• Economic and Environmental Geology
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• v.30 no.5
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• pp.417-431
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• 1997

Characteristics of sedimentary rocks and enrichment of toxic elements in shale and coal from the Chungnam coal field were investigated based upon geochemistry of major, trace and rare earth elements. Shale and coal of the area are interbedded along the Traissic to the Jurassic Daedong Supergroup, which can be subdivided into grey shale, black shale and coal. The coal had been mined, however all the mines are abandonded due to the economic problems. The shale and coal are characterized by relatively low contents of $SiO_2$, and $Al_2O_3$ and high levels of loss-on-ignition (LOI), CaO and $Na_2O$ in comparison with the North American Shale Composite (NASC). Light rare earth elements (La, Ce, Yb and Lu) are highly enriched with the coal. Ratios of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in shale and coal range from 30.0 to 351.8 and from 4.2 to 106.8, which have partly negative correlations against $SiO_2/Al_2O_3$ (1.24 to 6.06), respectively. Those are suggested that controls of mineral compositions in shale and coal can be due to substitution and migration of those elements by diagenesis and metamorphism. Shale and coal of the area may be deposited in terrestrial basin deduced from high C/S (39 to 895) and variable composition of organic carbon (0.39 to 18.40 wt.%) and low contents of reduced sulfur (0.01 to 0.05 wt.%). These shale and coal were originated from the high grade metamorphic and/or igneous rocks, and the rare earth elements of those rocks are slightly influenced with diagenesis and metamorphism on the basis of $Al_2O_3$ versus La, La against Ce, Zr versus Yb, the ratios of La/Ce (0.38 to 0.85) and Th/U (3.6 to 14.6). Characteristics of trace and rare earth elements as Co/Th (0.07 to 0.86), La/Sc (0.31 to 11.05), Se/Th (0.28 to 1.06), V/Ni (1.14 to 3.97), Cr/V (1.4 to 28.3), Ni/Co (2.12 to 8.00) and Zr/Hf (22.6~45.1) in the shale and coal argue for inefficient mixing of the simple source lithologies during sedimentation. These rocks also show much variation in $La_N/Yb_N$ (1.36 to 21.68), Th/Yb (3.5 to 20.0) and La/Th (0.31 to 7.89), and their origin is explained by derivation from a mixture of mainly acidic igneous and metamorphic rocks. Average concentrations in the shale and coal are As=7.2 and 7.5, Ba=913 and 974, Cr=500 and 145, Cu=20 and 26, Ni=38 and 35, Pb=30 and 36, and Zn=77 and 92 ppm, respectively, which are similar to those in the NASC. Average enrichment indices for major elements in the shale (0.79) and coal (0.77) are lower than those in the NASC. In addition, average enrichment index for rare earth elements in coal (2.39) is enriched rather than the shale (1.55). On the basis of the NASC, concentrations of minor and/or environmental toxic elements in the shale and coal were depleted of all the elements examined, excepting Cr, Pb, Rb and Th. Average enrichment indices of trace and/or potentially toxic elements (As, Cr, Cu, Ni, Pb, U and Zn) are 1.23 to 1.24 for shale and 1.06 to 1.22 for coal, respectively.

• Korean Journal of Metals and Materials
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• v.56 no.12
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• pp.870-877
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• 2018

Cyanex 272 shows the highest separation factor for the rare earth elements from hydrochloric acid solution among the organophosporus acidic extractants, D2EHPA and PC 88A. Solvent extraction of Tb(III) from weak hydrochloric acid solution with an initial pH 3 to 6 was compared with Cyanex 272, its mixture with Alamine 336, and ionic liquid with Aliquat 336. The solvent extraction reaction of Tb(III) using Cyanex 272 was the same as that of light rare earth elements. Synergism was observed for the extraction of Tb(III) by the mixture with Alamine 336 when the initial concentration ratio of Cyanex 272 to Alamine 336 was higher than 5. Use of the ionic liquid led to a great increase in the extraction percentage of Tb(III) from the same initial extraction conditions. While the equilibrium pH of the mixture was always lower than the initial pH, under some conditions extraction with the ionic liquid resulted in a higher equilibrium pH than the initial pH. The loading capacity of the mixture and the ionic liquid was the same and 2.6 times larger than that using Cyanex 272 alone. Ionic liquid was recommended as a suitable extractant for the extraction of Tb(III) from hydrochloric acid solution based on the ease of handling and higher extraction percentage.

• Journal of the Korean earth science society
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• v.43 no.2
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• pp.303-311
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• 2022

Gadolinium, commonly used as a contrast agent for magnetic resonance imaging (MRI), is discharged into aquatic environments without removal after treatment in wastewater treatment plants (WWTPs) because of its high stability. In this study, we collected water samples from Suyeong WWTP, Busan, to investigate the dissolved rare earth element (REE) removal capacity of each wastewater treatment process and to evaluate the discharge of anthropogenic Gd (Gd_anth) from effluents. As wastewater passed through each stage of treatment, the concentrations of light REEs (La-Eu) decreased, whereas those of heavy REEs (Tb-Lu) were relatively consistent. Negative Sm anomalies (<1) were observed in several samples, indicating that Sm can be removed by adsorption onto particles or phosphate during the biological removal process. Positive Gd anomalies (149±50, n=9) were observed in all samples. The ratios of Gd_anth concentrations to measured Gd concentrations in all wastewater treatment processes were higher than 97%. This indicates that Gd_anth was discharged to the Suyeong River without removal during the wastewater treatment process. Considering the daily treatment capacity in each process, the total flux of Gd_anth was estimated to be 259 mmol/day. Our results suggest that mid- and/or long-term monitoring of Gd is needed because Gd_anth is continuously discharged into Suyeong Bay through WWTPs.

• Analytical Science and Technology
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• v.21 no.4
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• pp.272-278
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• 2008

Methods to separate 14 rare earth elements (REEs) and yttrium by the $AG^{(R)}$ 50W-X8 cation exchange resin, and to determine REEs by inductively coupled plasma atomic emission spectrophotometry (ICP-AES) were described. Ion exchange capacities of REEs on the resin were so high that the REEs were quantitatively ion exchanged under the flow rate of 0.3~1.0 mL/min at pH 1~6. The breakthrough capacity curve of the REEs showed that ion exchange capacities of light REEs (Cerium group) were greater than that of the heavy REEs (Yttrium group). When $200{\mu}g$ of each REEs was ion exchanged on 100 mg of resin, most of the heavy REEs were quantitatively desorbed with 10 mL of 2.0 M of $HNO_3$, while most of the light REEs with 30 mL. The method was applied to the monazite sample. The REEs could be separated from matrix, since ion exchange capacities of matrix ions of Ca, Ti, Mg, Mn were much lower than that of the REEs. However the relative standard deviations of the analytical results by the present method were not improved, as high as 1~5%.

• Resources Recycling
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• v.26 no.4
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• pp.79-87
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• 2017

Extraction and separation behaviors of La, Ce, Pr, Nd and Sm from light rare earth multi - component mixed solutions by Cyanex 572 were studied. As extractant concentration increased, the $pH_{50}$ values of all the five components decreased. When extractant concentration was larger than 0.6 M, the separation factor of La and Ce, Nd and Sm was higher than 10, while the separation factor between Ce and Pr, Pr and Nd was as low as 0.5~2.2. Addition of TBP to the 0.6 M Cyanex 572 had little synergistic effect on the phase separation rate and separation factor. From the analysis of experiment results, group separation of [La]/[Pr, Nd, Sm] and [Pr, Nd]/[Sm] could be possible, but in case of the group separation between [La, Ce] and [Pr, Nd] was not available because of the low separation factor between Ce and Pr.

• Economic and Environmental Geology
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• v.20 no.2
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• pp.85-95
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• 1987

The host rocks of titaniferous magnetite deposits in Gonamsan are alkaline gabbros, which are typical of undersaturated alkaline rocks in terms of the lack of normative quartz. According to field occurrences and petrographic features, these alkaline gabbros are divided into 3 rock types: coarse-grained and pegmatitic rock, medium-grained rock with equigranular texture, and layered cumulate rock. All these rocks mainly contain clinopyroxene(salite), plagioclase(An 43-66), pargasite, and ilmenite. The accessory minerals are apatite, sphene, quartz, and sometimes titaniferous magnetite. Pargasite, sphene, and quartz are considered to be secondary minerals formed by the reaction among clinopyroxene, plagioclase and Fe-Ti oxide at deuteric stage. Fe-Ti oxides generally occur as ilmenite in the alkaline rocks, and titaniferous magnetite in the ore deposits. Layered cumulate rocks are characterized by a recurrence of discontinuous thin mesolayer of clinopyroxene-pargasite within leucolayer mainly composed of plagioclase. Clinopyroxene is cumulus mineral whereas plagioclase, ilmenite and apatite occur as intercumulus minerals. According to the variation diagrams of oxide and trace element contents against the differentiation index, incompatible elements, such as Na, Ba and Sr, show positive correlations whereas compatible elements, such as Mg and Cr, show negative correlations. However some compatible elements, such as Co, Ni and V show irregular variations, reflecting relative cumulate status of cumulus and intercumulus minerals. On the de la Roche multicationic diagram, these alkaline gabbros are distributed along the differentiation curve of undersaturated alkaline series from alkaline basaltic composition through basanitic composition to tephritic composition. Layered cumulate rocks, which are distributed between basanitic composition and tephritic composition, reflect their cumulate character, slightly scattering away from the curve. The medium-grained rock shows higher contents in Ba, Sr and light rare earch elements than the coarse-grained and pegmatitic rock. The former shows two times higher contents of total rare earth elements than the latter, $while(La/Lu)_{cn}$ ratios maintain fairly constant values of 5.08~5.06 in these two rocks. This means that coarse-grained and pegmatitic rock, as compared with the medium-grained rock, was formed by the earlier differentiated magma but rare-earth element distribution pattern remained almost parallel during differentiation. From the data the above mentioned, these alkaline gabbros are considered to be comagmatic and to be formed by intrusions of differentiated magmas in its reservoir.

• Resources Recycling
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• v.29 no.1
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• pp.17-24
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• 2020

In this study, rare earth elements (REE) leaching from a refractory REE ore containing goethite as a major gangue mineral was conducted, introducing a two-stage method of chemical decomposition-acid leaching. At the chemical decomposition step, using one of alkaline agent, NaOH, the ore was decomposed, changing NaOH concentration from 20 to 50 wt% at 10% (w/w) of pulp density and the maximum temperature achieved without boiling at each NaOH concentration. With increasing NaOH concentration, light REE (Ce, La and Nd) and iron were concentrated in the solid phase which is the decomposed product, while aluminum (Al) and phosphorus (P) were removed to the liquid phase, and their concentrations in the solid phase were down to 0.96 and 0.17%, respectively. In addition, through XRD analysis, it was found that the crystallinity of goethite was considerably decreased. At the acid leaching step, the product decomposed by 50 wt% NaOH was leached at 3.0 M HCl and 80 ℃ for 3 hr, then the REE leaching efficiency was above 94% (Ce 80%), and the leaching efficiencies of Al and P were decreased to 12 and 0%, respectively. Therefore, in terms of both REE leaching efficiency and impurity removal, those decomposition and leaching conditions were chosen as optimum processing methods of the investigated material. In terms of REE leaching mechanism, because REE and iron leaching efficiencies showed the positive correlation each other, so it can be concluded that decreasing crystallinity of goethite affect the improvement of REE leaching.

• Journal of the Mineralogical Society of Korea
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• v.26 no.4
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• pp.245-262
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• 2013

We analyzed 29 surface sediment samples in five submarine volcanoes (TA12, TA19, TA22, TA25, and TA26) located in the southern part of the Tonga arc for trace elements and rare earth elements to investigate characteristics of the hydrothermal alteration of surface sediments. Based on analytical results of trace element and rare earth element (REE), surface sediments of TA12, TA19, and TA22 submarine volcanoes, which are located in the northern part of the study area, were very little or not influenced by hydrothermal fluids. In contrast, some stations of TA25 and TA26 submarine volcanoes were strongly affected by hydrothermal fluids. However, these two submarine volcanoes showed different features in element concentration in the sediments. Some stations of TA25 submarine volcano showed enrichment of Ni, Cu, Sn, Zn, Pb, Cr, Cd, Sb, W, Ba, Ta, Rb, Sr, and As, however, those of TA26 submarine volcano showed enrichment of Sn, Zn, Pb, Cd, Sb, Ba, Rb, and Sr. Stations which enriched trace elements were observed, enriched REEs were also observed. Average upper continental crust (UCC)-normalized REE patterns of the surface sediments generally showed low light REE (LREE) abundances and increased heavy REE (HREE) abundances. Eu enrichment was identified at several stations of TA25 and TA26 submarine volcanoes. In addition, enrichment of Ce was found at some stations of TA26 submarine volcano and these enrichment patterns were similar with hydrothermal fluid of near stations. Furthermore, TA25 and TA26 submarine volcanoes showed different enrichment characteristics of trace elements and REE. Trace elements were concentrated at TA25 submarine volcano. TA26 submarine volcano, on the other hand, observed highly enrichment of REE especially, Eu and Ce. As a result of the investigation, the characteristics and concentrations of REEs and trace elements in the surface sediments of each submarine volcano can be applied to identify hydrothermal alteration of sediments during exploration for hydrothermal deposits.

• Economic and Environmental Geology
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• v.55 no.3
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• pp.241-259
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• 2022

In general, the REE were produced by mining conventional deposits, such as the carbonatite or the clay-hosted REE deposits. However, because of the recent demand increase for REE in modern industries, unconventional REE deposits emerged as a necessary research topic. Among the unconventional REE recovery methods, the REE-bearing coal deposits are recently receiving attentions. R-types generally have detrital originations from the bauxite deposits, and show LREE enriched REE patterns. Tuffaceous-types are formed by syngenetic volcanic activities and following input of volcanic ash into the basin. This type shows specific occurrence of the detrital volcanic ash-driven minerals and the authigenic phosphorous minerals focused at narrow horizon between coal seams and tonstein layers. REE patterns of tuffaceous-types show flat shape in general. Hydrothermal-types can be formed by epigenetic inflow of REE originated from granitic intrusions. Occurrence of the authigenic halogen-bearing phosphorous minerals and the water-bearing minerals are the specific characteristics of this type. They generally show HREE enriched REE patterns. Each type of REE-bearing coal deposits may occur by independent genesis, but most of REE-bearing coal deposits with high REE concentrations have multiple genesis. For the case of the US, the rare earth oxides (REO) with high purity has been produced from REE-bearing coals and their byproducts in pilot plants from 2018. Their goal is to supply about 7% of national REE demand. For the coal deposits in Korea, lignite layers found in Gyungju-Yeongil coal fields shows coexistence of tuff layers and coal seams. They are also based in Tertiary basins, and low affection from compaction and coalification might resulted into high-REE tuffaceous-type coal deposits. Thus, detailed geologic researches and explorations for domestic coal deposits are required.

• Advances in environmental research
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• v.5 no.1
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• pp.1-18
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• 2016

Magnetic nano-based sorbents have been synthesized for the recovery of two rare earth elements (REE: Nd(III) and Yb(III)). The magnetic nano-based particles are synthesized by a one-pot hydrothermal procedure involving co-precipitation under thermal conditions of Fe(III) and Fe(II) salts in the presence of chitosan. The composite magnetic/chitosan material is crosslinked with epichlorohydrin and modified by grafting alanine and serine amine-acids. These materials are tested for the binding of Nd(III) (light REE) and Yb(III) (heavy REE) through the study of pH effect, sorption isotherms, uptake kinetics, metal desorption and sorbent recycling. Sorption isotherms are well fitted by the Langmuir equation: the maximum sorption capacities range between 9 and 18 mg REE $g^{-1}$ (at pH 5). The sorption mechanism is endothermic (positive value of ${\Delta}H^{\circ}$) and contributes to increase the randomness of the system (positive value of ${\Delta}S^{\circ}$). The fast uptake kinetics can be described by the pseudo-second order rate equation: the equilibrium is reached within 4 hours of contact. The sub-micron size of sorbent particles strongly reduces the contribution of resistance to intraparticle diffusion in the control of uptake kinetics. Metal desorption using acidified thiourea solutions allows maintaining sorption efficiency for at least four successive cycles with limited loss in sorption capacity.