertilization success; (3) mitotic anomalies in REE-exposed embryos and in the offspring of REE-exposed sperm, and (4) reactive oxygen species (ROS) formation, and malondialdehyde (MDA) and nitric oxide (NO) levels. REEs affected P. lividus larvae with concentration-related increase in developmental defects, 10(-6) to 10(-4)M, ranking as: Gd(III)>Y(III)>La(III)>Nd(III)≅Eu(III)>Ce(III)≅Sm(III). Nominal concentrations of REE salts were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Significant increases in MDA levels, ROS formation, and NO levels were found in REE-exposed embryos. Sperm exposure to REEs (10(-5) to 10(-4)M) resulted in concentration-related decrease in fertilization success along with increase in offspring damage. Decreased mitotic activity and increased aberration rates were detected in REE-exposed embryos and in the offspring of REE-exposed sperm. REE-associated toxicity affecting embryogenesis, fertilization, cytogenetic and redox endpoints showed different activities of tested REEs. Damage to early life stages, along with redox and cytogenetic anomalies should be the focus of future REE toxicity studies. Copyright © 2016 Elsevier Inc. All rights reserved.

Anthropogenic rare earth elements and their spatial distributions in the Han River, South Korea.

PubMed

Song, Hyeongseok; Shin, Woo-Jin; Ryu, Jong-Sik; Shin, Hyung Seon; Chung, Heesun; Lee, Kwang-Sik

2017-04-01

Rare earth elements (REE) consist of lanthanides (from La to Lu), together with yttrium and scandium, in which anthropogenic REE, such as gadolinium (Gd), lanthanum (La), and samarium (Sm), has emerged as micro-contaminants in natural waters in highly developed countries. Here, we collected water samples in the Han River (HR) and its tributaries flowing through Seoul Capital Area, the world's second largest metropolitan area in order to examine how and to what extent anthropogenic REE anomalies may occur. Water samples show higher light REE concentrations than heavy REE concentrations, while wastewater treatment plant (WWTP) samples display much higher heavy REE concentrations due to high Gd concentration. The PAAS-normalized REE patterns indicate that WWTP samples display the pronounced positive Gd anomalies, in which anthropogenic Gd from magnetic resonance imaging (MRI) diagnostic system occurs as a form of Gd complexation with either Cl - or SO 4 2- . Due to the WWTP, both the HR and tributaries show also positive Gd anomalies and the anthropogenic Gd concentrations increase as a function of the distance from the Paldang dam. This result indicates a positive correlation between populaton, number of MRI instruments, and positive Gd anomaly. Similarly, positive La and Sm anomalies exist in the HR, indicating that the HR is also affected by their point sources. Based on the discharge rate and anthropogenic REE concentrations, their fluxes are estimated to be 952 ± 319 kg/yr, suggesting that this amount of fluxes could disturb REE distribution in the Yellow Sea, and pose harmful effects on aquatic ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS.

PubMed

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-11-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation. Graphical Abstract ᅟ.

Improved Precision and Accuracy of Quantification of Rare Earth Element Abundances via Medium-Resolution LA-ICP-MS

NASA Astrophysics Data System (ADS)

Funderburg, Rebecca; Arevalo, Ricardo; Locmelis, Marek; Adachi, Tomoko

2017-07-01

Laser ablation ICP-MS enables streamlined, high-sensitivity measurements of rare earth element (REE) abundances in geological materials. However, many REE isotope mass stations are plagued by isobaric interferences, particularly from diatomic oxides and argides. In this study, we compare REE abundances quantitated from mass spectra collected with low-resolution (m/Δm = 300 at 5% peak height) and medium-resolution (m/Δm = 2500) mass discrimination. A wide array of geological samples was analyzed, including USGS and NIST glasses ranging from mafic to felsic in composition, with NIST 610 employed as the bracketing calibrating reference material. The medium-resolution REE analyses are shown to be significantly more accurate and precise (at the 95% confidence level) than low-resolution analyses, particularly in samples characterized by low (<μg/g levels) REE abundances. A list of preferred mass stations that are least susceptible to isobaric interferences is reported. These findings impact the reliability of REE abundances derived from LA-ICP-MS methods, particularly those relying on mass analyzers that do not offer tuneable mass-resolution and/or collision cell technologies that can reduce oxide and/or argide formation.

The principal rare earth elements deposits of the United States-A summary of domestic deposits and a global perspective

USGS Publications Warehouse

Long, Keith R.; Van Gosen, Bradley S.; Foley, Nora K.; Cordier, Daniel

2010-01-01

The rare earth elements (REE) are fifteen elements with atomic numbers 57 through 71, from lanthanum to lutetium ('lanthanides'), plus yttrium (39), which is chemically similar to the lanthanide elements and thus typically included with the rare earth elements. Although industrial demand for these elements is relatively small in tonnage terms, they are essential for a diverse and expanding array of high-technology applications. REE-containing magnets, metal alloys for batteries and light-weight structures, and phosphors are essential for many current and emerging alternative energy technologies, such as electric vehicles, energy-efficient lighting, and wind power. REE are also critical for a number of key defense systems and other advanced materials. Section 843 of the National Defense Authorization Act for Fiscal Year 2010, Public Law 111-84, directs the Comptroller General to complete a report on REE materials in the defense supply chain. The Office of Industrial Policy, in collaboration with other U.S. Government agencies, has initiated (in addition to this report) a detailed study of REE. This latter study will assess the Department of Defense's use of REE, as well as the status and security of domestic and global supply chains. That study will also address vulnerabilities in the supply chain and recommend ways to mitigate any potential risks of supply disruption. To help conduct this study, the Office of Industrial Policy asked the U.S. Geological Survey (USGS) to report on domestic REE reserves and resources in a global context. To this end, the enclosed report is the initial USGS contribution to assessing and summarizing the domestic REE resources in a global perspective. In 2009, the Mineral Resources Program of the USGS organized a new project under the title Minerals at Risk and For Emerging Technologies in order to evaluate mineral resource and supply issues of rare metals that are of increasing importance to the national economy. Leaders and members of

Residual levels of rare earth elements in freshwater and marine fish and their health risk assessment from Shandong, China.

PubMed

Yang, Luping; Wang, Xining; Nie, Hongqian; Shao, Lijun; Wang, Guoling; Liu, Yongjun

2016-06-15

The total concentrations of rare earth elements (ΣREE) were quantified in 251 samples from 10 common species of freshwater and marine fish in seventeen cities of Shandong, China. ΣREE obtained from the freshwater fish ranged from 34.0 to 37.9ngg(-1) (wet weight) and marine fish from 12.7 to 37.6ngg(-1). The ratio of LREE to HREE was 13.7:1 and 10:1 for freshwater and marine fish, respectively. This suggests that freshwater fish exhibit greater REE concentrations than marine fish and the biological effects of LREE are higher than HREE. Results revealed a similar REE distribution pattern between those fish and coastal sediments, abiding the "abundance law". The health risk assessment demonstrated the EDIs of REEs in fish were significantly lower than the ADI, indicating that the consumption of these fish presents little risk to human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

The principal rare earth elements deposits of the United States: A summary of domestic deposits and a global perspective

USGS Publications Warehouse

Long, Keith R.; Van Gosen, Bradley S.; Foley, Nora K.; Cordier, Daniel

2012-01-01

Demand for the rare earth elements (REE, lanthanide elements) is estimated to be increasing at a rate of about 8% per year due to increasing applications in consumer products, computers, automobiles, aircraft, and other advanced technology products. Much of this demand growth is driven by new technologies that increase energy efficiency and substitute away from fossil fuels. Production of these elements is highly concentrated in China, which is reducing its exports of REE raw materials as part of its industrial policy. The ability of the rest of the world to replace supply from China depends on the quality of known REE resources and the degree to which those resources have been explored and evaluated. A review of United States resources in a global context finds that the United States could make significant contributions to future REE production. Aside from two advanced projects in the United States and Australia, however, there are no REE projects advanced enough to meet short-term demand.

High REE and Y concentrations in Co-Cu-Au ores of the Blackbird district, Idaho

USGS Publications Warehouse

Slack, J.F.

2006-01-01

Analysis of 11 samples of strata-bound Co-Cu-Au ore from the Blackbird district in Idaho shows previously unknown high concentrations of rare earth elements (REE) and Y, averaging 0.53 wt percent ???REE + Y oxides. Scanning electron microscopy indicates REE and Y residence in monazite, xenotime, and allanite that form complex intergrowths with cobaltite, suggesting coeval Co and REE + Y mineralization during the Mesoproterozoic. Occurrence of high REE and Y concentrations in the Blackbird ores, together with previously documented saline-rich fluid inclusions and Cl-rich biotite, suggest that these are not volcanogenic massive sulfide or sedimentary exhalative deposits but instead are iron oxide-copper-gold (IOCG) deposits. Other strata-bound Co deposits of Proterozoic age in the North American Cordillera and elsewhere in the world may have potential for REE and Y resources. IOCG deposits with abundant light REE should also be evaluated for possible unrecognized heavy REE and Y mineralization. ?? 2006 by Economic Geology.

Analyzing Solutions High in Total Dissolved Solids for Rare Earth Elements (REEs) Using Cation Exchange and Online Pre-Concentration with the seaFAST2 Unit; NETL-TRS-7-2017; NETL Technical Report Series; U.S. Department of Energy, National Energy Technology Laboratory: Albany, OR, 2017; p 32

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, J.; Torres, M.; Verba, C.

The accurate quantification of the rare earth element (REE) dissolved concentrations in natural waters are often inhibited by their low abundances in relation to other dissolved constituents such as alkali, alkaline earth elements, and dissolved solids. The high abundance of these constituents can suppress the overall analytical signal as well as create isobaric interferences on the REEs during analysis. Waters associated with natural gas operations on black shale plays are characterized by high salinities and high total dissolved solids (TDS) contents >150,000 mg/L. Methods used to isolate and quantify dissolved REEs in seawater were adapted in order to develop themore » capability of analyzing REEs in waters that are high in TDS. First, a synthetic fluid based on geochemical modelling of natural brine formation fluids was created within the Marcellus black shale with a TDS loading of 153,000 mg/L. To this solution, 1,000 ng/mL of REE standards was added based on preliminary analyses of experimental fluids reacted at high pressure and temperature with Marcellus black shale. These synthetic fluids were then run at three different dilution levels of 10, 100, and 1,000–fold dilutions through cation exchange columns using AG50-X8 exchange resin from Eichrom Industries. The eluent from the cation columns were then sent through a seaFAST2 unit directly connected to an inductively coupled plasma mass spectrometer (ICP-MS) to analyze the REEs. Percent recoveries of the REEs ranged from 80–110% and fell within error for the external reference standard used and no signal suppression or isobaric interferences on the REEs were observed. These results demonstrate that a combined use of cation exchange columns and seaFAST2 instrumentation are effective in accurately quantifying the dissolved REEs in fluids that are >150,000 mg/L in TDS and have Ba:Eu ratios in excess of 380,000.« less

The Not-So-Rare Earths.

ERIC Educational Resources Information Center

Muecke, Gunter K.; Moller, Peter

1988-01-01

Describes the characteristics of rare earth elements. Details the physical chemistry of rare earths. Reviews the history of rare earth chemistry and mineralogy. Discusses the mineralogy and crystallography of the formation of rare earth laden minerals found in the earth's crust. Characterizes the geologic history of rare earth elements. (CW)

Understanding rhizosphere processes to enhance phytoextraction of germanium and rare earth elements

NASA Astrophysics Data System (ADS)

Wiche, Oliver

2017-04-01

Germanium (Ge) and rare earth elements (REEs) are economically valuable raw materials that are not actually rare in terms of concentrations in soils but they are hardly available for plant uptake due to interactions with organic matter (SOM), secondary soil constituents such as Fe/Mn oxides and P bearing soil fractions. Processes in the rhizosphere might influence availability of Ge and REEs in the soil-plant system, since lowering of the pH and presence of carboxylates and siderophores (small molecules that strongly chelate Fe and other elements) strongly influences the chemical speciation of Ge and REEs in soil and consequently this comprehensive knowledge helps us to improve phytomining. In a series of field and greenhouse experiments 16 plant species from the functional groups of grasses, herbs and legumes were tested with regard to their accumulation efficiency of Ge and REEs in shoots. Subsequently, we conducted mixed culture experiments in which inefficient species (e.g. cereals like Avena sativa, Hordeum vulgare, Panicum miliaceum) were cultivated in mixed cultures with efficient species (Lupinus albus, Lupinus angustifolius). Based on the plant concentrations a principal component analysis (PCA) was performed to identify significant factors that explain the accumulation behavior of different plant species with regard to Ge, REEs, Si, Fe and Mn. In this analysis Mn was used to identify plant species with efficient mechanisms to access sparingly available P-resources in soils. Particularly in nonmycorrhizal species concentrations of Mn in leaves often indicate a carboxylate based P-mobilising strategy. Herbaceous plant species accumulated significantly higher amounts of REEs while grasses accumulated significantly higher amounts of Ge. Concentrations of Ge in shoots of grasses correlated significantly positive with Si, but negatively with concentrations of Mn. Indeed, the results of the PCA clearly show that plants with high Mn concentrations tend to have

Light rare earth element systematics as a tool for investigating the petrogenesis of phoscorite-carbonatite associations, as exemplified by the Phalaborwa Complex, South Africa

NASA Astrophysics Data System (ADS)

Milani, Lorenzo; Bolhar, Robert; Frei, Dirk; Harlov, Daniel E.; Samuel, Vinod O.

2017-12-01

In-situ trace element analyses of fluorapatite, calcite, dolomite, olivine, and phlogopite have been undertaken on representative phoscorite and carbonatite rocks of the Palaeoproterozoic Phalaborwa Complex. Textural and compositional characterization reveals uniformity of fluorapatite and calcite among most of the intrusions, and seems to favor a common genetic origin for the phoscorite-carbonatite association. Representing major repositories for rare earth elements (REE), fluorapatite and calcite exhibit tightly correlated light REE (LREE) abundances, suggesting that partitioning of LREE into these rock forming minerals was principally controlled by simple igneous differentiation. However, light rare earth element distribution in apatite and calcite cannot be adequately explained by equilibrium and fractional crystallization and instead favors a complex crystallization history involving mixing of compositionally distinct magma batches, in agreement with previously reported mineral isotope variability that requires open-system behaviour.

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

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.

The potential of sedimentary foraminiferal rare earth element patterns to trace water masses in the past

NASA Astrophysics Data System (ADS)

Osborne, Anne H.; Hathorne, Ed C.; Schijf, Johan; Plancherel, Yves; Böning, Philipp; Frank, Martin

2017-04-01

Dissolved rare earth element (REE) concentration data from intermediate and deep seawater form an array characterized by higher middle-REE enrichments (MREE/MREE*) in the North Atlantic and a progressive increase in heavy-to-light REE ratios (HREE/LREE) as water masses age. The REEs in foraminifera are fractionated toward higher MREE/MREE* and lower HREE/LREE relative to seawater. Calculations based on a scavenging model show that the REE patterns in uncleaned core-top foraminifera resemble those adsorbed onto calcite, particulate organic material, and hydrous ferric oxides but the full extent of the REE fractionation measured in foraminifera was not reproduced by the model. However, differences in the HREE/LREE and MREE/MREE* ratios and the cerium anomaly between ocean basins are preserved and are in agreement with the seawater REE distribution. Under oxic conditions, the HREE/LREE and MREE/MREE* compositions of uncleaned foraminifera at the sediment/seawater boundary are preserved during burial but the cerium anomaly is sensitive to burial depth. In suboxic sedimentary environments, all uncleaned foraminiferal REE concentrations are elevated relative to core-top values indicating addition of REEs from pore waters. The HREE/LREE ratio is highest when sedimentation rates were greatest and when high Fe/Ca ratios in the uncleaned foraminifera indicate that Fe was mobile. In sediments that have not experienced suboxic conditions during burial, uncleaned foraminifera preserve the seawater signal taken up at the sediment/seawater interface and are therefore suggested to be a suitable archive of changes in the REE signal of past bottom waters.

Geochemical characteristics of rare earth elements in the surface sediments from the Spratly Islands of China.

PubMed

Li, Jingxi; Sun, Chengjun; Zheng, Li; Yin, Xiaofei; Chen, Junhui; Jiang, Fenghua

2017-01-30

The geochemistry of rare earth elements (REE) in surface sediment from Cuarteron reef (N1), Johnson reef (N2), Hugh reef (N3), Gaven reef (N4), Fiery cross reef (N5), and Subi reef (N6) were firstly studied. The total REE abundance (∑REE) varied from 2.244μg·g -1 to 21.661μg·g -1 , with an average of 4.667μg·g -1 . The LREE/HREE was from 2.747 to 9.869, with an average of 3.687, which indicated that the light REE was evidently enriched. Fractionation was observed between LREE and HREE. Gd with a negative anomaly was also detected in all of the stations. The negative anomalies of δEu from 0.11 to 0.25, with an average of 0.22, and the positive anomalies of δCe from 1.38 to 3.86, with an average of 1.63. The REE individual correlation values with Ca, Mn, Mg, Sr were r Ca =-0.05, r Mn =0.26, r Mg =-0.14, and r Sr =0.08. Copyright © 2016 Elsevier Ltd. All rights reserved.

China's rare-earth industry

USGS Publications Warehouse

Tse, Pui-Kwan

2011-01-01

Introduction China's dominant position as the producer of over 95 percent of the world output of rare-earth minerals and rapid increases in the consumption of rare earths owing to the emergence of new clean-energy and defense-related technologies, combined with China's decisions to restrict exports of rare earths, have resulted in heightened concerns about the future availability of rare earths. As a result, industrial countries such as Japan, the United States, and countries of the European Union face tighter supplies and higher prices for rare earths. This paper briefly reviews China's rare-earth production, consumption, and reserves and the important policies and regulations regarding the production and trade of rare earths, including recently announced export quotas. The 15 lanthanide elements-lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium (atomic numbers 57-71)-were originally known as the rare earths from their occurrence in oxides mixtures. Recently, some researchers have included two other elements-scandium and yttrium-in their discussion of rare earths. Yttrium (atomic number 39), which lies above lanthanum in transition group III of the periodic table and has a similar 3+ ion with a noble gas core, has both atomic and ionic radii similar in size to those of terbium and dysprosium and is generally found in nature with lanthanides. Scandium (atomic number 21) has a smaller ionic radius than yttrium and the lanthanides, and its chemical behavior is intermediate between that of aluminum and the lanthanides. It is found in nature with the lanthanides and yttrium. Rare earths are used widely in high-technology and clean-energy products because they impart special properties of magnetism, luminescence, and strength. Rare earths are also used in weapon systems to obtain the same properties.

Trace Element Inputs to the Upper West Pacific from Nd Isotopes and Rare Earth Elements

NASA Astrophysics Data System (ADS)

Behrens, M. K.; Pahnke, K.; Schnetger, B.; Brumsack, H. J.

2015-12-01

Neodymium isotopes (143Nd/144Nd, expressed as ɛNd) and rare earth element (REE) concentrations in the ocean trace water mass transport and margin-seawater exchange processes. The distinct ɛNd and REE signatures of the lithogenic components of margin sediments of the West Pacific allow characterization of trace element inputs to the Pacific Ocean. We present dissolved ɛNdand REE concentrations from twelve vertical profiles of a transect from South Korea to Fiji. Near South Korea, surface waters are marked by unradiogenic ɛNd (as low as -7.3), high REE concentrations (e.g., Nd = 15.3 pmol/kg) and low salinity. Towards the open ocean, these parameters gradually change towards typical Pacific open ocean values (ɛNd = -3.3, [Nd] = 5.55 pmol/kg). Subsurface waters show REE depletions, followed by the typical REE increase with increasing water depth. These distributions indicate trace element input near South Korea and enhanced subsurface scavenging, as indicated by strong heavy REE to light REE fractionation. In the tropical West Pacific (10°N-15°S), high surface and subsurface water ɛNd values (+0.7) and positive Eu anomalies trace the influence of volcanic islands. Yet, absolute REE concentrations are extremely low at these depths (e.g., Nd = 2.77 pmol/kg). Using shale-normalized Nd/Er and Ho/Dy ratios, that show a much stronger surface to subsurface decrease in coastal waters compared to the open ocean, we suggest enhanced scavenging in this area. Eastward flowing intermediate waters (NPIW, AAIW) have ɛNd values up to +1.9 (NPIW) and +3.7 (AAIW) higher than those entering the tropical West Pacific from north and south, respectively. Modified ɛNd at intermediate depths and no change in REE patterns suggest that boundary exchange along volcanic island margins modifies the seawater ɛNd without changing the REE budget.

Rare earth elements in street dust and associated health risk in a municipal industrial base of central China.

PubMed

Sun, Guangyi; Li, Zhonggen; Liu, Ting; Chen, Ji; Wu, Tingting; Feng, Xinbin

2017-12-01

The content levels, distribution characteristics, and health risks associated with 15 rare earth elements (REEs) in urban street dust from an industrial city, Zhuzhou, in central China were investigated. The total REE content (∑REE) ranged from 66.1 to 237.4 mg kg -1 , with an average of 115.9 mg kg -1 , which is lower than that of Chinese background soil and Yangtze river sediment. Average content of the individual REE in street dust decreased in the order Ce > La > Nd > Y > Pr > Sm > Gd > Dy > Er > Yb > Eu > Ho > Tb > Tm > Lu. The chondrite-normalized REE pattern indicated light REE (LREE) enrichment, a relatively steep LREE trend, heavy REE (HREE) depletion, a flat HREE trend, a Eu-negative anomaly and a Ce-positive anomaly. Foremost heavy local soil and to less degree anthropogenic pollution are the main sources of REE present in street dust. Health risk associated with the exposure of REE in street dust was assessed based on the carcinogenic and non-carcinogenic effect and lifetime average daily dose. The obtained cancer and non-cancer risk values prompt for no augmented health hazard. However, children had greater health risks than that of adults.

Relationship between concentration of rare earth elements in soil and their distribution in plants growing near a frequented road.

PubMed

Mleczek, Patrycja; Borowiak, Klaudia; Budka, Anna; Niedzielski, Przemysław

2018-06-05

Rare earth elements (REEs) are a group of elements whose concentration in numerous environmental matrices continues to increase; therefore, the use of biological methods for their removal from soil would seem to be a safe and reasonable approach. The aim of this study was to estimate the phytoextraction efficiency and distribution of light and heavy (LREEs and HREEs) rare earth elements by three herbaceous plant species: Artemisia vulgaris L., Taraxacum officinale F.H. Wigg. and Trifolium repens L., growing at a distance of 1, 10, and 25 m from the edge of a frequented road in Poland. The concentration of REEs in soil and plants was highly correlated (r > 0.9300), which indicates the high potential of the studied plant species to phytoextraction of these elements. The largest proportion of REEs was from the group of LREEs, whereas HREEs comprised only an inconsiderable portion of the REEs group. The dominant elements in the group of LREEs were Nd and Ce, while Er was dominant in the HREEs group. Differences in the amounts of these elements influenced the total concentration of LREEs, HREEs, and finally REEs and their quantities which decreased with distance from the road. According to the Friedman rank sum test, significant differences in REEs concentration, mainly between A. vulgaris L., and T. repens L. were observed for plants growing at all three distances from the road. The same relation between A. vulgaris L. and T. officinale was observed. The efficiency of LREEs and REEs phytoextraction in the whole biomass of plants growing at all distances from the road was A. vulgaris L. > T. officinale L. > T. repens L. For HREEs, the same relationship was recorded only for plants growing at the distance 1 m from the road. Bioconcentration factor (BCF) values for LREEs and HREEs were respectively higher and lower than 1 for all studied plant species regardless of the distance from the road. The studied herbaceous plant species were able to effectively phytoextract

Fractionation of rare earth elements in the Mississippi River estuary and river sediments

NASA Astrophysics Data System (ADS)

Adebayo, S. B.; Johannesson, K. H.

2017-12-01

This study presents the first set of data on the fractionation of rare earth elements (REE) in the mixing zone between the Mississippi River and the Gulf of Mexico, as well as the fractionation of REE in the operationally defined fractions of Mississippi River sediments. This subject is particularly important because the Mississippi river is one of the world's major rivers, and contributes a substantial amount of water and sediment to the ocean. Hence, it is a major source of trace elements to the oceans. The geochemistry of the REE in natural systems is principally important because of their unique chemical properties, which prompt their application as tracers of mass transportation in modern and paleo-ocean environments. Another important consideration is the growth in the demand and utilization of REE in the green energy and technology industries, which has the potential to bring about a change in the background levels of these trace elements in the environment. The results of this study show a heavy REE enrichment of both the Mississippi River water and the more saline waters of the mixing zone. Our data demonstrate that coagulation and removal of REE in the low salinity region of the estuary is more pronounced among the Light REE ( 35% for Nd) compared to the Heavy REE. Remarkably, our data also indicate that REE removal in the Mississippi River estuary is significantly less than that observed in other estuaries, including the Amazon River system. We propose that the high pH/alkalinity of the Mississippi River is responsible for the greater stability of REE in the Mississippi River estuary. The results of sequential extraction of river sediments reveal different Sm/Nd ratios for the various fractions, which we submit implies different 143Nd/144Nd ratios of the labile fractions of the sediments. The possible impact of such hypothesized different Nd isotope signatures of labile fractions of the river sediments on Gulf of Mexico seawater is under investigation.

Determination of rare earth elements in geological materials by inductively coupled argon plasma/atomic emission spectrometry

USGS Publications Warehouse

Crock, J.G.; Lichte, F.E.

1982-01-01

Inductively coupled argon plasma/optical emission spectrometery (ICAP/OES) is useful as a simultaneous, multielement analytical technique for the determination of trace elements in geological materials. A method for the determination of trace-level rare earth elements (REE) in geological materials using an ICAP 63-channel emission spectrometer is described. Separation and preconcentration of the REE and yttrium from a sample digest are achieved by a nitric acid gradient cation exchange and hydrochloric acid anion exchange. Precision of 1-4% relative standard deviation and comparable accuracy are demonstrated by the triplicate analysis of three splits of BCR-1 and BHVO-1. Analyses of other geological materials including coals, soils, and rocks show comparable precision and accuracy.

Mineralogy and crystallization history of a highly differentiated REE-enriched hypabyssal rhyolite: Round Top laccolith, Trans-Pecos, Texas

NASA Astrophysics Data System (ADS)

O'Neill, L. Christine; Elliott, Brent A.; Kyle, J. Richard

2017-09-01

The Round Top hypabyssal rhyolite laccolith is a highly evolved magmatic system, enriched in incompatible elements including REE [Rare Earth Element(s)], U, Be, and F. The Round Top intrusion is part of a series of Paleogene intrusions emplaced as the Sierra Blanca Complex. These intrusions are situated within long-lived, complex tectonic regimes that have been subjected to regional compression and subduction, punctuated by extensional bimodal volcanism. The enrichment in the rhyolite that comprises Round Top is the result of the prolonged removal of compatible elements from the source magma chamber through the emplacement of earlier magmatic events. With the emplacement of each sequential laccolith, the F-rich source magma became more enriched in incompatible elements, with increasing HREE [Heavy Rare Earth Elements(s)] concentrations. The emplacement of Round Top as a laccolith (versus that of an extrusive rhyolitic flow) facilitated the retention of the volatile-rich vapor phase within the magma, forming ubiquitous REE-bearing minerals, mainly yttrofluorite and yttrocerite. The high temperature mineral-vapor phase alteration of the feldspar groundmass was essential to the formation of REE minerals, where the pervasive open pore space was occupied by the late-crystallizing minerals. These late-forming REE-bearing minerals also occur as crystals associated with other accessory and trace phases, as inclusions within other phases, along grain boundaries, and along fractures and within voids. The rhyolite at Round Top and other laccolith intrusions in the Sierra Blanca Complex represent a new sub-type of magmatic rare earth element hosting system.

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

TPE/REE separation with the use of zirconium salt of HDBP

NASA Astrophysics Data System (ADS)

Glekov, R. G.; Shmidt, O. V.; Palenik, Yu. V.; Goletsky, N. D.; Sukhareva, S. Yu.; Fedorov, Yu. S.; Zilberman, B. Ya.

2003-01-01

Partitioning of long-lived radionuclides (minor actinides, fission products) is considered as TBP-compatible ZEALEX-process for extraction separation of transplutonium elements (TPE) and rare-earth elements (REE), as well as Y, Mo, Fe and residual amounts of Np, Pu, U. Zirconium salt of dibutyl phosphoric acid (ZS-HDBP) dissolved in 30 % TBP is used as a solvent. The process was tested in multistage centrifugal contactors. Lanthanides, Y and TPE, as well as Mo, Fe were extracted from high-level Purex raffinate, Am and ceric subgroup of REE being separated from the polyvalent elements by stripping with HNO3. TPE/REE partitioning was achieved in the second cycle of the ZEALEX-process using DTPA in formic acid media. The integral decontamination factor of Am from La and Ce after both cycles is >200, from Pr and Nd 20-30 and from Sm and Eu 3.6; REE strips in both cycles contained <0,1% of the initial amount of TPE.

REE concentration processes in ion adsorption deposits: Evidence from Madagascar and China.

NASA Astrophysics Data System (ADS)

Smith, Martin; Estrade, Guillaume; Marquis, Eva; Goodenough, Kathryn; Nasun, Peter; Cheng, Xu; Kynicky, Jindrich

2017-04-01

Lateritic clay deposits, where the rare earth elements (REE) occur adsorbed to clay mineral surfaces, are the world's dominant supply of heavy REE (Gd-Lu). These deposits are currently only mined in China where there is a reported heavy REE enrichment, but other deposits are currently under exploration in Brazil, the Philippines and Madagascar. Concentration of REE within IADs has been proposed to be a dominantly supergene process, where easily degradable REE-minerals (e.g. REE-fluorcarbonates) break down and release REE that are then adsorbed to clay minerals resulting in HREE enrichment. Here we present data from the Ambohimirahavavy Complex, Madagascar, and compare them to data from mineralised profiles in China, with the aim of further constraining the formation and REE enrichment processes in ion adsorption deposits. Bulk rock total REE contents from Madagascar vary from 400-5000ppm, with the HREE varying from 10 to 20% of the TREE. Ammonium Sulphate leaches (designed to remove clay-adsorbed REE) of laterite show leachable TREE from 130-500ppm, with no preferential HREE adsorption. Within the sequential extraction procedure the reducible fraction (hydroxylammonium chloride leach) showed the highest REE, but this is largely attributable to Ce4+ in oxide layers. Analysis of laterite profiles show that the REE distribution is heterogeneous, with control from both bedrock heterogeneity, and the hydrological variation between pedolith and saprolith. Similar patterns are seen in Chinese profiles from Jiangxi province. X-ray diffraction shows the clay fraction in all sites is dominated by kaolinite and halloysite. These data are consistent with experimental data which show that kaolinite is only HREE selective in high ionic strength solutions (Coppin et al., 2002), and suggest that HREE enrichment in lateritic deposits may be a function of exceptional bed rock conditions. Petrographic investigation of the Zhaibei granite, immediately underlying HREE enriched

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults

PubMed Central

Cheng, Yu; Yang, Xue; Na, Li-Xin; Li, Ying; Sun, Chang-Hao

2016-01-01

Basic data on the resting energy expenditure (REE) of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20–79 years old). REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM) ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000) and men (p = 0.000), and we found that men have a higher REE (p = 0.000) and lower REE/FFM (p = 0.021) than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases. PMID:27598192

Gender- and Age-Specific REE and REE/FFM Distributions in Healthy Chinese Adults.

PubMed

Cheng, Yu; Yang, Xue; Na, Li-Xin; Li, Ying; Sun, Chang-Hao

2016-09-01

Basic data on the resting energy expenditure (REE) of healthy populations are currently rare, especially for developing countries. The aims of the present study were to describe gender- and age-specific REE distributions and to evaluate the relationships among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. This cross-sectional survey included 540 subjects (343 women and 197 men, 20-79 years old). REE was measured by indirect calorimetry and expressed as kcal/day/kg total body weight. The data were presented as the means and percentiles for REE and the REE to fat-free mass (FFM) ratio; differences were described by gender and age. Partial correlation analysis was used to analyze the correlations between REE, tertiles of REE/FFM, and glycolipid metabolism and eating behaviors. In this study, we confirmed a decline in REE with age in women (p = 0.000) and men (p = 0.000), and we found that men have a higher REE (p = 0.000) and lower REE/FFM (p = 0.021) than women. Furthermore, we observed no associations among glycolipid metabolism, eating behaviors, and REE in healthy Chinese adults. In conclusion, the results presented here may be useful to clinicians and nutritionists for comparing healthy and ill subjects and identifying changes in REE that are related to aging, malnutrition, and chronic diseases.

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

PubMed

Delgado, Joaquín; Pérez-López, Rafael; Galván, Laura; Nieto, José 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. Copyright © 2012 Elsevier Ltd. All rights reserved.

Rare earth element fingerprints in Korean coastal bay sediments: Association with provenance discrimination

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Woo, Han Jun; Jang, Seok; Jeong, Kap-Sik; Jung, Hoi-Soo; Hwang, Ha Gi; Lee, Jun-Ho; Cho, Jin Hyung

2016-09-01

Rare earth elements (REEs: La-Lu) in surface sediments collected from the mouth and middle tidal flats of Gomso Bay, South Korea, in August 2011 and May 2012 were analyzed to investigate the fine-grained sediment provenance. The upper continental crust (UCC)-normalized light REEs (LREEs: La to Nd) were more enriched than the middle REEs (MREEs: Sm to Dy) and heavy REEs (HREEs: Ho to Lu), resulting in large (La/Yb)UCC (1.9 ± 0.4) to (Gd/Yb)UCC (1.4 ± 0.2) ratios. The monthly (La/Yb)UCC values differed between the mouth and middle tidal flats due to deposition of fine-grained sediments that originated from distant rivers (the Geum and Yeongsan) and the Jujin Stream, located on the southern shore of the inner bay. We observed relative reductions in the (La/Yb)UCC value and REE content in the sediments from the mouth of the bay compared with those from Jujin Stream sediments. Confined to the middle tidal flat around the KH Line of Jujin Stream, the sediments, most enriched in LREEs but depleted in Eu, were distributed in August as strong Jujin Stream runs. Here, we suggest that an increase in LREE/HREE and decrease in MREE/LREE ratios can be used as a proxy to identify the Jujin Stream provenance in mixed riverine sediments and to trace Jujin Stream sediments within the Gomso Bay tidal flat, especially in the summer rainy season.

Anomalous REE patterns in unequilibrated enstatite chondrites: Evidence and implications

NASA Technical Reports Server (NTRS)

Crozaz, Ghislaine; Hsu, Weibiao

1993-01-01

We present here a study of Rare Earth Element (REE) microdistributions in unequilibrated enstatite chondrites (EOC's). Although the whole rock REE contents are similar in both unequilibrated and equilibrated chondrites, the host minerals of these refractory elements are different. In the least equilibrated ordinary chondrites (UOC's), the REE reside mainly in glass whereas, in their more equilibrated counterparts, the bulk of the REE is in calcium phosphate, a metamorphic mineral that formed by oxidation of phosphorous originally contained in metal. In the smaller group of enstatite (E) chondrites, calcium phosphate is absent and the phase that contains the highest REE concentrations is a minor mineral, CaS (oldhamite), which contains approximately 50 percent of the total Ca present. In E chondrites, elements typically considered to be lithophiles (such as Ca and Mn) occur in sulfides rather than silicates. This indicates formation under extremely reducing conditions, thus in a region of the solar nebula distinct from those that supplied the more abundant ordinary and carbonaceous chondrites. Previously, we observed a variety of REE patterns in the oldhamite of UEC's; they range from almost flat to some with pronounced positive Eu and Yb anomalies. Here, we searched for complementary REE patterns in other minerals from E chondrites and found them in the major mineral, enstatite. Whenever Eu and Yb anomalies are present in this mineral, they are always negative.

Resolution of rare earth element interferences in fossil energy by-product samples using sector-field ICP-MS

DOE PAGES

Thompson, Robert L.; Bank, Tracy; Roth, Elliot; ...

2016-07-30

Here, the supply and price of rare earth elements (REEs) have become a concern to many countries in the world, which has led to renewed interest in exploration and recovery of REEs from secondary or waste sources. Potential high REE waste sources that are of particular interest are coal mining, preparation, combustion, and other fossil energy by-products, including those from natural gas production. In this work, we have examined a set of five solid samples from the treatment of produced and flowback water containing elevated concentrations of barium. In order to confirm the correct concentrations of Eu, we studied thesemore » materials using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), which is capable of resolving species of nearly identical masses, including Eu and BaO. While the use of quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) for the REE analysis of most geological sample matrices should pose no problem, the presence of large amounts of Ba, as encountered in water treatment solids from natural gas produced and flowback samples may require SF-ICP-MS for accurate determination of all REEs.« less

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

PubMed

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

2016-06-07

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

Application of unsupervised pattern recognition approaches for exploration of rare earth elements in Se-Chahun iron ore, central Iran

NASA Astrophysics Data System (ADS)

Sarparandeh, Mohammadali; Hezarkhani, Ardeshir

2017-12-01

The use of efficient methods for data processing has always been of interest to researchers in the field of earth sciences. Pattern recognition techniques are appropriate methods for high-dimensional data such as geochemical data. Evaluation of the geochemical distribution of rare earth elements (REEs) requires the use of such methods. In particular, the multivariate nature of REE data makes them a good target for numerical analysis. The main subject of this paper is application of unsupervised pattern recognition approaches in evaluating geochemical distribution of REEs in the Kiruna type magnetite-apatite deposit of Se-Chahun. For this purpose, 42 bulk lithology samples were collected from the Se-Chahun iron ore deposit. In this study, 14 rare earth elements were measured with inductively coupled plasma mass spectrometry (ICP-MS). Pattern recognition makes it possible to evaluate the relations between the samples based on all these 14 features, simultaneously. In addition to providing easy solutions, discovery of the hidden information and relations of data samples is the advantage of these methods. Therefore, four clustering methods (unsupervised pattern recognition) - including a modified basic sequential algorithmic scheme (MBSAS), hierarchical (agglomerative) clustering, k-means clustering and self-organizing map (SOM) - were applied and results were evaluated using the silhouette criterion. Samples were clustered in four types. Finally, the results of this study were validated with geological facts and analysis results from, for example, scanning electron microscopy (SEM), X-ray diffraction (XRD), ICP-MS and optical mineralogy. The results of the k-means clustering and SOM methods have the best matches with reality, with experimental studies of samples and with field surveys. Since only the rare earth elements are used in this division, a good agreement of the results with lithology is considerable. It is concluded that the combination of the proposed

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE PAGES

Balboni, Enrica; Spano, T; Cook, N; ...

2017-10-20

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Spano, T; Cook, N

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the

Transfer of rare earth elements from natural metalliferous (copper and cobalt rich) soils into plant shoot biomass of metallophytes from Katanga (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Pourret, Olivier; Lange, Bastien; Jitaru, Petru; Mahy, Grégory; Faucon, Michel-Pierre

2014-05-01

The geochemical behavior of rare earth elements (REE) is generally assessed for the characterization of the geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. REE behavior is investigated according to their concentrations normalized with respect to the upper continental crust. In this study, the geochemical fingerprint of REE in plant shoot biomass of an unique metallicolous flora (i.e., Crepidorhopalon tenuis and Anisopappus chinensis) was investigated. The plants originate from extremely copper and cobalt rich soils, deriving from Cu and Co outcrops in Katanga, Democratic Republic of Congo. Some of the species investigated in this study are able to accumulate high amounts of Cu and Co in shoot hence being considered as Cu and Co hyperaccumulators. Therefore, assessing the behavior of REE may lead to a better understanding of the mechanisms of metal accumulation by this flora. The data obtained in this study indicate that REE uptake by plants is not primarily controlled by their concentration and speciation in the soil as previously shown in the literature (Brioschi et al. 2013). Indeed, the REE patterns in shoots are relatively flat whereas soils patterns are Middle REE enriched. In addition, it is worth noting that Eu enrichments occur in aerial parts of the plants. These positive Eu anomalies suggest that Eu3 + can form stable organic complexes replacing Ca2 + in several biological processes as in xylem fluids associated with the general nutrient flux. Therefore, is is possible that the Eu mobility in these fluids is enhanced by its reductive speciation as Eu2 +. Eventually, the geochemical behavior of REE illustrates that metals accumulation in aerial parts of C. tenuis and A. chinensis is mainly driven by dissolved complexation. Brioschi, L., Steinmann, M., Lucot, E., Pierret, M., Stille, P., Prunier, J., Badot, P., 2013. Transfer of rare earth elements (REE) from

Extraction of rare earth elements from a contaminated cropland soil using nitric acid, citric acid, and EDTA.

PubMed

Tang, Hailong; Shuai, Weitao; Wang, Xiaojing; Liu, Yangsheng

2017-08-01

Rare earth elements (REEs) contamination to the surrounding soil has increased the concerns of health risk to the local residents. Soil washing was first attempted in our study to remediate REEs-contaminated cropland soil using nitric acid, citric acid, and ethylene diamine tetraacetic acid (EDTA) for soil decontamination and possible recovery of REEs. The extraction time, washing agent concentration, and pH value of the washing solution were optimized. The sequential extraction analysis proposed by Tessier was adopted to study the speciation changes of the REEs before and after soil washing. The extract containing citric acid was dried to obtain solid for the X-ray fluorescence (XRF) analysis. The results revealed that the optimal extraction time was 72 h, and the REEs extraction efficiency increased as the agent concentration increased from 0.01 to 0.1 mol/L. EDTA was efficient to extract REEs over a wide range of pH values, while citric acid was around pH 6.0. Under optimized conditions, the average extraction efficiencies of the major REEs in the contaminated soil were 70.96%, 64.38%, and 62.12% by EDTA, nitric acid, and citric acid, respectively. The sequential extraction analyses revealed that most soil-bounded REEs were mobilized or extracted except for those in the residual fraction. Under a comprehensive consideration of the extraction efficiency and the environmental impact, citric acid was recommended as the most suitable agent for extraction of the REEs from the contaminated cropland soils. The XRF analysis revealed that Mn, Al, Si, Pb, Fe, and REEs were the major elements in the extract indicating a possibile recovery of the REEs.

REE Partitioning in Lunar Minerals

NASA Technical Reports Server (NTRS)

Rapp, J. F.; Lapen, T. J.; Draper, D. S.

2015-01-01

Rare earth elements (REE) are an extremely useful tool in modeling lunar magmatic processes. Here we present the first experimentally derived plagioclase/melt partition coefficients in lunar compositions covering the entire suite of REE. Positive europium anomalies are ubiquitous in the plagioclase-rich rocks of the lunar highlands, and complementary negative Eu anomalies are found in most lunar basalts. These features are taken as evidence of a large-scale differentiation event, with crystallization of a global-scale lunar magma ocean (LMO) resulting in a plagioclase flotation crust and a mafic lunar interior from which mare basalts were subsequently derived. However, the extent of the Eu anomaly in lunar rocks is variable. Fagan and Neal [1] reported highly anorthitic plagioclase grains in lunar impact melt rock 60635,19 that displayed negative Eu anomalies as well as the more usual positive anomalies. Indeed some grains in the sample are reported to display both positive and negative anomalies. Judging from cathodoluminescence images, these anomalies do not appear to be associated with crystal overgrowths or zones.

Isomorphous Substitution of Rare-Earth Elements in Lacunary Apatite Pb8Na2(PO4)6.

PubMed

Get'man, Evgeni I; Loboda, Stanislav N; Ignatov, Alexey V; Prisedsky, Vadim V; Abdul Jabar, Mohammed A B; Ardanova, Lyudmyla I

2016-03-07

The substitution of rare-earth elements (REEs) for Pb in the lacunary apatite Pb8Na2(PO4)6 with void structural channels was studied by means of powder X-ray diffraction (including the Rietveld refinement), scanning electron microscopy, energy-dispersive X-ray microanalysis, and IR spectroscopy and also measurements of the electrical conductivity. The substitution limits (xmax in Pb8-xLnxNa2(PO4)6Ox/2) at 800 °C were found to decrease with the atomic number of the REE from 1.40 for La to 0.12 for Yb with a rapid drop from light to heavy lanthanides (between Gd and Tb). The REE atoms substitute for Pb predominantly at Pb2 sites of the apatite structure according to the scheme 2Pb(2+) + □ → 2Ln(3+) + O(2-), where □ is a vacancy in the structural channel. The substitution in lacunary apatite produces quite different changes in the structural parameters compared with broadly studied alkaline-earth hydroxyapatites. In spite of the much lower ionic radii of REE than that of Pb(2+), the mean distances ⟨Pb1-O⟩ somewhat increase, whereas the distances ⟨Pb2-Pb2⟩ and ⟨Pb2-O4⟩ do not change considerably with the degree of substitution. This implies control of the substitution by not only spatial and charge accommodation of REE ions but also the availability of a stereochemically active 6s(2) electron pair on Pb(2+). The high-temperature electrical conductivity shows dependence on the degree of substitution with a minimum at x = 0.2 indicative of a possible change of the type of conductivity.

Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

USGS Publications Warehouse

Burruss, R.C.; Ging, T.G.; Eppinger, R.G.; Samson, a.M.

1992-01-01

Fluorescence emission spectra of three samples of fluorite containing 226-867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines ( 0.9 for Eu2+ and 0.99 for Er3+. Detection limits for three micrometer spots are about 0.01 ppm Eu2+ and 0.07 ppm Er3+. These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons. ?? 1992.

Rare earth element metasomatism in hydrothermal systems: The Willsboro-Lewis wollastonite ores, New York, USA

USGS Publications Warehouse

Whitney, P.R.; Olmsted, J.F.

1998-01-01

Wollastonite ores and garnet-pyroxene skarns in the Willsboro-Lewis district, New York, USA were formed in a complex hydrothermal system associated with the emplacement of a large anorthosite pluton. Contact-metamorphic marbles were replaced by wollastonite, garnet, and clinopyroxene during infiltration metasomatism involving large volumes of water of chiefly meteoric origin. Rare earth elements (REE) in these rocks show large departures from the protolith REE distribution, indicative of substantial REE mobility. Three types of chondrite-normalized REE distribution patterns are present. The most common, found in ores and skarns containing andradite-rich garnet, is convex-up in the light REE (LREE) with a maximum at Pr and a positive Eu anomaly. Europium anomalies and Pr/Yb ratios are correlated with X(Ad) in garnet. This pattern (type C) results from uptake of REE from hydrothermal fluids by growing crystals of calcsilicate minerals, principally andradite, with amounts of LREE controlled by the difference in ionic radius between Ca++ and REE3+ in garnet X sites. The Eu anomaly results either from prior interaction of the fluids with plagioclase-rich, Eu-positive anorthositic rocks in and near the ore zone, or by enrichment of divalent Eu on growth surfaces of garnet followed by entrapment, or both. Relative enrichment in heavy REE (type H) occurs in ores and skarn where calcsilicates, including grossularitic garnet, in contact-metamorphic marble have been concentrated by dissolution of calcite. In most cases a negative Eu anomaly is inherited from the marble protolith. Skarns containing titanite and apatite exhibit high total REE, relative light REE enrichment, and negative Eu anomalies (type L). These appear to be intrusive igneous rocks (ferrodiorites or anorthositic gabbros) that have been converted to skarn by Ca metasomatism. REE, sequestered in titanite, apatite, and garnet, preserve the approximate REE distribution pattern of the igneous protolith. Post

Rare earth element distributions in the West Pacific: Trace element sources and conservative vs. non-conservative behavior

NASA Astrophysics Data System (ADS)

Behrens, Melanie K.; Pahnke, Katharina; Paffrath, Ronja; Schnetger, Bernhard; Brumsack, Hans-Jürgen

2018-03-01

Recent studies suggest that transport and water mass mixing may play a dominant role in controlling the distribution of dissolved rare earth element concentrations ([REE]) at least in parts of the North and South Atlantic and the Pacific Southern Ocean. Here we report vertically and spatially high-resolution profiles of dissolved REE concentrations ([REE]) along a NW-SE transect in the West Pacific and examine the processes affecting the [REE] distributions in this area. Surface water REE patterns reveal sources of trace element (TE) input near South Korea and in the tropical equatorial West Pacific. Positive europium anomalies and middle REE enrichments in surface and subsurface waters are indicative of TE input from volcanic islands and fingerprint in detail small-scale equatorial zonal eastward transport of TEs to the iron-limited tropical East Pacific. The low [REE] of North and South Pacific Tropical Waters and Antarctic Intermediate Water are a long-range (i.e., preformed) laterally advected signal, whereas increasing [REE] with depth within North Pacific Intermediate Water result from release from particles. Optimum multiparameter analysis of deep to bottom waters indicates a dominant control of lateral transport and mixing on [REE] at the depth of Lower Circumpolar Deep Water (≥3000 m water depth; ∼75-100% explained by water mass mixing), allowing the northward tracing of LCDW to ∼28°N in the Northwest Pacific. In contrast, scavenging in the hydrothermal plumes of the Lau Basin and Tonga-Fiji area at 1500-2000 m water depth leads to [REE] deficits (∼40-60% removal) and marked REE fractionation in the tropical West Pacific. Overall, our data provide evidence for active trace element input both near South Korea and Papua New Guinea, and for a strong lateral transport component in the distribution of dissolved REEs in large parts of the West Pacific.

Submarine groundwater discharge is an important source of REEs to the coastal ocean

NASA Astrophysics Data System (ADS)

Johannesson, K. H.; Chevis, D. A.; Palmore, C. D.; Telfeyan, K.; Burdige, D.; Cable, J. E.; Hemming, S. R.; Rasbury, T.; Moran, S. B.; Prouty, N.; Swarzenski, P. W.

2014-12-01

Rare earth element (REE) concentrations of submarine groundwater discharge (SGD) were measured in three subterranean estuaries (i.e., Indian River Lagoon, Florida; Pettaquamscutt estuary, Rhode Island; Kona Coast, Hawaii). Using site-specific SGD estimates previously obtained by a variety of techniques (e.g., seepage meters, Ra, and Rn), we estimated SGD-derived fluxes of REEs to the coastal ocean using simple, one-dimensional modeling techniques. Our results indicate that the SGD fluxes of REEs are either of the same magnitude as riverine REE fluxes (Indian River Lagoon; Pettaquamscutt estuary), or far exceed surface runoff sources of REEs to the coastal ocean (Kona Coast). At each site important biogeochemical reactions occurring in the subterranean estuary, such as redox reactions, sediment bioirrigation, mineral dissolution and re-precipitation, and salt-induced mobilization from "nano-colloids", appear to facilitate release of REEs into solution, which are then advected to the coastal ocean via SGD. Neodymium isotope analysis of SGD and aquifer sediment are consistent with sediment diagenesis and redox transformations of Fe(III) oxides/oxyhydroxides, as well as preferential weathering of REE-bearing minerals like apatite, as being important sources of REEs to coastal seawater. Our investigations demonstrate that geochemical reactions occurring in the studied subterranean estuaries represent a net source of light and middle REEs to coastal seawater, whereas the heavy REEs appear to be sequestered in the subterranean estuary sediment.

Distribution pattern of rare earth ions between water and montmorillonite and its relation to the sorbed species of the ions.

PubMed

Takahashi, Yoshio; Tada, Akisa; Shimizu, Hiroshi

2004-09-01

REE (rare earth element) distribution coefficients (Kd) between the aqueous phase and montmorillonite surface were obtained to investigate the relation between the REE distribution patterns and the species of REE sorbed on the solid-water interface. It was shown that the features in the REE patterns, such as the slope of the REE patterns, the tetrad effect, and the Y/Ho ratio, were closely related to the REE species at the montmorillonite-water interface. In a binary system (REE-montmorillonite) below pH 5, three features (a larger Kd value for a lighter REE, the absence of the tetrad effect, and the Y/Ho ratio being unchanged from its initial value) suggest that hydrated REE are directly sorbed as an outer-sphere complex at the montmorillonite-water interface. Above pH 5.5, the features in the REE patterns, the larger Kd value for heavier REE, the M-type tetrad effect, and the reduced Y/Ho ratio, showed the formation of an inner-sphere complex of REE with -OH group at the montmorillonite surface. In addition, the REE patterns in the presence of humic acid at pH 5.9 were also studied, where the REE patterns became flat, suggesting that the humate complex is dominant as both dissolved and sorbed species of REE in the ternary system. All of these results were consistent with the spectroscopic data (laser-induced fluorescence spectroscopy) showing the local structure of Eu(III) conducted in the same experimental system. The present results suggest that the features in the REE distribution patterns include information on the REE species at the solid-water interface.

Quantifying Post-Fire Aeolian Sediment Transport Using Rare Earth Element Tracers.

NASA Astrophysics Data System (ADS)

Dukes, D.; Ravi, S.; Grandstaff, D. E.; Gonzales, H. B.; Li, J. J.; Sankey, J. B.; Wang, G.; Van Pelt, R. S.

2016-12-01

Grasslands and rangelands in arid and semi-arid regions of the world, which provide fundamental ecosystem services, are undergoing rapid increases in fire activity and are highly susceptible to post-fire accelerated soil erosion by wind. A quantitative assessment that integrates fire-wind erosion feedbacks is therefore critically needed in understanding vegetation change, soil biogeochemical cycling, air quality, and landscape evolution. We investigated the applicability of a novel tracer technique - the use of rare earth element (REE) tracers - to quantify soil erosion by wind and to identify sources and sinks of wind-blown sediments in both a burned and unburned shrub-grass transition zone within the Chihuahuan desert (New Mexico, USA). At the beginning of the windy season, March 2016, silt and sand sized particles in shrub, grass, and bare microsites were each tagged with a unique REE oxide, Ho, Eu, and Yb respectively. Samples were then taken directly after application prior to a prescribed fire and again at the end of the windy season in June 2016. All REE tracers showed signs of depletion and mixing, with the depletion in the burned site up to 20% greater than the unburned. REE concentration comparisons between the burned and unburned plots reveal a shift in the source and sink dynamics of sediment post fire. In unburned plots, changes in microsite REE concentrations indicate that sediment moved from the bare to vegetated microsites, whereas the opposite occurred in burned plots. However, burned plot grass microsites acted as a sink for sediment from shrub microsites, whereas unburned plot grass microsites exhibited no enrichment from shrub microsite-sourced sediment. Though fires are known to immediately increase aeolian sediment transport, accompanying changes in the sources and sinks of wind borne sediment may influence biogeochemical cycling and vegetation shifts possibly providing a feedback mechanism for land degradation in dryland ecosystems.

A human health risk assessment of rare earth elements in soil and vegetables from a mining area in Fujian Province, Southeast China.

PubMed

Li, Xiaofei; Chen, Zhibiao; Chen, Zhiqiang; Zhang, Yonghe

2013-10-01

Contaminated food through dietary intake has become the main potential risk impacts on human health. This study investigated concentrations of rare earth elements (REEs) in soil, vegetables, human hair and blood, and assessed human health risk through vegetables consumption in the vicinity of a large-scale mining area located in Hetian Town of Changting County, Fujian Province, Southeast China. The results of the study included the following mean concentrations for total and bio-available REEs of 242.92 ± 68.98 (135.85-327.56)μg g(-1) and 118.59 ± 38.49 (57.89-158.96)μg g(-1) dry weight (dw) in agricultural soil, respectively, and total REEs of 3.58 ± 5.28 (0.07-64.42)μg g(-1) dw in vegetable samples. Concentrations of total REEs in blood and hair collected from the local residents ranged from 424.76 to 1274.80 μg L(-1) with an average of 689.74 ± 254.25 μg L(-1) and from 0.06 to 1.59 μg g(-1) with an average of 0.48 ± 0.59 μg g(-1) of the study, respectively. In addition, a significant correlation was observed between REEs in blood and corresponding soil samples (R(2)=0.6556, p<0.05), however there was no correlation between REEs in hair and corresponding soils (p>0.05). Mean concentrations of REEs of 2.85 (0.59-10.24)μg L(-1) in well water from the local households was 53-fold than that in the drinking water of Fuzhou city (0.054 μg L(-1)). The health risk assessment indicated that vegetable consumption would not result in exceeding the safe values of estimate daily intake (EDI) REEs (100-110 μg kg(-1)d(-1)) for adults and children, but attention should be paid to monitoring human beings health in such rare earth mining areas due to long-term exposure to high dose REEs from food consumptions. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Technospheric Mining of Rare Earth Elements from Bauxite Residue (Red Mud): Process Optimization, Kinetic Investigation, and Microwave Pretreatment.

PubMed

Reid, Sable; Tam, Jason; Yang, Mingfan; Azimi, Gisele

2017-11-10

Some rare earth elements (REEs) are classified under critical materials, i.e., essential in use and subject to supply risk, due to their increasing demand, monopolistic supply, and environmentally unsustainable and expensive mining practices. To tackle the REE supply challenge, new initiatives have been started focusing on their extraction from alternative secondary resources. This study puts the emphasis on technospheric mining of REEs from bauxite residue (red mud) produced by the aluminum industry. Characterization results showed the bauxite residue sample contains about 0.03 wt% REEs. Systematic leaching experiments showed that concentrated HNO 3 is the most effective lixiviant. However, because of the process complexities, H 2 SO 4 was selected as the lixiviant. To further enhance the leaching efficiency, a novel process based on microwave pretreatment was employed. Results indicated that microwave pretreatment creates cracks and pores in the particles, enabling the lixiviant to diffuse further into the particles, bringing more REEs into solution, yielding of 64.2% and 78.7% for Sc and Nd, respectively, which are higher than the maximum obtained when HNO 3 was used. This novel process of "H 2 SO 4 leaching-coupled with-microwave pretreatment" proves to be a promising technique that can help realize the technological potential of REE recovery from secondary resources, particularly bauxite residue.

Syntrophic effect of indigenous and inoculated microorganisms in the leaching of rare earth elements from Western Australian monazite.

PubMed

Corbett, Melissa K; Eksteen, Jacques J; Niu, Xi-Zhi; Watkin, Elizabeth Lj

2018-05-28

The unique physiochemical properties exhibited by rare earth elements (REEs) and their increasing application in high-tech industries has created a demand for secure supply lines with established recovery procedures that create minimal environmental damage. Bioleaching experiments conducted on a non-sterile monazite concentrate with a known phosphate solubilising microorganism (PSM) resulted in greater mobilisation of REEs into solution in comparison to experiments conducted on sterile monazite. By combining the native consortia with an introduced PSM, a syntrophic effect between the populations effectively leached a greater amount of REEs than either a single PSM or the indigenous population alone. With sterile monazite, Penicillium sp.CF1 inoculated experiments released a total REE concentration of 12.32 mg L -1 after incubation for 8 days, whereas on non-sterile ore, double the soluble REE concentration was recorded (23.7 mg L -1 ). Comparable effects were recorded with Enterobacter aerogenes, Pantoea agglomerans and Pseudomonas putida. Alterations in the microbial populations during bioleaching of the monazite ore were determined by diversity profiling and demonstrated noticeable changes in community inhabitants over 14 days. The presence of native Firmicutes on the monazite appears to greatly contribute to the increased leaching recorded when using non-sterile monazite for REE recovery. Copyright © 2018. Published by Elsevier Masson SAS.

Geochemistry of rare earth elements in minesoils from São Domingos mining district (Iberian Pyrite Belt)

NASA Astrophysics Data System (ADS)

Delgado, Joaquin; Perez-Lopez, Rafael; Nieto, Jose Miguel; Ayora, Carles

2010-05-01

The São Domingos mine is one of the most emblematic mining districts in the lower part of the Guadiana River Basin (SW of Iberian Peninsula). It is located in Portugal (about 5 km from the Spanish border), in the northern sector of the Iberian Pyrite Belt (IPB), one of the largest metallogenetic provinces of massive sulphides in the world. Although mining activity has ceased at present, the large-scale exploitation of this deposit between the second half of the XIX century and the first half of the XX century, has favoured the production of enormous waste dumps, where oxidation of pyrite and associated sulphides is resulting in the production of acid mine drainage (AMD). Mining wastes, minesoils, and acid mine drainage have been analyzed for their major ions and rare earth elements (REE) with the aim of understanding the REE mobility during sulphide weathering so that lanthanoid series can be used both as a proxy for the extent of water-rock interaction and as a tool for identifying impacts of AMD on natural ecosystems. Chemical speciation of REE in extracts from minesoils indicates that REE sulphate complexes (mainly LnSO4+) are the primary aqueous form (60-90%), and free ionic species (Ln3+, 10-40%) are the next most abundant form of soil water-soluble fraction and controls the REE speciation model. The REE from this fraction have NASC-normalized patterns with middle-REE (MREE) enriched signature compared to the light-REE (LREE) and heavy-REE (HREE), showing convex MREE-signatures and convexity index values of +1.29 +/- 1.13. These results are consistent with the typical REE fractionation patterns reported for AMD. Poorly crystalline iron oxyhydroxysulphates act as a source of labile MREE by dissolution and/or desorption processes and could explain the MREE-enriched signatures in solution.

Determination of trace rare earth elements in gadolinium aluminate by inductively coupled plasma time of flight mass spectrometry

NASA Astrophysics Data System (ADS)

Saha, Abhijit; Deb, S. B.; Nagar, B. K.; Saxena, M. K.

An analytical methodology was developed for the precise quantification of ten trace rare earth elements (REEs), namely, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Tm, in gadolinium aluminate (GdAlO3) employing an ultrasonic nebulizer (USN)-desolvating device based inductively coupled plasma mass spectrometry (ICP-MS). A microwave digestion procedure was optimized for digesting 100 mg of the refractory oxide using a mixture of sulphuric acid (H2SO4), phosphoric acid (H3PO4) and water (H2O) with 1400 W power, 10 min ramp and 60 min hold time. An USN-desolvating sample introduction system was employed to enhance analyte sensitivities by minimizing their oxide ion formation in the plasma. Studies on the effect of various matrix concentrations on the analyte intensities revealed that precise quantification of the analytes was possible with matrix level of 250 mg L- 1. The possibility of using indium as an internal standard was explored and applied to correct for matrix effect and variation in analyte sensitivity under plasma operating conditions. Individual oxide ion formation yields were determined in matrix matched solution and employed for correcting polyatomic interferences of light REE (LREE) oxide ions on the intensities of middle and heavy rare earth elements (MREEs and HREEs). Recoveries of ≥ 90% were achieved for the analytes employing standard addition technique. Three real samples were analyzed for traces of REEs by the proposed method and cross validated for Eu and Nd by isotope dilution mass spectrometry (IDMS). The results show no significant difference in the values at 95% confidence level. The expanded uncertainty (coverage factor 1σ) in the determination of trace REEs in the samples were found to be between 3 and 8%. The instrument detection limits (IDLs) and the method detection limits (MDLs) for the ten REEs lie in the ranges 1-5 ng L- 1 and 7-64 μg kg- 1 respectively.

Separation and preconcentration of the rare-earth elements and yttrium from geological materials by ion-exchange and sequential acid elution

USGS Publications Warehouse

Crock, J.G.; Lichte, F.E.; Riddle, G.O.; Beech, C.L.

1986-01-01

The abundance of rare-earth elements (REE) and yttrium in geological materials is generally low, and most samples contain elements that interfere in the determination of the REE and Y, so a separation and/or preconcentration step is often necessary. This is often achieved by ion-exchange chromatography with either nitric or hydrochloric acid. It is advantageous, however, to use both acids sequentially. The final solution thus obtained contains only the REE and Y, with minor amounts of Al, Ba, Ca, Sc, Sr and Ti. Elements that potentially interfere, such as Be, Co, Cr, Fe, Mn, Th, U, V and Zr, are virtually eliminated. Inductively-coupled argon plasma atomic-emission spectroscopy can then be used for a final precise and accurate measurement. The method can also be used with other instrumental methods of analysis. ?? 1986.

Formation of the world's largest REE deposit through protracted fluxing of carbonatite by subduction-derived fluids

PubMed Central

Ling, Ming-Xing; Liu, Yu-Long; Williams, Ian S.; Teng, Fang-Zhen; Yang, Xiao-Yong; Ding, Xing; Wei, Gang-Jian; Xie, Lu-Hua; Deng, Wen-Feng; Sun, Wei-Dong

2013-01-01

Rare Earth Elements (REE) are essential to modern society but the origins of many large REE deposits remain unclear. The U-Th-Pb ages, chemical compositions and C, O and Mg isotopic compositions of Bayan Obo, the world's largest REE deposit, indicate a protracted mineralisation history with unusual chemical and isotopic features. Coexisting calcite and dolomite are in O isotope disequilibrium; some calcitic carbonatite samples show highly varied δ26Mg which increases with increasing Si and Mg; and ankerite crystals show decreases in Fe and REE from rim to centre, with highly varied REE patterns. These and many other observations are consistent with an unusual mineralisation process not previously considered; protracted fluxing of calcitic carbonatite by subduction-released high-Si fluids during the closure of the Palaeo-Asian Ocean. The fluids leached Fe and Mg from the mantle wedge and scavenged REE, Nb and Th from carbonatite, forming the deposit through metasomatism of overlying sedimentary carbonate.

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.

Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

DOEpatents

Ellis, Timothy W.; Schmidt, Frederick A.

1995-08-01

Method of treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation.

Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry

PubMed Central

Xiong, Xiaohong; Jiang, Tao; Qi, Wenhao; Zuo, Jun; Yang, Meiling; Fei, Qiang; Xiao, Saijin; Yu, Aimin; Zhu, Zhiqiang; Chen, Huanwen

2015-01-01

A sensitive mass spectrometric analysis method based on the microwave plasma technique is developed for the fast detection of trace rare earth elements (REEs) in aqueous solution. The plasma was produced from a microwave plasma torch (MPT) under atmospheric pressure and was used as ambient ion source of a linear ion trap mass spectrometer (LTQ). Water samples were directly pneumatically nebulized to flow into the plasma through the central tube of MPT. For some REEs, the generated composite ions were detected in both positive and negative ion modes and further characterized in tandem mass spectrometry. Under the optimized conditions, the limit of detection (LOD) was at the level 0.1 ng/mL using MS2 procedure in negative mode. A single REE analysis can be completed within 2~3 minutes with the relative standard deviation ranging between 2.4% and 21.2% (six repeated measurements) for the 5 experimental runs. Moreover, the recovery rates of these REEs are between the range of 97.6%–122.1%. Two real samples have also been analyzed, including well and orange juice. These experimental data demonstrated that this method is a useful tool for the field analysis of REEs in water and can be used as an alternative supplement of ICP-MS. PMID:26421013

Environmental life cycle assessment on the separation of rare earth oxides through solvent extraction.

PubMed

Vahidi, Ehsan; Zhao, Fu

2017-12-01

Over the past decade, Rare Earth Elements (REEs) have gained special interests due to their significance in many industrial applications, especially those related to clean energy. While REEs production is known to cause damage to the ecosystem, only a handful of Life Cycle Assessment (LCA) investigations have been conducted in recent years, mainly due to lack of data and information. This is especially true for the solvent extraction separation of REEs from aqueous solution which is a challenging step in the REEs production route. In the current investigation, an LCA is carried out on a typical REE solvent extraction process using P204/kerosene and the energy/material flows and emissions data were collected from two different solvent extraction facilities in Inner Mongolia and Fujian provinces in China. In order to develop life cycle inventories, Ecoinvent 3 and SimaPro 8 software together with energy/mass stoichiometry and balance were utilized. TRACI and ILCD were applied as impact assessment tools and LCA outcomes were employed to examine and determine ecological burdens of the REEs solvent extraction operation. Based on the results, in comparison with the production of generic organic solvent in the Ecoinvent dataset, P204 production has greater burdens on all TRACI impact categories. However, due to the small amount of consumption, the contribution of P204 remains minimal. Additionally, sodium hydroxide and hydrochloric acid are the two impactful chemicals on most environmental categories used in the solvent extraction operation. On average, the solvent extraction step accounts for 30% of the total environmental impacts associated with individual REOs. Finally, opportunities and challenges for an enhanced environmental performance of the REEs solvent extraction operation were investigated. Copyright © 2017 Elsevier Ltd. All rights reserved.

A geological reconnaissance of electrical and electronic waste as a source for rare earth metals.

PubMed

Mueller, Sandra R; Wäger, Patrick A; Widmer, Rolf; Williams, Ian D

2015-11-01

The mining of material resources requires knowledge about geogenic and anthropogenic deposits, in particular on the location of the deposits with the comparatively highest concentration of raw materials. In this study, we develop a framework that allows the establishment of analogies between geological and anthropogenic processes. These analogies were applied to three selected products containing rare earth elements (REE) in order to identify the most concentrated deposits in the anthropogenic cycle. The three identified anthropogenic deposits were characterised according to criteria such as "host rock", "REE mineralisation" and "age of mineralisation", i.e. regarding their "geological" setting. The results of this characterisation demonstrated that anthropogenic deposits have both a higher concentration of REE and a longer mine life than the evaluated geogenic deposit (Mount Weld, Australia). The results were further evaluated by comparison with the geological knowledge category of the United Nations Framework Classification for Fossil Energy and Mineral Reserves and Resources 2009 (UNFC-2009) to determine the confidence level in the deposit quantities. The application of our approach to the three selected cases shows a potential for recovery of REE in anthropogenic deposits; however, further exploration of both potential and limitations is required. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

High resolution rare-earth elements analyses of natural apatite and its application in geo-sciences: Combined micro-PIXE, quantitative CL spectroscopy and electron spin resonance analyses

NASA Astrophysics Data System (ADS)

Habermann, D.; Götte, T.; Meijer, J.; Stephan, A.; Richter, D. K.; Niklas, J. R.

2000-03-01

The rare-earth element (REE) distribution in natural apatite is analysed by micro-PIXE, cathodoluminescence (CL) microscopy and spectroscopy and electron spin resonance (ESR) spectroscopy. The micro-PIXE analyses of an apatite crystal from Cerro de Mercado (Mexico) and the summary of 20 analyses of six francolite (conodonts of Triassic age) samples indicate that most of the REEs are enriched in apatite and francolite comparative to average shale standard (NASC). The analyses of fossil francolite revealing the REE-distribution not to be in balance with the REE-distribution of seawater and fish bone debris. Strong inhomogenous lateral REE-distribution in fossil conodont material is shown by CL-mapping and most probably not being a vital effect. Therefore, the resulting REE-signal from fossil francolite is the sum of vital and post-mortem incorporation. The necessary charge compensation for the substitution of divalent Ca by trivalent REE being done by different kind of electron defects and defect ions.

Geochemical and mineralogical constraints on the distribution and enrichment of the rare earth elements during pedogenesis and tropical weathering

NASA Astrophysics Data System (ADS)

Hardy, Liam; Smith, Martin; Moles, Norman; Marsellos, Antonios

2015-04-01

Current European manufacturing relies heavily on imports from the USA & China for unprocessed rare earth elements (REEs) and rare earth oxides (REOs). It has been suggested that the EU holds viable reserves of REEs that, with adequate research, could satisfy 10% of EU industrial demand, by the recycling of mine waste from bauxite production (red muds) alone (Deady, E. (BGS), 2014). Focus has been turned to the potential for Mount Weld type laterite deposits being exploited in the EU, but limited exploration and understanding of EU laterite (& paleo laterite) formations currently makes them unattractive to investment. Although previously researched, the full range of factors influencing the transition of rare earth (primarily lanthanide series, Y & Sc) elements between mineral and clay phases in allochthonous soils, saprolites and laterites is not fully understood, especially in present and Paleo-European environments (Herrington, Boni, Skarpelis, & Large, 2007) (Deady, E. (BGS), 2014) but several deposits globally are suggested to have formed at economically viable concentrations due to this secondary remobilisation & transition from mineral to clay phase and subsequent seasonal leaching and evaporation system, to form depositional buffer zones other than the soil base. (Hoatson, Jaireth, & Miezitis, 2011) (Berger, Janots, Gnos, Frei, & Bernier, 2014). This project intends to use new techniques in sequential extractions, ICP-MS, Quantitative XRD & SEM analysis to expand current knowledge around lateritic & allochtonous ore forming, & weathering processes. Heavy REE content and mineralogical variations in clays will be examined, with examples from a selection of profiles across Southern Europe (and potentially paleo soils from Scandinavia) to define the main influencing factors on REE concentration. Are the specific sites enriched simply by the nature of their source rock (protolith), by the soil formation (pedogenesis), or by biogenic & meteorological factors

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