• Journal of the Mineralogical Society of Korea
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• v.6 no.1
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• pp.38-47
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• 1993

Clinoptilolite and mordenite are important constituents of the Nuldaeri Trachytic Tuff and Guryongpo Dacitic Tuff of the Tertiary Janggi Group which were deposited in a lacustrine environment. The diagenetic cystallization sequences of zeolites in different tuffaceous sediments and their chemical behaviors have been studied to know the process of their formation. The paragenetic sequence established from textural observations and chemical data : Ca-smectite ${\leftrightarrow}$(Ca, K)-clinoptilolite${\leftrightarrow}$(K, Na)-mordenite, indicates that the chemical activities of alkalic ions and Si/Al activity ratio in pore fluids changed systematically with diagenetic alteration. The chemical trend of zeolite formation is characterized by decreasing Ca and Mg, non-variable Na and increasing K in the Nuldaeri Trachytic Tuff and by decreasing Ca and Mg, non-variable Na and increasing-decreasing K in the Guryongpo Dacitic Tuff. The paragenesis from glass via smectite to alkali zeolites indicates a sequence of incongruent dissolution reactions and subsequent crystallization. Inhomogeneity in chemical composition of each zeolite may be attributed to such processes.

• Journal of the Mineralogical Society of Korea
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• v.21 no.1
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• pp.45-56
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• 2008

This study was carried out to determine the effects of mineral composition and grain size of zeolite and bentonite from Po-hang and Kyung-ju, South Korea on the adsorption of heavy metals. Zeolite specimen consists mainly of mordenite, clinoptilolite, heulandite etc. And bentonite specimen is mainly composed of montmorillonite. Five heavy metals, Cd, Cr, Cu, Mn, and Pb were used to conduct the relevant adsorption experiments with the fixed concentrations of 10 ppm and 20 ppm, respectively. Host specimens excluding specimen for Cr resulted in the adsorption rate over average 80 percent, and over 95 percent for Pb. This study indicates that zeolite is more efficient in the adsorption of the heavy metals than bentonite, and its adsorption rate tends to decrease with increasing concentration of the heavy metals.

• Journal of the Mineralogical Society of Korea
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• v.16 no.3
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• pp.201-213
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• 2003

The adsorption property and ability of domestic zeolites for some heavy metal ions (Ag, Pb, Cr, Cu, Zn, Mn), which may cause a serious environmental problem in industrial wastewater, were evaluated on ore unit through a series of adsorption experiments together with careful examinations of mineral composition and properties of the zeolites. Though the adsorption behavior basically took place in the form of a cation exchange reaction, the higher CEC value does not necessarily to imply the higher adsorption capacity for a specific heavy metal. A general trend of the adsorption selectivity for heavy metals in the zeolites is determined to be as follow: $Ag\geq$Pb>Cr,Cu$\geq$Zn>Mn, but the adsorption properties of heavy metal ions somewhat depend on the species and composition of zeolite. Clinoptilolite tends to adsorb selectively Cu in case of Cr and Cu, whereas heulandite prefers Cr to Cu. A dominant adsorption selectivity of the zeolite ores for Ag and Pb is generally conspicuous regardless of their zeolite species and composition. The zeolite ores exhibit a preferential adsorption especially for $Ag^{+}$ so as not to regenerate when treated with $Na^{+}$ . In the adsorption capacity for heavy meta ions, the zeolites differ in great depending on their species: ferrierite>clinoptilolite>heulandite. Considering the CEC value of mordenite, the mordenite-rich ore appears to be similar to the clinoptilolite ore in the adsorption capacity. The adsorption capacity for heavy metals is not positively proportional to the CEC values of the zeolites measured by the exchange reaction with ammonium ion. In addition, the adsorption capacity roughly tends to depend on the zeolite contents, i.e., the grade of zeolite ore, but the trend is not consistent at all in some ores. These may be caused by the adsorption selectivity for some specific heavy metals, the presence of possible stacking micro-faults and natural cations such as K hardly to exchange in the zeolite. Considering the economic availability and functional effectiveness as natural zeolite resources, clinoptilolite ores could be applicable to utilize the domestic zeolites for the removal of heavy metals.

• Journal of the Korean Chemical Society
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• v.37 no.3
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• pp.317-326
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• 1993

The acid catalytic reactions of toluene with n-propylalcohol were investigated and the adsorption experiments of dialkylbenzene isomers were carried out at 100$^{\circ}C$ over modified HZSM-5 zeolites. ZSM-5 zeolite was synthesized by the hydrothermal reaction using 4-propylammonium ion, sodium aluminate and colloidal silica etc., and several zeolite catalysts, including H-, K-, Sr-, P-Mg-HZSM-5, H-Y and H-mordenite, were prepared by conventional methods. The main reaction products of toluene with n-propylalcohol over HZSM-5 catalyst include not only xylenes, propyltoluenes, but also ethyltoluenes and high para-selectivity among dialkylbenzene isomers was observed on P-Mg-HZSM-5 zeolite. The diffusion coefficients of various p-dialkylbenzenes are nearly the same, about 1 ${times}$ 10$^{-10}$ cm$^2$/sec and that of m-xylene was about one tenth of o-xylene. These reaction and adsorption characteristics were interpreted in the light of the shape-selectivity related to related to the zeolite pore structure and the zeolitic acidity.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.135-142
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• 1989

Methyl tert-butyl ether(MTBE) was synthesized from vapor phase reaction of methanol with iso-butylene over HZSM-5 catalysts, and effects of SiO$_2/Al_2O_3$ ratio in the HZSM-5 catalysts and reaction conditions on products distribution have been examined. Acid strength and acid type of each catalyst with different SiO$_2/Al_2O_3$ ratio were measured using pyridine adsorption followed by temperature programmed desorption(TPD) and IR analysis. Reactants and products adsorption characteristics on different acid sites have also been examined. As the SiO$_2/Al_2O_3$ ratio of HZSM-5 catalyst was increased, selectivity to MTBE was improved as a result of decrease in dimethylether(DME) formation at the strong acid sites. Conversion and selectivity to MTBE were also greatly enhanced as $i-C_4H_8/CH_3OH$ reactant ratio was increased, and overall about 80$^{\circ}$C was adequate for the MTBE synthesis. The properties of deposited coke on spent catalysts were examined by TG, DTA and IR spectrum analysis, indicating the amount of the coke deposit in the order of HY > H-Mordenite > HZSM-5. Even if the coke deposited on H-Mordenite was little more in amount than to that on HZSM-5, the former deactivated quickly due to its non-interconnected channel structure. For HY, owing to its lange pore size, significant $i-C_4H_8$ polymerization was occured, and rapid deactivation and severe coke formation has resulted within few hours.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.8 no.2
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• pp.254-263
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• 1998

A worker employed in a serpentine mine was found developed mesothelioma as the first case of Korea in 1997. Asbestos was known as a causative agent for mesothelioma. Thus, asbestos contamination in mines could be a big health threat to those workers who were unknowingly exposed. However, there was no report that any minerals found in Korea contained asbestos. This study was carried out to find the presence of any asbestiform fibers in minerals which could be obtained in Korean mines. We examined fifteen minerals from 44 mines which were suspected contaminated with asbestiform fibers. Asbestiform analysis was done with high resolution transmission electron microscope(TEM), with energy dispersive X-ray spectroscope(EDX) and X-ray diffraction(XRD) analyses. Among asbestiform fibers, chrysotile was found in chrysotile, serpentine, talc and pyrophylite specimens from 11 mines. Tremolite was found in tremolite and talc specimens from three mines. Mordenite was found in zeolite specimens from two mines. Wallastonite and sepiolite were found in wallastonite and sepiolite specimens respectively. Crocidolite, antigorite and actinolite were found from talc specimens. But no asbestiform fiber contaminants were found in doromite, vermiculite, limestone, marble, gypsum, kaolin, and clary specimens. Thus, these asbestiform fibers such as such as chrysotile, tremolite, mordenite, crocidolite, antigorite and actinolite could be the responsible agents for the health hazards such as mesothelioma and other cancers.

• Economic and Environmental Geology
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• v.55 no.1
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• pp.63-76
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• 2022

Dacitic tuffs, 97 to 118 m thick, were recovered from the lower part of the subsurface Seongdongri Formation, Janggi Basin, which was drilled to assess the potential for underground storage of carbon dioxide. The tuffs are divided into four depositional units(Unit 1 to 4) based on internal structures and particle componentry. Unit 1 and Units 3/4 are ignimbrites that accumulated in subaerial and subaqueous settings, respectively, whereas Unit 2 is braided-stream deposits that accumulated during a volcanic quiescence, and no dacitic tuff is observed. A series of analysis shows that mordenite and clinoptilolite mainly fill the vesicles of glass shards, suggesting their formation by replacement and dissolution of volcanic glass and precipitation from interstitial water during burial and diagenesis. Glass-replaced clinoptilolite has higher Si/Al ratios and Na contents than the vesicle-filling clinoptilolite in Units 3. However, the composition of clinoptilolite becomes identical in Unit 4, irrespective of the occurrence and location. This suggests that the Si/Al ratio and pH in the interstitial water increased with time because of the replacement and leaching of volcanic glass, and that the composition of interstitial water was different between the eastern and western parts of the basin during the formation of the clinoptilolite in Units 1 and 3. It is also inferred that the formation of the two zeolite minerals was sequential according to the depositional units, i.e., the clinoptilolite formed after the growth of mordenite. To summarize, during a volcanic quiescence after the deposition of Unit 1, pH was higher in the western part of the basin because of eastward tilting of the basin floor, and the zeolite ceased to grow because of the closure of the pore space as a result of the growth of smectite. On the other hand, clinoptilolite could grow in the eastern part of the basin in an open system affected by groundwater, where braided stream was developed. Afterwards, Units 3 and 4 were submerged under water because of the basin subsidence, and the alkali content of the interstitial water increased gradually, eventually becoming identical in the eastern and western parts of the basin. This study thus shows that volcanic deposits of similar composition can have variable distribution of zeolite mineral depending on the drainage and depositional environment of basins.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.2
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• pp.117-124
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• 2023

X-ray diffraction analysis, X-ray fluorescence analysis, thermal differential and thermos gravimetric analysis, cation exchange capacity analysis, and Cesium (Cs), Strontium (Sr) adsorption experiments were performed to investigate the physical and chemical properties of natural zeolite from Guryongpo in Korea. As a result of X-ray diffraction analysis, minerals such as mordenite, heulandite, clinoptilolite, and illite are contained, and as a result of X-ray fluorescence analysis, elements such as SiO₂, Al₂O₃, CaO, K₂O, MgO, Fe₂O₃ and Na₂O are contained, and the cation exchange capacity was 148.6 meq/100 g. As a result of thermal differential and thermos gravimetric analysis, it was confirmed that the thermal stability was excellent up to 600 ℃. As a result of the adsorption equilibrium experiment over time, the equilibrium was reached within 30 min. for Cesium (Cs) and within 8 hr. for Strontium (Sr), and the adsorption rates of Cesium (Cs) and Strontium (Sr) were 80% and 18%, respectively. As a result of the single-component isothermal adsorption experiment, in conformed to the Langmuir model, and the maximum Cesium (Cs) adsorption amount was 131.5 mg/g, which was high, while the Strontium (Sr) maximum adsorption amount was 29.5 mg/g, which was low. In the case of the natural zeolite used in this study, the content of minerals including 8-rings such as clinoptilolite, heulandite, and mordenite is high, showing high selectivity for Cesium (Cs).

• Korean Journal of Mineralogy and Petrology
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• v.35 no.2
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• pp.141-151
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• 2022

The 16 natural zeolites collected from Mongolia (6 types), the United States (1 type), and Korea (9 types) were characterized by XRD, XRF, TGA, DTA, and CEC analysis. All 16 samples are composite minerals. Two or more mineral phases co-exist and consist primarily of minerals such as clinoptilolite, heulandite, mordenite, and chabazite. In certain samples, minerals like illite and quartz were present as impurities. The XRF analysis showed that the 16 natural zeolites contain SiO₂, Al₂O₃, K₂O, CaO, Na₂O, MgO, and Fe₂O₃ oxides. The cation exchange capacity of the U-1 sample was 223.3 meg/100 g, which is higher than the rest of the samples. M-6 sample in Mongolian natural zeolite and K-1 sample in Korean natural zeolite showed the highest cation exchange capacity at 166.6 meg/100 g. As a result of thermal differential and thermos gravimetric analysis, all 16 samples showed excellent thermal stability up to 600℃.

• The Journal of Engineering Geology
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• v.14 no.4 s.41
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• pp.381-390
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• 2004

This study was performed to relate the weathering properties of Oyaish tuff from Japan to mechanical properties of rocks in terms of mineralogical alteration and chemistry. The tuff is composed of clinoptilolite, quartz, feldspars, mordenite, opal C-T, and smectite. Since fresh tuff contains approximately $30\~50\%$ zeolite, it is expected that the rock is subjected to weathering process ascribed to water contents on earth surface, significantly reducing mechanical strength of tuff. It is also anticipated that weathering process and properties may be different even in the same rock mass, due to the differences in local mineralogy, chemistry and microtextures in tuff.