유봉철 Bong Chul Yoo

DOI: Vol.35(No.2) 83-100, 2022

The Zhenzigou Pb-Zn deposit, which is one of the largest Pb-Zn deposit in the northeast of China, is located at the Qingchengzi mineral field in Jiao Liao Ji belt. The geology of this deposit consists of Archean granulite, Paleoproterozoinc migmatitic granite, Paleo-Mesoproterozoic sodic granite, Paleoproterozoic Liaohe group, Mesozoic diorite and Mesozoic monzoritic granite. The Zhenzigou deposit which is a strata bound SEDEX or SEDEX type deposit occurs as layer ore and vein ore in Langzishan formation and Dashiqiao formation of the Paleoproterozoic Liaohe group. White mica from this deposit are occured only in layer ore and are classified four type (Type I : weak alteration (clastic dolomitic marble), Type II : strong alteration (dolomitic clastic rock), Type III : layer ore (dolomitic clastic rock), Type IV : layer ore (clastic dolomitic marble)). Type I white mica in weak alteration zone is associated with dolomite that is formed by dolomitization of hydrothermal metasomatism. Type II white mica in strong alteration zone is associated with dolomite, ankerite, quartz and alteration of K-feldspar by hydrothermal metasomatism. Type III white mica in layer ore is associated with dolomite, ankerite, calcite, quartz and alteration of K-feldspar by hydrothermal metasomatism. And type IV white mica in layer ore is associated with dolomite, quartz and alteration of K-feldspar by hydrothermal metasomatism. The structural formulars of white micas are determined to be (K_0.92-0.80Na_0.01-0.00Ca_0.02-0.01Ba_0.00Sr_0.01-0.00)_0.95-0.83(Al_1.72-1.57Mg_0.33-0.20Fe_0.01-0.00Mn_0.00Ti_0.02-0.00Cr_0.01-0.00V_0.00Sb_0.02-0.00 Ni_0.00Co_0.02-0.00)_1.99-1.90(Si_3.40-3.29Al_0.71-0.60)_4.00O₁₀(OH_2.00-1.83 F_0.17-0.00)_2.00, (K_1.03-0.84Na_0.03-0.00Ca_0.08-0.00Ba_0.00Sr_0.01-0.00)_1.08-0.85 (Al_1.85-1.65Mg_0.20-0.06Fe_0.10-0.03Mn_0.00Ti_0.05-0.00Cr_0.03-0.00V_0.01-0.00Sb_0.02-0.00Ni_0.00Co_0.03-0.00)_1.99-1.93(Si_3.28-2.99Al_1.01-0.72)_4.00 O₁₀(OH_1.96-1.90F_0.10-0.04)_2.00, (K_1.06-0.90Na_0.01-0.00Ca_0.01-0.00Ba_0.00Sr_0.02-0.01)_1.10-0.93(Al_1.93-1.64Mg_0.19-0.00Fe_0.12-0.01Mn_0.00Ti_0.01-0.00 Cr_0.01-0.00V_0.00Sb_0.00Ni_0.00Co_0.05-0.01)_2.01-1.94(Si_3.32-2.96Al_1.04-0.68)_4.00O₁₀(OH_2.00-1.91F_0.09-0.00)_2.00 and (K_0.91-0.83Na_0.02-0.01Ca_0.02-0.00 Ba_0.01-0.00Sr_0.00)_0.93-0.83(Al_1.84-1.67Mg_0.15-0.08Fe_0.07-0.02Mn_0.00Ti_0.04-0.00Cr_0.06-0.00V_0.02-0.00Sb_0.02-0.01Ni_0.00Co_0.00)_2.00-1.92(Si_3.27-3.16 Al_0.84-0.73)_4.00O₁₀(OH_1.97-1.88F_0.12-0.03)_2.00, respectively. It indicated that white mica of from the Zhenzigou deposit has less K, Na and Ca, and more Si than theoretical dioctahedral mica. Compositional variations in white mica from the Zhenzigou deposit are caused by phengitic or Tschermark substitution [(Al³⁺)^VI+ (Al³⁺)^{IV <->} (Fe²⁺ or Mg²⁺)^VI+(Si⁴⁺)^IV] substitution. It means that the Fe in white mica exists as Fe²⁺ and Fe³⁺, but mainly as Fe²⁺. Therefore, white mica from layer ore of the Zhenzigou deposit was formed in the process of remelting and re-precipitation of pre-existed minerals by hydrothermal metasomatism origined metamorphism (greenschist facies) associated with Paleoproterozoic intrusion. And compositional variations in white mica from the Zhenzigou deposit are caused by phengitic or Tschermark substitution [(Al³⁺)^VI+ (Al³⁺)^{IV <->} (Fe²⁺ or Mg²⁺)^VI+(Si⁴⁺)^IV] substitution during hydrothermal metasomatism depending on wallrock type, alteration degree and ore/gangue mineral occurrence frequency.

Zhenzigou 연-아연 광상, 백색운모, 산상, 화학조성, Zhenzigou Pb-Zn deposit, White mica, Occurrence, Chemical composition

조수빈 Subin Cho , 권기덕 Kideok D. Kwon , 현성필 Sung Pil Hyun

DOI: Vol.35(No.2) 101-109, 2022

The mobility and transport of radioactive cesium are crucial factors to consider for the safety assessment of high-level radioactive waste disposal sites in granite. The retardation of radionuclides in the fractured crystalline rock is mainly controlled by the hydrochemical condition of groundwater and surface reactions with minerals present in the fractures. This paper reports the experimental results of cesium sorption to the Wonju Granite, a typical Mesozoic granite in Korea, performed in an anaerobic chamber that mimics the anoxic environment of a deep disposal site. We measured the rates and amounts of cesium (¹³³Cs) removed by crushed granite samples in different electrolyte (NaCl, KCl, and CaCl₂) solutions and a synthetic groundwater solution, with variations in the initial cesium concentration (10^-5, 5×10^-6, 10^-6, 5×10^-7 M). The cesium sorption kinetic and isotherm data were successfully simulated by the pseudo-second-order kinetic model (r²= 0.99) and the Freundlich isotherm model (r²= 0.99), respectively. The sorption distribution coefficient of granite increased almost linearly with increasing biotite content in granite samples, indicating that biotite is an effective cesium scavenger. The cesium removal was minimal in KCl solution compared to that in NaCl or CaCl₂ solution, regardless of the ionic strength and initial cesium concentration that we examined, showing that K⁺ is the most competitive ion against cesium in sorption to granite. Because it is the main source mineral of K⁺ in fracture fluids, biotite may also hinder the sorption of cesium, which warrants further research.

세슘, 화강암, 수착, 흑운모, 포타슘, Cesium, Granite, Sorption, Biotite, Potassium

이선용 Seon Yong Lee , 최수연 Su-yeon Choi , 장봉수 Bongsu Chang , 이영재 Young Jae Lee

DOI: Vol.35(No.2) 111-123, 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 A and c = 22.52 A for CGR and a (=b) = 5.50 A and c = 10.97 A 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.

이중층수산화물, 탄산염 그린 러스트, 황산염 그린 러스트, 공침법, 형성 메커니즘, 이화학적 특성, Layered double hydroxide, Carbonate green rust, Sulfate green rust, Co-precipitation, Formation mechanisms, Physicochemical properties

유봉철 Bong Chul Yoo

DOI: Vol.35(No.2) 125-140, 2022

The Xiquegou Pb-Zn deposit is located at the Qingchengzi orefield which is one of the largest Pb-Zn mineralized zone in the northeast of China. The geology of this deposit consists of Archean granulite, Paleoproterozoinc migmatitic granite, Paleo-Mesoproterozoic sodic granite, Paleoproterozoic Liaohe group, Mesozoic diorite and Mesozoic monzoritic granite. The Xiquegou deposit which is a Triassic magma-hydrothermal type deposit occurs as vein ore filled fractures along fault zone in unit 3 (dolomitic marble and schist) of Dashiqiao formation of the Paleoproterozoic Liaohe group. Xiquegou Pb-Zn deposit consists of quartz, apatite, calcite, pyrite, arsenopyrite, pyrrhotite, marcasite, sphalerite, chalcopyrite, stannite, galena, tetrahedrite, electrum, argentite, native silver and pyrargyrite. Wallrock alteration of this deposit contains silicification, pyritization, dolomitization, chloritization and sericitization. Based on mineral petrography and paragenesis, dolomites from this deposit are classified two type (1. dolomite (D₀) as wallrock, 2. dolomite (D₁) as wallrock alteration in Pb-Zn mineralization quartz vein ore). The structural formulars of dolomites are determined to be Ca_1.03-1.01Mg_0.95-0.83Fe_0.12-0.02Mn_0.02-0.00(CO₃)₂(D₀) and Ca_1.16-1.00Mg_0.79-0.44Fe_0.53-0.13Mn_0.03-0.00As_0.01-0.00 (CO₃)₂(D₁), respectively. It means that dolomites from the Xiquegou deposit have higher content of trace elements compared to the theoretical composition of dolomite. The dolomite (D₁) from quartz vein ore has higher content of these trace elements (FeO, PbO, Sb₂O₅ and As₂O₅) than dolomite (D₀) from wallrock. Dolomites correspond to Ferroan dolomite (D₀), and ankerite and Ferroan dolomite (D₁), respectively. The structural formular of chlorite from quartz vein ore is (Mg_1.65-1.08Fe_2.94-2.50Mn_0.01-0.00Zn_0.01-0.00Ni_0.01-0.00Cr_0.02-0.00 V_0.01-0.00Hf_0.01-0.00Pb_0.01-0.00Cu_0.01-0.00As_0.03-0.00Ca_0.02-0.01Al_1.68-1.61)_5.77-5.73(Si_2.84-2.76Al_1.24-1.16)_4.00O₁₀(OH)₈. It indicated that chlorite of quartz vein ore is similar with theoretical chlorite and corresponds to Fe-rich chlorite. Compositional variations in chlorite from quartz vein ore are caused by mainly octahedral Fe²⁺ <-> Mg²⁺ (Mn²⁺) substitution and partly phengitic or Tschermark substitution (Al^3+,VI+Al^3+,IV <-> (Fe²⁺ 또는 Mg²⁺)^VI+(Si⁴⁺)^IV).

Xiquegou 연-아연 광상, 돌로마이트, 녹니석, 산상, 화학조성, Xiquegou Pb-Zn deposit, Dolomite, Chlorite, Occurrence, Chemical composition

바야르사이칸바트체첵 Bayarsaikhan Battsetseg , 김후식 Hu Sik Kim , 김영훈 Young Hun Kim , 김정진 Jeong Jin Kim , 임우택 Woo Taik Lim

DOI: Vol.35(No.2) 141-151, 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℃.

천연 제올라이트, 양이온 교환, 특성분석, Natural zeolite, cation exchange, characterization

김형규 Hyeong-gyu Kim , 이상우 Sang-woo Lee , 김순오 Soon-oh Kim , 정도환 Do-hwan Jeong , 김문수 Moon-su Kim , 김현구 Hyun-koo Kim , 정종옥 Jong Ok Jeong

DOI: Vol.35(No.2) 153-168, 2022

Petrological and mineralogical analyses were conducted to identify minerals containing radioactive elements (uranium) in the Chiaksan gneiss complex and to confirm their association with the surrounding groundwater. Fourteen minerals were identified through the microscopic and electron microscopy (SEMEDS) investigation. The principal minerals included plagioclase, biotite, quartz, alkali feldspar, chlorite, and calcite. Minor minerals were sphene, allanite, apatite, zircon, thorite, titanite, pyrite, and galena. A small amount of thorite was observed in the size of ~1 mm within macrocrystalline allanite. Allanite, which includes a large amount of rare earth elements, appeared in three distinctive patterns. The results of the EPMA analyses indicated that macrocrystalline allanite had higher elemental contents of TiO₂ ~1.70 wt.%, Ce₂O₃ ~11.86 wt.%, FeO ~13.31 wt.%, MgO ~0.90 wt.% and ThO₂ ~1.06 wt.% with the lowest average content of Al₂O₃ 17.35 ± 2.15 wt.% (n = 7), CaO 12.13 ± 1.81 wt.% (n = 7). An allanite existing at the edge of the sphenes encompassing titanites had a higher element content of Al₂O₃ ~24.00 wt.%, Nd₂O₃ ~5.10 wt.%, Sm₂O₃ ~0.66 wt.%, Dy₂O₃ ~0.86 wt.% and Y₂O₃ ~1.38 wt.% with the lowest average content of TiO₂ 0.35 ± 0.21 wt.% (n = 11), Ce₂O₃ 5.25 ± 1.03 wt.% (n = 11), FeO 9.84 ± 0.26 wt.% (n = 11), MgO 0.12 ± 0.05 wt.% (n = 11), and La₂O₃ 1.49 ± 0.29 wt.% (n = 11). Allanites in a matrix of parental rocks exhibited intermediate values between the two elemental compositions mentioned above. None of the uranium-rich minerals were observed in the migmatitic gneiss within the study area. Consequently, the origin of uranium in the groundwater was not associated with the geology of the surrounding environment, but our investigation proved the existence of abundant allanites containing significant amounts of radioactive thorium and rare earth elements.

지하수, 방사성 원소, 치악산 편마암 복합체, 갈렴석, 토륨, Groundwater, Radioactive elements, Chiaksan gneiss complex, Allanite, Thorium