• Journal of the Mineralogical Society of Korea
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• v.15 no.1
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• pp.1-10
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• 2002

The present study is focused on the granite weathering and soil formation, and the heavy metal contamination in soils in the Onsan industrial area. For profile study, soil sampling was conducted on each depth and experimental analyses have been conducted on those samples. X-ray diffraction analyses show that clay minerals consist mainly of kaolin minerals, vermiculite, and minor illite. Most of kaolin minerals in the lower kiwi of the profile consist of halloysite as confirmed by formamide intercalation, but the content of halloysite decreases gradually toward the surface since it has been transformed to kaolinite in the upper part of the profile. Thermal treatment by heating at $110^{\circ}C,\;300^{\circ}C,\;and\;550^{\circ}C$ shows a diffuse and broad peak the between 10 and $14\;{\AA}$ region in X-ray diffractograms. This suggests the possible existence of the hydroxy-Al interlayerecl vermiculite. Na-citrate extraction method reaconfirms this result showing transition of $14\;{\AA}$ peak to $10\;{\AA}$ In by removing the interlayer materials and restoring the vermiculite to its original state. The occurrence of hydroxy-Al interlayered vermiculite is also supported by soil pH distribution room 3.9 In the lower part to 3.6 in the upper part of the profile. Sequential extraction experiment was conducted to investigate the states of heavy metals in soils. The experiment shows that relatively high amounts of heavy metals are concentrated in the upper part of the profile and that most of them are bound to Fe/Mn oxides and organic matters while less concentration in clay minerals. The result indicates that most of heavy metal pollutants are concentrated in the surface soil and that the low concentrations of heavy metals in clays are mainly due to the low adsorption capacities of clay minerals such as kaolin minerals and hydroxy-Al interlayered vermiculite in acidified soil condition.

• Economic and Environmental Geology
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• v.28 no.4
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• pp.351-367
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• 1995

The elemental geochemistry and oxygen isotopes of illite/smectite (I/S) have been studied in relationship to the mineralogical trend in the Reindeer D-27 well, Beaufort-Mackenzie Basin. The increase in concentrations of $K_2O$, Rb and rare earth elements (REE), the decrease in concentrations of tetrahedral elements such as Mg, Ti, Sc, Zn and Zr, and the increase in concentrations of tetrahedral elements such as Be and V can be related to I/S compositions that vary systematically with depth. Layer formulae of S- and I-layers are estimated as $[Al_{1.57}Fe_{.19}Mg_{.31}Ti_{.07}][Si_{3.84}Al_{.16}]O_{10}(OH)_2$ and $[Al_{1.84}Mg_{.16}][Si_{3.33}Al_{.67}]O_{10}(OH)_2$, respectively. The mobilization of REE appears to occur during illitization. The increase in concentrations of REE, especially La and Ce, with depth is probably linked to incorporation of ions with high valency (e.g. $V^{5+}$) in tetrahedral sites. The excess valency due to V is partly counter-balanced by ions with low valency (e.g. $Be^{2+}$) and, in turn, the local valency deficiency caused by $Be^{2+}$ could be compensated by high-charge interlayer cations such as REE (＋3). ${\delta}^{18}O$ values of I/S range from 2.91 to 15.72‰ (SMOW), and increase with depth, contrasting to trends observed in the Gulf Coast and elsewhere. The increase in ${\delta}^{18}O$ of I/S results from the rapid increase in ${\delta}^{18}O$ of pore water that overcomes the decrease in temperature-dependent fractionation values with increasing burial depth (${\delta}^{18}O_{pore\;water}>-d{\Delta}/_{I/S-water};\;d{\delta}^{18}O_{I/S}>0$). Calculated ${\delta}^{18}O$ values of pore water in equilibrium with I/S suggest that the original water was probably meteoric water. The stratification of pore water is postulated from the presence of an isotopically light interval, about 450m thick. The depth range of the isotopically light zone overlaps, but does not coincide with the interval of lowered I-content and $K_2O$ concentrations, suggesting that oxygens may have been exchanged independently of mineralogical and geochemical reactions.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.2
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• pp.111-123
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• 2022

Carbonate green rust (CGR) and sulfate green rust (SGR) commonly occur in nature. In this study, CGR and SGR were synthesized through co-precipitation, and their formation mechanisms and physicochemical properties were investigated. X-ray diffraction (XRD) and Rietveld refinement showed both CGR and SGR with layered double hydroxide structure were successfully synthesized without any secondary phases under each synthetic condition. Refined structural parameters (unit cell) for two green rusts were a (=b) = 3.17 Å and c = 22.52 Å for CGR and a (=b) = 5.50 Å and c = 10.97 Å for SGR with the crystallite size 57.8 nm in diameter from (003) reflection and 40.1 nm from (001) reflections, respectively. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) results showed that both CGR and SGR had typical hexagonal plate-like crystal morphologies but their chemical composition is different in the content of C and S. In addition, Fourier transform infrared (FT-IR) spectroscopy analysis revealed that carbonate (CO₃^2-) and sulfate (SO₄^2-) molecules were occupied as interlayer anions of CGR and SGR, respectively. These SEM/EDS and FT-IR results were in good agreement with XRD results. Changes in the solution chemistry (i.e., pH, Eh and residual iron concentrations (Fe(II):Fe(III)) of the mixed solution) were observed as a function of the injection time of hydroxyl ion (OH^-) into the iron solution. Three different stages were observed in the formation of both CGR and SGR; precursor, intermediator, and green rust in the formation of both CGR and SGR. This study provides co-precipitation methods for CGR and SGR in a way of the stable synthesis. In addition, our findings for the formation mechanisms of the two green rusts and their physicochemical properties will provide crucial information with researches and industrials in utilizing green rust.

• Journal of the Mineralogical Society of Korea
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• v.25 no.3
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• pp.143-153
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• 2012

Mica-type minerals (illites) in the shales of the Jigunsan formation at Seokgaejae in Samchuk-City, Gangwon-do are studied using electron probe micro analysis (EPMA). The average chemical formula of the mica-type mineral obtained from the quantitative analysis is $(K_{1.17}Na_{0.04}Ca_{0.01})(Al_{2.80}Mg_{1.17}Fe_{0.78})(Si_{6.34}Al_{1.66})O_{20}(OH)_4$, which shows a chemical formula within the range of illite. These illites so called can be considered as mixed-phases among muscovite, pyrophyllite and chlorite due to the low contents of interlayer cations and high Mg, Fe. The formula of illite is separated into those three minerals and the method for the separation is newly formulated and proposed in this study. From the formula of illite, the content of muscovite is estimated from K (Na and Ca included), the content of chlorite by Mg+Fe, and the rest remains as pyrophyllite. The chemical formula of muscovite can be calculated by subtracting the compositions of pyrophyllite and chlorite from the analyzed composition of illite using an ideal formula for pyrophyllite and analyzed average formula for chlorite. The calculated formula of muscovite is supposed to be stoichiometric in principle. The result of the separation of analyzed illite is 61% muscovite, 27.3% chlorite and 11.7% pyrophyllite and the calculated formula of muscovite after separation is $(K,Na,Ca)_{2.00}Al_{3.69}(Si_{6.75}Al_{1.25})O_{20}(OH)_4$. The calculated formula of muscovite slightly low in Al content can be considered to be reasonable in general when the low content of Al in the rock and the uncertainties of chlorite compositions used in the calculation are counted. This supports that the method of separation proposed in this study is also applicable.

• Korean Journal of Microbiology
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• v.39 no.3
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• pp.166-174
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• 2003

Microcystin produced by cyanobacteria in surface waters, such as eutrophic lake and river, is a kind of serious environmental problems due to its toxicity to human and wild animals. Microcystin is synthesized nonribosomally by the large modular multi-functional enzyme complex known as microcystin synthetase encoded by the mcy gene cluster. Amplification of mcy genes by PCR from cultures and environmental samples is a simple and efficient method to detect the toxigenic Microcystis. In order to evaluate primers designed to detect toxic microcystin-producing strains, 17 cyanobacterial strains and 20 environmental samples were examined by PCR with 7 pairs of primers. Some microcystin-producing cyanobacteria were not detected with FAA-RAA, TOX4F-TOX4R and FP-RP primers. The fragment of unexpected size was amplified with NSZW2-NSZW1 primers in Microcystis strains isolated from the lakes in Korea. TOX1P-TOX1F primers failed in amplification of toxin-producing strains. Only MSF-MSR and TOX2P- TOX2F primers amplified the fragments of mcy genes from 11 strains of microcystin-producing Microcystis. The water samples taken from 20 lakes in Korea were analyzed by PCR using each of the primers. In all the water samples, cyanobacteria capable of producing microcystin were detected by the PCR with TOX2P-TOX2F primers. These results indicate that TOX2P-TOX2F primers are better than the other primers for detection of microcystin-producing Microcystis strains in Korea. The nucleotide sequences of mcy gene in Microcystis aeruginosa NIER10010 suggest genetic diversity of Korean isolates.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

• Journal of the Mineralogical Society of Korea
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• v.17 no.3
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• pp.245-265
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• 2004

This study was to compare the geological occurrences and geneses of the Myogi, Tsukinuno, Dobuyama and Kawasaki bentonite deposits distributed in the Tertiary sedimentary basins of NE Japan, and to compare the mineralogical and physicochemical properties of their bentonites. The Japanese bentonite deposits are mainly distributed in the Green-tuff region which was formed in Neogene. The shape of ore body of the Myogi, Tsukinuno and Kawasaki deposits formed by the diagenesis are layered and stratiform. In contrast to this, the Dobuyama deposit formed by hydrothermal alteration shows the cone shape. The mineralization age of four deposits are 1.8 ～ 21 Ha from Early Miocene to Pliocene. The Dobuyama bentonite with the highest montmorillonite content shows the highest surface area, CEC, MB adsorption, and strengths. The Tsukinuno bentonite with a little high montmorillonite content is characterized by strong alkalinity, high viscosity and swelling. The Kawasaki bentonite, the Na-Ca mixed type, shows higher viscosity and swelling than the Ca-type Dobuyama bentonite. The Myogi bentonite with the lowest montmorillonite content shows the properties of low viscosity, In adsorption, strengths and a little high CEC and surface area. The high CEC and surface area of this deposit is due to the sufficient occurrence of zeolite. A strong dispersion in the Na-type bentonite and a strong flocculation in the Ca-type bentonite took place, and both the types show a slow flocculation with time. The physicochemical properties of the bentonite are mainly controlled by the montmorillonite content, interlayer cations, and impurity minerals such as zeolite. But bentonites inconsistent to this factors are sometimes occurred. This is maybe due to the crystal chemistry such as layer charge of montmorillonite and crystal morphology of montmorillonite such as aspect ratio.

• Economic and Environmental Geology
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• v.18 no.4
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• pp.399-410
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• 1985

Bentonites from the Janggi Group of the Lower Miocene age from the Geumgwangdong area, Korea, have been studied for mineralogical and genetic characterization. The Janggi Group is subdivided, in ascending order, into the Janggi Conglomerate, the Nuldaeri Tuff, the Geumgwangdong Shale, the Lower Coal-bearing Formation, the Basaltic Tuff, and the Upper Coalbearing Formation. Bentonites occur as thin or thick beds in all sedimentary units of the Janggi Group, except for the Janggi Conglomerate. Significant bentonite deposits are found in the Nuldaeri Tuff, the Lower Coal-bearing Formation and the Basaltic Tuff. Bentonites consist mainly of smectite (mainly montmorillonite), with minor quartz, cristobalite, opal-CT and feldspar. Occasionally, kaolinite, clinoptilolite or gypsum is associated with bentonites. Bentonites were studied by the methods of petrographic microscopy, X-ray diffraction, thermal analysis (DT A and TG), infrared absorption spectroscopic analysis, SEM, intercalation reaction, and chemical analysis. Smectites commonly occur as irregular boxwork-like masses with characteristic curled thin edges, but occasionally as smoothly curved to nearly flat thin flakes. Most of smectites have layer charge of 0.25-0.42, indicating typical montmorillonite. Crystal-chemical relations suggest that Fe is the dominant substituent for Al in the octahedral layer and there are generally no significant substituents for Si in the tetrahedral layer. Ca is the dominant interlayer cation in montmorillonite. Therefore, montmorillonite from the study area is dioctahedral Ca-montmorillonite. Occurrence and fabrics of bentonites suggest that smectites as well as cristobalite, opal-CT and zeolites have been formed diagenetically from tuffaceous materials. The precursor of smectites is trachytic or basaltic tuff. Smectites derived from the former contain relatively more $Al_2O$ a and less $Fe_2O_3$ than those from the latter.

• Journal of the Mineralogical Society of Korea
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• v.26 no.1
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• pp.55-64
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• 2013

The generation of staurolite from the mixed-phase muscovite and the metamorphic environment of shales in the Baekunsa formation, Hongsan, Buyeo, were studied using electron probe micro analysis (EPMA). The average chemical composition of mica-type mineral is $(K_{1.11}Na_{0.26}Ca_{0.04})(Al_{3.93}Fe_{0.21}Mg_{0.07})(Si_{6.08}Al_{1.92})O_{20}(OH)_4$, and shows a characteristics of the so-called illite with a low content of interlayer cations and Fe, Mg in octahedral sites. The mica-type mineral shows a typical chemical composition of the mixed-phase among muscovite, pyrophyllite, and chlorite (mixed-phase muscovite, $Mu_{70.5}Py_{23.5}Ch_{6.0}$). The staurolite, in general, occurs with the mixed-phase muscovites, pyrophyllites, and aluminosilicates in the rock. We consider that staurolite can be formed by a reaction involving pyrophyllite such as pyrophyllite+chloritoid. The chloritoid is formed by a reaction between pyrophyllite and chlorite and is supposed to be used up in the process of staurolite formation. As a result, the mixed-phase muscovite, formed during the transition of illite to muscovite, plays an important role for the generation of the staurolite. Considering that the reaction occurs at the temperature higher than $300^{\circ}C$ and pyrophyllites transform into aluminosilicates at $350^{\circ}C$, the shale in the Baekunsa formation can be considered to have been experienced a metamorphic temperature between $300{\sim}350^{\circ}C$.

• Journal of the Mineralogical Society of Korea
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• v.22 no.1
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• pp.23-34
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• 2009

The adsorption of iodide on untreated bentonite and bentonites modified with organic cation (i.e., hexadecylpyridinium chloride monohydrate ($HDP^+$)) was investigated, and the organobentonites were characterized using uptake measurements, ${\mu}$-XRD, and electrophoretic mobilities measurement. Uptake measurements indicate that bentonite has a high affinity for $HDP^+$. Our ${\mu}$-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of bentonite. The electrophoretic mobility indicates that organobentonite tht is modified with organic cations in excess of the CEC of bentonite is completely different from untreated bentonite in the surface charge distribution. We found significant differences in adsorption capacities of iodide depending on the bentonite properties as follows: iodide adsorption capacities were 439 mmol/kg for the bentonite modified with $HDP^+$ at an equivalent amount corresponding to 200% of the CEC of bentonite whereas no adsorption of iodide was observed for the untreated bentonite. The molecular environments of iodine adsorbed on organobentonites were further studied using I K-edge and $L_{III}$-edge x-ray absorption spectroscopy (XAS). The X-ray absorption near-edge structure (XANES) of iodine spectra from organobentonites was similar to that of KI reference solution. Linear combination fitting of EXAFS data suggests the fraction of iodine reacted with the organic compound increased with increasing loading of the organic compound on organobentonites. In this study, we observed significant differences in the adsorption environments of iodide depending on the modified property of bentonite and suggest that an organobentonite has potential as reactive barrier material around a nuclear waste repository containing anionic radioactive iodide.