Low Rare Earth Element Contents Research Articles

Efficient extraction and stripping of Nd(III), Eu(III) and Er(III) by membrane dispersion micro-extractors

The extraction of low concentration rare earth elements at high phase ratio was investigated. The traditional extraction set-up, such as mixer-settler, have drawbacks of easy emulsification, difficult separation and low efficiency if operated at the above condition. Membrane dispersion micro-extractor, owing to its well-dispersed, high surface-to-volume ratio and fast mass transfer rate, was employed in our work. Nd(III), Eu(III), Er(III) were chosen to represent light, medium, heavy rare earth elements (REEs). The extraction process of REEs with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (P507) was investigated by membrane dispersion micro-extractors. Firstly, the extraction equilibrium of these three elements was explored in the stirred conical flasks, and it is indicated that the extraction efficiencies can be 0.95, 0.97 and 0.98, respectively within 40 min at phase ratio of 100:1. Then the effects of operational conditions such as the residence time, organic and aqueous flow rates on extraction efficiency were also explored in micro-extractors. The results indicate that the efficiency decreases and then increases if increasing aqueous phase flow rate, residence time and droplets' diameter are the key factors of this process. Increasing the phase ratio reduces the extraction efficiency significantly. When the REEs solution has an initial pH of 4.00, the flow rates of continuous and dispersed phase are 40 and 1.6 mL/min, respectively, and 90 mg/L Nd (III), Eu(III) and Er(III) is extracted by 1 mol/L P507 at the out-let length of 8 m. The extraction efficiencies are 0.978, 0.983 and 0.991, respectively. Finally the stripping process was also studied with the micro-extractor. The stripping efficiencies of Nd(III), Eu(III) and Er(III) can reach 0.99, 0.96 and 0.91, respectively when the out-let length is 8 m and the concentration of hydrochloric acid is 1 mol/L. The developed approach offers a novel and simple strategy on the fast extraction and enrichment of low concentration rare earth elements from waste water.

ThMn12-type phases for magnets with low rare-earth content: Crystal-field analysis of the full magnetization process

Rare-earth (R)-iron alloys are a backbone of permanent magnets. Recent increase in price of rare earths has pushed the industry to seek ways to reduce the R-content in the hard magnetic materials. For this reason strong magnets with the ThMn12 type of structure came into focus. Functional properties of R(Fe,T)12 (T-element stabilizes the structure) compounds or their interstitially modified derivatives, R(Fe,T)12-X (X is an atom of hydrogen or nitrogen) are determined by the crystal-electric-field (CEF) and exchange interaction (EI) parameters. We have calculated the parameters using high-field magnetization data. We choose the ferrimagnetic Tm-containing compounds, which are most sensitive to magnetic field and demonstrate that TmFe11Ti-H reaches the ferromagnetic state in the magnetic field of 52 T. Knowledge of exact CEF and EI parameters and their variation in the compounds modified by the interstitial atoms is a cornerstone of the quest for hard magnetic materials with low rare-earth content.

Lithologically-related rare earth element variations the Mio-Pliocene Poznań Formation (Poland)

Concentrations of rare earth elements (REEs) were determined in 129 clay samples collected from the Mio-Pliocene Poznan Formation in Poland. The REEs occur in a relatively wide range from 58.2 to 1,709 mg/kg. Low North American Shale Composite (NASC)-normalized total REE contents with heavy rare earth element (HREE) depletion were noted in most of the samples analysed. Small variations were detected in the REE contents in the lithologies distinguished. Red clays are characterised by slightly lower REE concentrations relative to green and grey clays. All the Poznan Formation clays exhibit a negative Eu anomaly when normalized to the average of chondrites. Values increase according to the following sequence: grey clays grey clays > red clays. The variability of the REE contents of the Poznan Formation decreased from west to east.

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field, Okinawa Trough: constraints from rare earth element and sulfur isotopic compositions

ABSTRACT For the first time, we present the rare earth element (REE) and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF), Okinawa Trough at a water depth of 1206 m. The natural sulfur samples exhibit the lowest ΣREE concentrations (ΣREE= 0.65×10–6–4.580×10–6) followed by metal sulfides (ΣREE=1.71×10–6–11.63×10–6). By contrast, the natural sulfur-sediment samples have maximum ΣREE concentrations (ΣREE=11.54×10–6–33.06×10–6), significantly lower than those of the volcanic and sediment samples. Nevertheless, the δEu, δCe, (La/Yb)N, La/Sm, (Gd/Yb)N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment. Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09–24.53) and slightly negative Eu anomalies or no anomaly (δEu=0.48–0.99), which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-arc basins, but identical to the sulfides from the Jade hydrothermal field. The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid, inducing lower REE concentrations for natural sulfur compared with metal sulfide; meanwhile, the negative Eu anomaly is also weakened or almost absent. The sulfur isotopic compositions of the natural sulfur (δ34S=3.20‰–5.01‰, mean 4.23‰) and metal sulfide samples (δ34S=0.82‰–0.89‰, mean 0.85‰) reveal that the sulfur of the chimney is sourced from magmatic degassing.

Geochemical features of sulfides from the Deyin-1 hydrothermal field at the southern Mid-Atlantic Ridge near 15°S

In this study, geochemical compositions of elements in sulfide samples collected from the Deyin-1 hydrothermal field near the 15°S southern Mid-Atlantic Ridge (SMAR) were analyzed by the X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) to examine the enrichment regulations of ore-forming elements and hydrothermal mineralization. These sulfide precipitates can be classified macroscopically into three types: Fe-rich sulfide, Fe-Cu-rich sulfide and Fe-Zn-rich sulfide, and are characterized by the enrichment of base metal elements along with a sequence of Fe>Zn>Cu. Compared with sulfides from other hydrothermal fields on MAR, Zn concentrations of sulfides in the research area are significantly high, while Cu concentrations are relatively low. For all major, trace or rare-earth elements (REE), their concentrations and related characteristic parameters exhibit significant variations (up to one or two orders of magnitude), which indicates the sulfides from different hydrothermal vents or even a same station were formed at different stages of hydrothermal mineralization, and suggests the variations of chemical compositions of the hydrothermal fluid with respect to time. The hydrothermal temperatures of sulfides precipitation decreased gradually from station TVG10 (st.TVG10) to st.TVG12, and to st.TVG11, indicating that the precipitation of hydrothermal sulfides is subjected to conditions changed from high temperature to low temperature, and that the hydrothermal activity of study area was at the late stage of a general trend of evolution from strong to weak. The abnormally low concentrations of REE in sulfides and their similar chondrite-normalized REE patterns show that REEs in all sulfides were derived from a same source, but underwent different processes of migration or enrichment, or sulfides were formed at different stages of hydrothermal mineralization. The sulfides collected from the active hydrothermal vent were mainly attributed to precipitating directly from the hydrothermal fluid, while those collected from the extinct hydrothermal chimney might have already been altered by the seawater. Generally, ore-forming elements in the sulfides can be divided into three groups: Fe-based element group, Cu-based element group and Zn-based element group. The first group includes Fe, Mn, Cr, Mo, Sn, Rb and bio-enriching elements, such as P and Si, reflecting the similar characteristics to Fe in the study area. And the second group contains Cu, W, Co, Se, Te and Bi, suggesting the similar behavior with Cu. Moreover, the third group includes Zn, Hf, Hg, Cd, Ta, Ga, Pb, As, Ag, Ni and Sb, which indicates the geochemical characteristics of most dispersed trace elements controlled by Zn-bearing minerals to some extent.

The Geochemistry of Volcanogenic Mineralization in the Northwestern Segment of the Pacific Ore Belt: Northeast Russia

This paper considers the geochemistry of volcanogenic mineralization in the northeastern segment of the Pacific Ore Belt (Northeast Russia). We give new evidence for the compositions and concentrations of trace and rare-earth elements (REE) in the ores of volcanogenic fields: Au-Ag epithermal (of various types and ages), Cu-Mo-Au porphyritic, Au-Bi related to granitoidal intrusions, Sn-Ag subvolcanic and kies polymetallic enriched in Au and Ag, as well as REEs in alkaline volcanic rocks. Geochemical signatures have been compiled for 17 formation types of volcanogenic fields. It was found that the ore-forming fluids in most fields belonged to an NaCl-H2O hydrothermal system that was enriched in Cl relative to F; the values of Y/Ho in the ores of nearly all types correspond with the interval of ratios characteristic for present-day hydrothermal fluids in backarc basins; most of the ores that we studied had near-chondrite spectra with configurations similar to those of the REE spectra in volcanic rock sequences of the andesite-diorite series. Comparative analysis of REE spectra in the distribution of trace elements over classes of gold concentration shows synchronous enrichment of ores in similar sets of trace elements. The high Co/Ni ratio in volcanogenic ores probably reflects the superposition of a later magmatic fluid upon an earlier mineralization. Samples from ores of volcanogenic fields, except for Kuroko, show δCe and δEu varying from negative to mildly positive values, thus indicating low-oxidizing conditions during deposition. It was found for Au-Ag epithermal ores that they are enriched in a wide range of trace elements; they have low concentrations of REEs, the light REEs are more abundant than the heavy ones, and the Eu anomalies vary considerably from small negative to low and high positive values. The results provide evidence of an exhalation hydrothermal origin of the Khotoidokh field. It has been shown that the REEs in the ores of the Bol’shoe field are of the type that is most valuable to industry. The results can be used to deal with practical problems: determining the formation type and evaluating the industrial value of a field; detecting accessory components in ores; and discriminating between the types of geochemical anomalies (in rocks or in soil) and stray fluxes as to the potential of a field.

Distribution of rare earth elements in coal combustion fly ash, determined by SHRIMP-RG ion microprobe

During coal combustion for electric power generation, rare earth elements (REE) are strongly retained in the ash fraction leading to significant enrichment compared to the REE content of the respective feed coals. Knowing how the REE are distributed in coal ash is essential to devising effective approaches for REE extraction from this potential resource. To better understand the distribution of REE in coal ash, we used the Stanford-USGS SHRIMP-RG ion microprobe to determine grain-scale REE partitioning in a suite of 19 U.S. and international coal fly ash samples. SHRIMP-RG microanalysis used a nominal spot size of 15μm and an oxygen negative-ion primary beam. NIST multi-element glass standards SRM 611 and SRM 613 were used for REE calibration. Prior to SHRIMP-RG analysis, samples were characterized by backscattered electron imaging and wavelength-dispersive elemental mapping to delineate constituents of interest for REE microanalysis. Results confirm the occurrence of REE in aluminosilicate glasses consistent with previous results that showed a strong positive correlation between Al and REE content in a larger group of U.S. and international coal fly ash samples. Among these glasses, aluminosilicates consisting of Al and Si and lacking other major constituents tend to have REE contents similar to, or slightly lower than the bulk sample REE content, whereas Ca- and/or Fe-enriched aluminosilicate glasses are similar to, or more REE-enriched than the bulk sample. Co-occurring quartz and/or high-silica glass is almost always the most REE depleted fly ash constituent, having much lower REE contents than the aluminosilicate glasses. Fe-oxide magnetospheres have REE content with relative proportions of light (LREE) to heavy (HREE) rare earths that are more variable than in the aluminosilicate glasses. Results suggest that extraction of REE from the aluminosilicate glass fraction in coal ash will yield a significant portion of the REE present and therefore, this fraction should be targeted in ongoing efforts to recover REE from coal fly ash.

Rare earth elements and Sm-Nd isotope redistribution in apatite and accessory minerals in retrogressed lower crust material (Bergen Arcs, Norway)

In the Bergen Arcs (Norway), Grenvillian granulite retrogressed under eclogite- and amphibolite-facies conditions during Caledonian subduction/collision offer a unique opportunity to investigate rare earth elements (REE) and Sm-Nd isotope redistribution in accessory minerals during fluid-assisted metamorphism. Our sampling targeted apatite-bearing REE-rich protoliths (mangerite and jotunite) that preserve distinct mineral assemblages, depending on the external fluid availability and metamorphic conditions. REE concentrations in apatite are the highest in the granulite. Two populations are present: magmatic apatite (Ap1) relics that occur as inclusions in ilmenite-hematite, and intergranular apatite (Ap2) formed under granulite-facies conditions. The presence of abundant needle-like monazite and sulphide inclusions in Ap2 indicate that granulite reactions were fluid assisted. A thin (typically <10μm) rim of REE-rich epidote (Ep1) commonly surrounds Ap2. In these accessory minerals, U and Th contents are too low, or grains are too small, for in situ U-Th-Pb dating. Sm-Nd isotope data of Ap2, monazite and Ep1 give an isochron age of 601±69Ma, which is interpreted to represent a partially reset Grenvillian age, affected by Caledonian fluid-assisted mineral growth. In amphibolitized samples, granulite Ap2 is replaced by apatite (Ap3) with lower REE contents and no monazite inclusions. The REE released by this replacement are redistributed in a corona of epidote group minerals (Ep2) surrounding Ap3. The in situ Sm-Nd isotope data for Ep2 and titanite, found in replacement of ilmenite-hematite, return an isochron age of 395±65Ma, recording the timing of amphibolite-facies mineral growth when fluids were introduced into the rock. In eclogitized samples, eclogitic apatite (Ap4) occurs as polycrystalline aggregates, suggesting for a complex replacement process during deformation. REE contents of Ap4 are low, as REE originally contained in the precursor apatite were redistributed mainly into zoisite. Apatite shielded as inclusions in ilmenite and garnet preserve the REE-rich signature of the initial magmatic (Ap1) and granulite (Ap2) apatite, indicating these grains did not undergo further re-equilibration during Caledonian metamorphism. The resistance of apatite to compositional re-equilibration in this case confirms the petrological potential of apatite inclusions shielded in chemically inert minerals to track early magmatic, or metamorphic, crystallisation stages.

Remarkably enhanced mechanical properties of Mg-8Gd-1Er-0.5Zr alloy on the route of extrusion, rolling and aging

The remarkably enhanced mechanical performance of Mg-8Gd-1Er-0.5Zr alloy with lower rare-earth content was achieved on the route of extrusion, rolling and aging processes in the present investigation. Results indicated that the ultrahigh UTS of 560 MPa and YTS of 518 MPa as well as elongation of 4.8% at ambient temperature were obtained. The β phase with size of 100–200 nm was precipitated during rolling in accompany with refined grains and strong basal texture, and the layer-structured precipitates with nanoscale were formed during aging. The fine β phase coordinating with strong basal texture as well as fine grain size controlled the mechanical performance of the rolled alloy, whereas the layer-structured precipitates contributed to the remarkably enhanced mechanical properties of the aged alloy.

Trace and rare earth element geochemistry of Holocene hydromagnesite from Dujiali Lake, central Qinghai–Tibetan Plateau, China

The genesis of hydromagnesite [Mg5(CO3)4(OH)2·4H2O] has attracted great interest as a pathway for sequestering anthropogenic CO2 and because of its importance to Mg carbonate depositional environments; however, there remain uncertainties regarding the chemical environment for hydromagnesite precipitation in modern and ancient geologic systems. Trace and rare earth element (REE) concentrations in hydromagnesite from Dujiali Lake, central Qinghai–Tibetan Plateau, China identified the formation conditions in the context of the depositional environment. The analyzed hydromagnesite samples had low total REE concentrations, varying from 0.62 to 3.11 ppm, with an average ∑REE value of 1.75 ppm. Comparisons of Ce/Ce* with LaN/SmN, DyN/SmN, and ∑REE showed no correlation indicating preservation of the original redox conditions during hydromagnesite precipitation. Redox-sensitive trace element ratios (U/Th, Ni/Co, V/Cr and V/V + Ni), negative Mn* values, and low authigenic uranium (Ua) values all indicate oxic conditions at the time of hydromagnesite formation. Furthermore, the Post-Archean Australian Shale-normalized REE patterns of the hydromagnesite display slight heavy REE enrichment, a slightly negative Ce anomaly, and a consistently positive Eu anomaly, which are consistent with precipitation in a predominantly oxidizing environment. Data indicate that hydromagnesite precipitated from waters influenced by both Mg-rich hydrothermal fluids and meteoric water with a similar composition to the lake water. This study provides new insights into the conditions of hydromagnesite formation at Dujiali Lake with implications for the understanding of the genesis of modern and ancient Mg carbonate deposits.

On the limits of coercivity in permanent magnets

The maximum coercivity that can be achieved for a given hard magnetic alloy is estimated by computing the energy barrier for the nucleation of a reversed domain in an idealized microstructure without any structural defects and without any soft magnetic secondary phases. For Sm1–zZrz(Fe1–yCoy)12–xTix based alloys, which are considered an alternative to Nd2Fe14B magnets with a lower rare-earth content, the coercive field of a small magnetic cube is reduced to 60% of the anisotropy field at room temperature and to 50% of the anisotropy field at elevated temperature (473 K). This decrease of the coercive field is caused by misorientation, demagnetizing fields, and thermal fluctuations.

Rare Earth Elements Recovery and Sulphate Removal from Phosphogypsum Waste Waters with Sulphate Reducing Bacteria

Phosphogypsum waste, originating from phosphoric acid production from apatite ores, is well known for its high production rate and possible release of sulphate-rich seepage waters. In addition to negative environmental impacts, phosphogypsum waste heaps are also remarkable secondary sources of Rare Earth Elements (REE); in the phosphoric acid production process a majority of REE, occurring in apatite, are precipitated to the phosphogypsum waste. Therefore, a method treating both sulphate-rich waters and recovering REE from phosphogypsum heaps and seepage waters would offer both economic and environmental benefits. In this ongoing study, seepage waters from a phosphogypsum heap are treated with Sulphate Reducing Bacteria (SRB) and ethanol as a substrate. Sulphate is first reduced to hydrogen sulphide, which then precipitates REE as sulphides. The main challenge, low concentration of REE in seepage waters (e.g. 2.87 μg/l La, 5.13 μg/l Ce, 0.67 μg/l Y and 3.32 μg/l Nd), is overcome by utilizing continuous mode, semi-passive and cost effective column apparatus, requiring no agitation and performing both sulphate reduction and REE recovery in a single reactor. The SRB method results in a sulphate reduction rate of 40-80 % (from app. 1400 mg/l to 276-844 mg/l sulphate in the effluent) and efficient REE recovery from seepage water. The concentrate obtained from the column consists of a mixture of anaerobic sludge and precipitated REE, with respective REE concentrations of 202 mg/kg La, 477 mg/kg Ce, 49 mg/kg Y and 295 mg/kg Nd.

Trace element composition and U-Pb age of zircons from Estherville: Constraints on the timing of the metal-silicate mixing event on the mesosiderite parent body

Mesosiderites are a group of stony-iron meteorites, which are thought to be the result of mixing of silicates with Fe-Ni metal. In this study, we combined textural observations with geochemical and chronological studies of two zircon grains found in the Estherville mesosiderite. One of the zircons (Zrc1) occurs with pyroxene, plagioclase, troilite, and silica, and the other (Zrc2) is located at a boundary between Fe-Ni metal and a silicate part mainly composed of pyroxene and plagioclase. The textural observations demonstrate that Zrc1 is relatively homogenous, whereas Zrc2 is composed of at least two chemically distinct domains. Trace element analyses of Zrc2 resolve large concentration gradients within this single grain with variations that are an order of magnitude for rare earth elements (REE) and two orders of magnitude for U and Th. The lowest trace element concentration in Zrc2 is more than an order of magnitude lower than those of lunar and eucritic zircons. However, it is similar to those of Zrc1 and a zircon from the Vaca Muerta mesosiderite. The calculated REE composition of the melt in equilibrium with Zrc2 shows that Zrc2 and perhaps also Zrc1 did not crystallize from a melt that was produced by fractional crystallization of the primary magmatic mineral assemblages. The zircons with low REE, U, and Th concentrations can be interpreted to have formed in a residual melt after incorporation of large amounts of REE, U, and Th into secondary phosphate minerals, which formed during the metal-silicate mixing event. The large concentration gradients observed in Zrc2 suggest significant heterogeneities in the melt from which the zircon crystallized. Alternatively, either mixing or diffusion between a relict zircon and a newly formed zircon could explain the observed concentration gradients. However, the REE patterns of Zrc2 cannot be explained by mixing or diffusion between the two distinct generations of zircons. These considerations suggest that Zrc1 and Zrc2 formed during a high-temperature reheating event, which is probably related to the metal-silicate mixing event. The weighted average 207Pb-206Pb age obtained by SIMS from both zircons is 4521±26Ma (2σ). This age is younger than that of a primary magmatic zircon from Vaca Muerta (4563±15Ma) and probably corresponds to the timing of the metal-silicate mixing event or a later impact event.

Controls on rare earth element distributions in ancient organic-rich sedimentary sequences: Role of post-depositional diagenesis of phosphorus phases

The processes that dictate the formation and preservation of rare earth element (REE) signatures in ancient marine black shales are incompletely understood, thus potentially limiting the utility of the REEs as geochemical tracers. Here, we report on whole-rock REE analyses of six black shale formations from different ages and depositional settings, which fall within three general groupings: Group 1 is characterized by low whole-rock REE content (ΣREE) (<250μg/g) and middle- and heavy-REE-enriched patterns (GdN/LaN<2, YbN/LaN<2.5); Group 2 is characterized by low ΣREE (<250μg/g) but greater middle-REE-enriched patterns (GdN/LaN>2, YbN/LaN<3); and Group 3 is characterized by high ΣREE (>250μg/g) and moderately middle-REE-enriched patterns (GdN/LaN~1.5–2.5, YbN/LaN~1). Representative samples from these groups were selected from the Marcellus and Hushpuckney shales and subjected to a multi-step leaching procedure, to isolate four extractable P-phases (reducible, authigenic carbonate-associated, detrital apatite, organic). In Group 1 samples with low carbonate content (<4% CaCO3), REEs were hosted mainly in the organic (50% of ΣREE) and siliciclastic fractions (37%); whereas in samples with greater carbonate content (>25% CaCO3), REEs were hosted mainly in carbonate-associated phases (53%). In Group 2, REEs were hosted mainly in the carbonate-associated (64%) and organic fractions (30%), and in Group 3, REEs were hosted mainly in the carbonate-associated (60%), detrital apatite (23%), and siliciclastic fractions (16%). Authigenic phases include minerals such as carbonate fluorapatite and authigenic calcite that, if present, tend to dominate the whole-rock REE inventory. In the absence of carbonate, whole-rock REE content depends on the relative REE contributions of the organic and siliciclastic fractions.

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

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. Log10 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 (δ15N), 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.

Geochemical signatures and processes in a stream contaminated by heavy mineral processing near Ipoh city, Malaysia

The environmental impacts of a heavy mineral processing involving rare earth elements (REEs) in the Kinta River and its tributaries near Ipoh city in Malaysia is investigated using geochemical and isotopic signatures and geochemical modeling. Analysis of water, sediment, suspended particulate matter, and rock samples reveals that stream waters close to the heavy mineral processing plant site are anthropogenically influenced, as indicated by slightly low pH (4.98–6.24) and elevated concentrations of Fe (up to 129 mg/L), Cl− (1540 mg/L), total REEs (1580 μg/L), U (17.2 μg/L), and Th (0.33 μg/L). REE patterns and Pb isotope ratios of waters and sediments from a tributary are similar to those of tailings pond seepage and sediments, suggesting that not only these elements but also U and Th are derived from heavy mineral processing. The δ56Fe values of water in the tributary decrease downstream, accompanied by a decrease in Fe concentration, which is likely due to isotope fractionation via oxidative precipitation of Fe hydroxides. The concentrations of REEs, U, and Th decrease downstream, accompanied by an increase in pH, with different removal factors (Th > U > REEs). The influence of contamination is confined to within ∼1.5 km downstream of the source. Tamm's acid oxalate extraction (to dissolve only low crystalline phases) showed that Th and Al concentrations were lower while U and Fe concentrations were higher in downstream suspended particulate samples, suggesting that Th and U may be removed by different mechanisms from stream water. The results of geochemical modeling suggest that Th precipitated as a solid phase, such as an intermediate between ThO2 and Th(OH)4, with increasing stream water pH. In contrast, U may have been removed by adsorption onto Fe hydroxides, as supported by surface complexation modeling. The geochemical signatures and processes discussed in this study may be applicable for environmental assessment of REE processing.

Rare Earth Elements in Alberta Oil Sand Process Streams

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 wt %), 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 extract 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 valu...

Genetic significance of zircon in orthogneisses from Sierra Nevada (Betic Cordillera, Spain)

AbstractZircon from two types of orthogneisses (inheritance-rich and inheritance-poor) from Sierra Nevada (Betic Cordillera, Spain) was investigated by integrating U–Pb geochronology, cathodoluminescence and back-scattered SEM imaging, laser-ablation inductively coupled plasma mass spectrometry analyses and Raman spectroscopy to examine the conditions of magmatic zircon growth and the variable extent and mechanisms of the Alpine modifications. Zircon from inheritance-rich gneiss consists of two main domains: inherited (Neoproterozoic-to-Early Paleozoic and Devonian) cores and magmatic overgrowths, which provided 206Pb/238U concordant ages of 286 ± 3 Ma. In inheritance-poor gneiss, zircons consist of magmatic cores and very altered rims defining a discordia with an upper intercept with the Concordia at 287 + 21 –22 Ma and a lower intercept at 20.8 + 48.6 –20.8 Ma. Magmatic domains of zircon from inheritance-rich gneiss have lower rare-earth element (REE) contents than magmatic domains from inheritance-poor gneiss, reflecting the less evolved nature of the melt. Altered domains in zircon from inheritance-poor gneisss how greater U concentrations, lower REE concentrations and lower Th/U ratios relative to the cores, interpreted as representing Pb loss from the U-rich magmatic domains during the Alpine event. Morphological changes within single grains and between populations reflects the evolution during magmatic cooling. We show that, whereas classic methods allow two different interpretations for the geodynamic setting of the two types of gneisses, a complete study of composition, morphology and structure of zircon can help to decide that a model based on a common source for the granitic melt better fits the zircon characteristics than a model based on melts generated in two different geotectonic settings.

Fast extraction and enrichment of rare earth elements from waste water via microfluidic-based hollow droplet

Abstract The conventional solvent extraction set-up for low-concentration rare earth elements (REEs) at high phase ratios has shortcomings including large factories, long mixing times, high energy consumption, extractant loss and easy emulsification. In this work, a solvent extraction system for Nd(III) using 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (P507) was investigated to enhance extraction in a microfluidic device to solve the above problems. The effects of residence time and phase ratio on the extraction efficiency of a liquid-liquid system were studied. The results showed that extraction efficiency increased as the residence time increased significantly, and a longer channel was required to reach equilibrium for higher phase ratios than for others owing to the decreased oil flow rate and increased mass transfer distance. We also investigated the effects of outlet length, phase ratio, and gas flow rate on the extraction efficiency of a gas-liquid-liquid system. The results indicated that only 0.3 m of the outlet channel was required to reach equilibrium for the entire process, and the overall volume mass transfer coefficient kLa was 5–50 times larger than in systems without a gas phase. The enrichment factor could reach 200–450 with an initial concentration of 30–90 ppm, and the extraction efficiency was higher than 90% even at a high phase ratio of 200. A theoretical model was built to predict the intensification of extraction by the gas-filled hollow droplet. Finally, europium and erbium were chosen as the typical medium and heavy rare earth systems to prove the applicability of this method.

Adaptation of a Rare Earth Element Pre-concentration Method for Water Enriched in Al, Ca, Fe, and Mg

The use of rare earth elements (REE) as process indicators in water-rock interactions can be hampered by the fact that samples with high concentrations of total dissolved solids require dilution before ICP-MS analysis, which can lower REE concentrations close to or below detection limits. A pre-concentration method originally developed for chloride-dominated water with very low REE concentrations was tested for and adapted to sulfate-rich water from a mining-affected area with a pH of 6 and high concentrations of Ca, Fe, Mg, and sometimes Al. The adapted approach proved easy to implement in the field and produced very good recoveries and reliable REE patterns. Two factors, sample volume and ionic strength, were tested. Pre-concentration with high sample volumes (1000 mL) resulted in poor recoveries (1.8 ± 0.3 % for La up to 17.8 ± 0.6 % for Yb). When the sample volume was reduced to 25 mL, much better recoveries were achieved. Reducing the ionic strength by diluting the sample 1:100 or 1:1000 resulted in comparable recoveries than the approach with reduced sample volume, indicating that sample volume was more important than ionic strength. Among the tested competing elements, high concentrations of Ca, Fe, and Mg resulted in loss of light REE (La-Nd), while Al was found to reduce the recovery of all REE. Also for water with high concentrations of Ca and Fe and very low REE concentrations (ppt-range), especially La results should be considered with care after pre-concentration, and be neglected in REE patterns if necessary.