• Journal of the Mineralogical Society of Korea
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• v.16 no.2
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• pp.135-149
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• 2003

Domestic zeolite ores are mostly composed of Ca-type clinoptilolite, accompanying a little amounts of mordenite. However, other types of zeolite ores rich in ferrierite, heulandite, or mordenite are less commonly found. Based on the quantitative XRD analysis, zeolite contents are determined to be nearly 50∼90 wt%. Impurities (mostly ＞ 10 wt%) in the zeolite ores chiefly consist of quartz, feldspar, smectite, and opal-CT. The determined CEC values ($CEC_{AA}$ ) of powdery samples (grain size: < 125 $\mu\textrm{m}$) of zeolite ores by the Ammonium Acetate method are mostly higher than 100 meq/100 g. Some zeolites from the Guryongpo area, corresponding to the clinoptilolite ore, are measured to be dominantly high in CEC values ranging 170∼190 meq/100 g. Cation exchange property of the zeolite ores varies greatly depending on the types or zeolite species present in the ores. Despite of the lower grade in zeolite content, the $CEC_{AA}$ of ferrierite ore is comparatively high. Compared to this, the $CEC_{AA }$ of heulandite ore is very low, though the zeolite ore exhibits the highest grade ranging up to about 90 wt%. In addition, the CEC values calculated theoretically from the framework composition of clinoptilolite-heulandite series are not consistent with those determined by the cation exchage experiment. The measured $CEC_{AA}$ of clinoptilolite ores are generally higher than those of heulandite ores. This may be due to the higher Ca abundance in exchangeable cation composition and the presence of probable stacking faults in heulandite. The variation of $CEC_{CEC}$ is roughly proportional, though not strictly compatible, to the zeolite contents in clinoptilolite ores. It seems to be caused by the fact that the $CEC_{AA}$ of clinoptilolite locally varies depending on crystal-chemical diversity, i. e., the variation in framework composition (Si/Al) and exchangeable cation composition (especially, the contents of Ca and K). In addition, the determined CEC values ($CEC_{MB}$ ) of zeolite ores by the Methylene Blue method are much higher than those calculated from smectite contents. It suggests a probable reaction of Methylene Blue ion ($C_{16}$ $H_{18}$ $N_3$S+) with larger-pore zeolites than clinoptlolite-heulandite series, i.e., ferrierite and mordenite as well as with smectite. This can be supported by the fact that the ferrierite ore accompanying little amount of smectite has the highest value in CE $C_{MB}$ .

• 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.

• 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.

• Journal of the Mineralogical Society of Korea
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• v.19 no.3 s.49
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• pp.197-207
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• 2006

In the coal-bearing formations of the Janggi Group, which are reported as typical clastic sediments, several beds of volcaniclastic rocks are actually found in the Yeongil area. The coal-bearing formations generally exhibit alternating lithologic characteristics of pyroclastic and epiclastic sedimentary facies. Tuff and tuffaceous sandstone rich in pumice fragments are characteristic in the coal-bearing fermations. Diagenetic minerals found in the pyroclastic rocks of the upper and lower coal-bearing formations are montmorillonite, clinoptilolite, opal-CT, and quartz. Several tuffaceous beds correspond to the low-grade ores of zeolites and bentonite, and moreover, these ores mostly occur as thin beds less than 1 m in thickness. Thus, the potential of altered tuffaceous rocks as the resources typical of zeolite and bentonite seems to be low. However, based on mineral composition and CEC determinations, it can be evaluated that these tuffaceous rocks mostly have the promising potential for utilization as the absorbent-functional mineral resources such as acid clays, if these low-grade ores plus adjacent tuffaceous rocks are collectively exploited.

• Journal of the Mineralogical Society of Korea
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• v.17 no.2
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• pp.135-145
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• 2004

A zeolitic bentonite, which exhibits whitish appearance and contains considerable amounts (nearly 〉 5%) of zeolites, frequently occurs as thin beds less than 1 m in Yeongil area. The bentonites are mostly found in closely association with zeolite beds in the Nuldaeri Tuff and Coal-bearing formations of the Janggi Croup. A discordant occurrence of the bentonite against the bedding plane is also locally found. Montmorillonite, the major mineral constituent of the bentonite, is mostly associated with clinoptilolite as a zeolite. However, instead of clinoptilolite, mordenite is sometimes included in the case of more silicic bentonite, and heulandite in the less silicic one. It is characteristic that the mordenite is accompanied by lots of opal-CT in the silicic bentonite. SEM observations characteristically indicate that these authigenic phases, especially the montmorillonite and zeolite, nearly coexist as mixtures not forming a fine-scale zoning. The zeolitic bentonite seems to be formed in the comparatively silicic pore fluid at the alkaline condition accompanying pH fluctuation Compared to the zeolite-free normal bentonite, the zeolitic types exhibit somewhat higher REE abundance. These chemical characteristics, together with modes of occurrences and authigenic mineral associations, may suggest that the zeolitic bentonite is not merely diagenetic products and a possible hydrothermal alteration could not be excluded in the bentonite genesis.

• Journal of the Mineralogical Society of Korea
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• v.8 no.2
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• pp.118-125
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• 1995

경북 구룡포에 소재한 구룡광산에서 산출하는 불석(클리놉틸로라이트와 모데나이트의 집합체)에 대한 Pb2+, Cd2+, Zn2+, Co2+, Fe2+ 및 NH4+ 등 양이온의 치환성질을 알아보기 위하여 베치실험을 실시하였다. 60∼80 메쉬 및 230 메쉬의 시료를 사용하여 각각 50ppm의 농도를 가진 용액과 반응시켰다. 반응후의 용액은 AA 및 전극 (NH4+)으로 분석하여 치환양을 측정하였다. 본 연구결과 Pb2+와 NH4+가 다른 이온들보다 훨씬 높은 선택성을 보여 주었다. 불석에 대한 이온들의 선택성은 NH4+, Pb2+》Zn2+, Cu2-, Co2->Cd2-, Fe2+와 같다. 실험결과 불석시료가 용액으로부터 흡착한 양이 시료로부터 용액으로 추출된 양보다 훨씬 높게 나타나고 있는 바 이는 이온치환보다는 불석의 시브(sieve) 효과에 의한 이온흡착현상이 우세하게 일어났다는 것을 지시해준다. 본 실험은 이 불석이 중금속과 암모니아와 같은 오염물을 제거하는데 사용될 수 있음을 보여준다.

• Journal of the Mineralogical Society of Korea
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• v.9 no.2
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• pp.82-92
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• 1996

The coarse-grained (0.05∼0.2mm) zeolites occur as the single-crystal cement in the sandstones of the Chunbuk Formation in the Pohang area. The zeolite cements unusually consist of the composite phases of heulandite and clinoptilolite and in a crystal. The zeolite crystals show chemical zoning ranging from 3.56 to 4.10 in Si/(Al+Fe), and tend to become continuously more silicic and alkalic from the margin toward inside of the crystal. The DTA and high-temperature XRD analyses also show complex patterns of both zeolites. Such a composite crystal showing chemical zoning and complex thermo-chemical behaviors indicates that heulandite and clinoptilolite are constituting a solid solution resulted from the coupled substitution of K+Si4+=Ca2+Al3+.

• Journal of the Mineralogical Society of Korea
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• v.15 no.4
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• pp.329-344
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• 2002

Mineralogical and chemical characterization of some domestic bentonites, such as quantitative XRD analysis, chemical leaching experiments, pH and CEC determinations, were done without any separation procedures to understand their relationships among mineral composition, characteristics, and cation exchange properties. XRD quantification results based on Rietveld method reveal that the bentonites contain totally more than 25 wt% of impurities, such as zeolites, opal-CT, and feldspars, in addition to montmorillonite ranging 30～75 wt%. Cation exchange properties of the zeolitic bentonites are deeply affected by the content of zeolites identified as clinoptilolite-heulandite series. Clinoptilolite is common in the silicic bentonites with lighter color. and occurs closely in association with opal-CT. Ca is mostly the dominant exchangeable cation, but some zeolitic bentonites have K as a major exchangeable cation, The values of cation exchange capacity (CEC) determined by Methylene Blue method are comparatively low and have roughly a linear relationship with the montmorillonite content of the bentonite, though the correlated data tend to be rather dispersed. Compared to this, the CEC determined by Ammonium Acetate method, i.e.‘Total CEC’, has much higher values (50～115 meq/100 g). The differences between those CEC values are much greater in zeolitic bentonites, which obviously indicates the CEC increase affected by zeolite. Other impurities such as opal-CT and feldspars seem to affect insignificantly on the CEC of bentonites. When dispersed in distilled water, the pH of bentonites roughly tends to increase up to 9.3 with increasing the alkali abundance, especially Na, in exchangeable cation composition. However, some bentonites exhibit lower pH (5～6) so as to regard as ‘acid clay’. This may be due to the presence of $H^{＋}$ in part as an exchangeable cation in the layer site of montmorillonite. All the works of this study ultimately suggest that an assesment of domestic bentonites in grade and quality should be accomplished through the quantitative XRD analysis and the ‘Total CEC’measurement.