김주혁 Juhyeok Kim , 권기덕 Kideok D. Kwon

DOI: Vol.36(No.4) 221-232, 2023

Carbon neutrality requires carbon dioxide reduction technology and alternative green energy sources. Palygorskite is a clay mineral with a ribbon structure and possess a large surface area due to the nanoscale pore size. The clay mineral has been proposed as a potential material to capture carbon dioxide (CO₂) and possibly to store eco-friendly hydrogen gas (H₂). We report our preliminary results of grand canonical Monte Carlo (GCMC) simulations that investigated the adsorption isotherms and mechanisms of CO₂ and H₂ into palygorskite nanopores at room temperature. As the chemical potential of gas increased, the adsorbed amount of CO₂ or H₂ within the palygorskite nanopores increased. Compared to CO₂, injection of H₂ into palygorskite required higher energy. The mean squared displacement within palygorskite nanopores was much higher for H₂ than for CO₂, which is consistent with experiments. Our simulations found that CO₂ molecules were arranged in a row in the nanopores, while H₂ molecules showed highly disordered arrangement. This simulation method is promising for finding Earth materials suitable for CO₂ capture and H₂ storage and also expected to contribute to fundamental understanding of fluid-mineral interactions in the geological underground.

이산화탄소, 수소, 팔리고스카이트, 몬테 카를로 시뮬레이션, 흡착 등온선, Carbon dioxide, Hydrogen, Palygorskite, Monte carlo simulations, Adsorption isotherm

송석환 Seokhwan Song

DOI: Vol.36(No.4) 233-257, 2023

Asbestos minerals are found at rocks and soils of the Hongseong and Bibong serpentine mines, western part of Chungnam. The area consists of and metasediment, and Mesozoic igneous intrusives with minor age-known gneiss complexes and Mesozoic sediments. With detailed geological investigations, rock samples for the serpentinite and amphibolite areas are collected at sites containing asbestos. Representative asbestos and rock samples are analysed by PLM, XRD, SEM and EPMA. Serpentinites are found as steeply dipping faults with adjacent gneiss complex to the NNE direction. Repeated alteration, including serpenitization and talcification, is found at the emplacement direction for the serpentinite body. Amphibollites occur as intrusives and stratiforms within the Precambrian gneiss complex. Serpentinite and amphibolite (or amphibole schist) contain amphiboles either as asbestiform or non-asbestiform. Varying amounts of asbestos minerals, including chrysotile, tremolite asbestos and actinolite asbestos, are found within the serpentinites. The asbestos minerals are found near the cracks or fractures and along the bedding plane. They occur as cross fiber, slip fiber and mass fiber types. Varying amounts of amphibole asbestos minerals, such as tremolite and actinolite asbestos, are found within amphibolites and as a mass fiber type. Overall results suggest that rocks of the serpentine mines contain serpentine and amphibole type asbestos minerals originated from the hydrothermal alteration. Considering construction nearby the mines and environmental risks by the asbestos, additional land management plans are required.

사문석 광산, 각섬암, 백석면, 각섬석계 석면, 토지관리방안, Serpentine mine, Amphibolite, Chrysotile, Amphibole asbestos, Land management plans

김창성 Chang Seong Kim , 정래윤 Raeyoon Jeong , 김순오 Soon-oh Kim , 차지만 Ji-man Cha

DOI: Vol.36(No.4) 259-271, 2023

Since the short-wave infrared spectrum has a significant range of variation depending on the production environment, countries with advanced resource exploration are collecting the spectrum and building a database. Representative organizations include the USGS and CSIRO, and they are currently carrying out a project in China that can synthesize and use a large number of existing data. The USGS library provides a total of 2,457 spectra targeting not only minerals but also various materials that respond to infrared radiation. Among these, there are 1,276 mineral spectra, which are about half of the total. The spectrum title includes information, such as analysis devices (NIC4, BECK, ASDNG, etc.), purity codes (a, b, c, d, u), and measurement methods (AREF, RREF, RTGC, TRAN). Analyzed raw data are provided in ASCII and GIF format. The CSIRO library has a total of 502 spectra, of which the majority, 493, correspond to mineral spectra. The USGS library is a free, publically available resource, while the CSIRO library is bundled with TSG8 or must be purchased separately. Among these, when comparing the eight spectra whose spectral shapes can be analyzed with the spectra of domestic illite, the positions of the absorption peaks are significantly different from those of domestic illite, except for one Japanese illite. Additional research will be needed to determine the causes of such differences, and the domestically relevant databases should be established as well.

단파장 적외선, 미국 지질조사국, 호주 연방과학산업연구기구, 일라이트, 스펙트럼 라이브러리, Short-wave infrared, USGS, CISRO, Illite, Spectrum library

유봉철 Bong Chul Yoo

DOI: Vol.36(No.4) 273-288, 2023

The Gubong Au-Ag deposit, which has been one of the largest deposits (Unsan, Daeyudong, Kwangyang) in Korea, consists of eight lens-shaped quartz veins (a mix of orogenic-type and intrusionrelated types) that filled fractures along fault zones within Precambrian metasedimentary rock. Korea Mining Promotion Corporation found a quartz vein (referred to as the No. 6 vein with a grade of 27.9 g/t Au and a width of 0.9 m) at a depth of -728 ML by drilling (No. 90-12) conducted in 1989. Korea Mining Promotion Corporation conducted drilling (No. 04-1) in 2004 to investigate the redevelopment’s possibility of the No. 6 vein. The author studied the occurrence and chemical composition of chlorite and white mica using wallrock, wallrock alteration and quartz vein samples collected from the No. 04-1 drilling core in 2004. The alteration of studied samples occurs chloritization, sericitization, silicification and pyritization. Chlorite and white mica from mineralized zone at a depth of -275 ML occur with quartz, K-feldspar, calcite, rutile and pyrite in wallrock alteration zone and quartz vein. Chlorite and white mica from ore vein (No. 6 vein) at a depth of -779 ML occur with quartz, calcite, apatite, zircon, rutile, ilmenite, pyrrhotite and pyrite in wallrock alteration zone and quartz vein. Chlorite from a depth of -779 ML has a higher content of Al and Mg elements and a lower content of Si and Fe elements than chlorite from a depth of -275 ML. Also, Chlorites from a depth of - 275 ML and -779 ML have higher content of Si element than theoretical chlorite. Compositional variation in chlorite from a depth of -275 ML was mainly caused by phengitic or Tschermark substitution [Al_3+,VI + Al_3+,VI <-> (Fe₂₊ or Mg₂₊)_VI + (Si₄₊)_IV], but compositional variation from a depth of -779 ML was mainly caused by octahedral Fe₂₊ <-> Mg₂₊ (Mn2+) substitution. The interlayer cation site occupancy (K+Na+Ca+Ba+Sr = 0.76~0.82 apfu, 0.72~0.91 apfu) of white mica from a depth of -275 ML and -779 ML have lower contents than theoretical dioctahedral micas, but octahedral site occupancy (Fe+Mg+Mn+Ti+Cr+V+Ni = 2.09~2.13 apfu, 2.06~2.14 apfu) have higher contents than theoretical dioctahedral micas. Compositional variation in white mica from a depth of -275 ML was caused by phengitic or Tschermark substitution [(Al₃₊)_VI + (Al₃₊)_IV <-> (Fe₂₊ or Mg₂₊)_VI + (Si₄₊)_IV], illitic substitution and direct (Fe₃₊)_VI <-> (Al₃₊)_VI substitution. But, compositional variation in white mica from a depth of -779 ML was caused by phengitic or Tschermark substitution [(Al₃₊)_VI + (Al₃₊)_IV <-> (Fe₂₊ or Mg₂₊)_VI + (Si₄₊)_IV] and direct (Fe₃₊)_VI <-> (Al₃₊)_VI substitution.

구봉 금-은 광상, 녹니석, 백색운모, 산상, 화학조성, Gubong Au-Ag deposit, Chlorite, White mica, Occurrence, Chemical composition

이우춘 Woo-chun Lee , 이상우 Sang-woo Lee , 김형규 Hyeong-gyu Kim , 정도환 Do-hwan Jeong , 김문수 Moon-su Kim , 김현구 Hyun-koo Kim , 김순오 Soon-oh Kim

DOI: Vol.36(No.4) 289-302, 2023

The study area was Gangnim-myeon, Hoengseong-gun, Gangwon-do, composed of the Chiaksan gneiss complex, and it was revealed that the concentrations of uranium (U) and thorium (Th) within the groundwater of the study area exceeded their water quality standards. Hence, artificial weathering experiments were conducted to elucidate mineralogically the mechanisms of their leaching using drilling cores obtained from the corresponding groundwater aquifers. First of all, the mineralogical compositions of core samples were observed, and the results indicated that the content of clinochlore, a member of the chlorite group of minerals that can form through low- and intermediate-temperature metamorphisms, was relatively higher. In addition, the Th concentration was measured ten times higher than that of U. The results of artificial weathering experiments suggested that the Th concentrations gradually increased through the dissolution of radioactive-element-bearing minerals up to the first day, and then they tended to decrease. It could be attributed to the fact that Th was leached with the dissolution of thorite, which might be a secondary mineral, and then dissolved Th was re-precipitated as the various forms of salt, such as sulfate. Even though the U content was lower than that of Th in the core samples, the U concentration was one hundred times higher than that of Th after the weathering experiments. It is likely caused by the gradual dissolution and desorption of U included in intensively weathered thorite or adsorbed as a form of UO₂ ²⁺ on the mineral surface. In addition, the leaching tendency of U and Th was positively correlated with the bicarbonate concentration. However, the concentrations between U and Th in groundwater exhibited a relatively lower correlation, which might result from the fact that they occurred from different sources, as aforementioned. Among various kinetic models, the parabolic diffusion and pseudosecond- order kinetic models were confirmed to best fit the dissolution kinetics of both elements. The period that would be taken for the U concentration to exceed its drinking-water standard was inferred using the regressed parameters of the best-fitted models, and the duration of 29.4 years was predicted in the neutral-pH aquifers with relatively higher concentrations of HCO₃, indicating that U could be relatively quickly leached out into groundwater.

토륨, 우라늄, 지하수, 함방사성원소 광물, 인공풍화 실험, 풍화 속도, Thorium, Uranium, Groundwater, Radioactive-element-bearing minerals, Artificial weathering experiments, Weathering rate

김효임 Hyo-im Kim , 이상미 Sangmi Lee , 구효진 Yoon Ji , 지윤 Hyo-jin Koo , 조현구 Hyen-goo Cho

DOI: Vol.36(No.4) 303-312, 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn₄₊ content, approximately 67.9%, while the outermost part showed about 63% of Mn₄₊ due to an increase in the Mn₃₊+Mn₂₊. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleoenvironmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.

X선 광전자 분광분석, 망가니즈 단괴, 망가니즈 산화수, 토도로카이트, 버네사이트, X-ray photoelectron spectroscopy, manganese nodule, Mn oxidation state, todorokite, birnessite

김영규 Yeongkyoo Kim

DOI: Vol.36(No.4) 313-321, 2023

Numerous studies have investigated the adsorptive sequestration of radioactive cesium in the natural environment. Among these studies, adsorption onto minerals and high-temperature treatment stand out as highly effective, as demonstrated by the use of zeolite. In this study, cesium was ion-exchanged with birnessite and subsequently underwent high-temperature treatment up to 1100℃ to investigate both mineral phase transformation and the leaching characteristics of cesium. Birnessite has a layered structure consisting of MnO₆ octahedrons that share edges, demonstrating excellent cation adsorption capacity. The high-temperature treatment of cesium-ion-exchanged birnessite resulted in changes in the mineral phase, progressing from cryptomelane, bixbyite, birnessite to hausmannite as the temperature increased. This differs from the phase transformation observed in the tunneled manganese oxide mineral todorokite ion-exchanged with cesium, which shows phase transformation only to birnessite and hausmannite. The leaching of cesium from cesiumion- exchanged birnessite was estimated by varying the reaction time using both distilled water and a 1M NaCl solution. The leaching quantity changed according to the treatment temperature, reaction time, and type of reaction solution. Specifically, the cesium leaching was higher in the sample reacted with 1 M NaCl compared to the sample with distilled water and also increased with longer reaction time. For the samples reacted with distilled water, the cesium leaching initially increased and then decreased, while in the NaCl solution, the leaching decreased, increased again, and finally nearly stopped like the sample in the distilled water for the sample treated at 1100℃. These changes in leaching are closely associated with the mineral phases formed at different temperatures. The phase transformation to cryptomelane and birnessite enhanced cesium leaching, whereas bixbyite and hausmannite hindered leaching. Notably, hausmannite, the most stable phase occurring at the highest temperature, demonstrated the greatest ability to inhibit cesium leaching. This results strongly suggest that high-temperature treatment of cesium-ion-exchanged birnessite effectively immobilizes and sequesters cesium.

버네사이트, 고온처리, 상변화, Cs 용출, 이온교환, Birnessite, High temperature, Phase transformation, Cs leaching, Ion exchange

김이정 Ijeung Kim , 고상모 Sang-mo Koh , 오트곤-에르덴다바슈렌 Otgon-erdene Davaasuren , 안기문 Gi Moon Ahn , 허철호 Chul-ho Heo , 이범한 Bum Han Lee

DOI: Vol.36(No.4) 323-336, 2023

We investigated the nickel potential and genesis of ultramafic rocks in the Yugu area to secure nickel resources in South Korea. The Yugu ultramafic rocks, located in the southwest of the Gyeonggi Massif, are characterized by spinel peridotite and exhibit strong serpentinization along their boundaries. The serpentinization is observed as olivine transformed to antigorite and chrysotile, while pentlandite, the nickel sulfide mineral, altered into millerite and awaruite. Serpentine displays distinct foliation, aligning subparallel to the ultramafic rock boundaries and foliation of Yugu gneiss. This suggests that the uplift of ultramafic rocks resulted in hydrothermal infiltration likely sourced from the Yugu gneiss metamorphism. The Yugu ultramafic rocks are residues after 5~18% partial melting of abyssal peridotite. Enriched light rare earth elements and Eu imply secondary metasomatism. Geochemistry suggests a link between the formation of Yugu ultramafic rock and the Triassic collision of the North and South China continents. The nickel content is around 0.17~0.21%, mainly contained in olivine and serpentine. Hence, in addition to the mineral processing study on the sulfide minerals, focused studies on oxide minerals for enhanced nickel recovery within the Yugu ultramafic rock are strongly suggested.

유구, 초염기성암, 니켈, 감람석, 사문석, 사문석화작용, Yugu, Ultramafic rocks, Nickel, Olivine, Serpentine, Serpentinization

정기영 Gi Young Jeong

DOI: Vol.36(No.4) 337-343, 2023

Olivine is a complete solid solution of fayalite and forsterite that is abundant in Earth and extraterrestrial materials such as rocky planets, meteorites, asteroids, and interplanetary dust. Due to the wide range of olivine compositions, diverse olivine standards are required for quantitative mineralogical analysis of olivine-bearing materials. Olivine standards were synthesized using an electric furnace and stainless steel tubes at temperatures ranging from 1000~1100℃. Overall, olivine was synthesized covering the full range of composition, with some synthetic impurities and unreacted material. The synthesized olivine showed a linear increase in the unit cell dimension in proportion to the molar ratio of fayalite in the starting materials, and the diffraction intensity was consistent with that of natural olivine. However, iron-rich synthetic olivine samples tend to have a higher content of impurity, suggesting that not all synthetic olivine can be used as a standard material yet, and improvements in the synthesis process, such as using high purity starting materials and control of reaction time and temperature, are required.

감람석, 엑스선회절, 합성, 전기로, 스테인리스강관, Olivine, X-ray diffraction, Synthesis, Electric furnace, Stainless steel tube

백은지 Eunji Baek , 이유나 Yu Na Lee , 김은정 Eun Jeong Kim , 김영석 Youngseuk Keehm , 김현나 Hyun Na Kim

DOI: Vol.36(No.4) 345-353, 2023

This study aimed to investigate the differences in the commercial powder products of the Yeongdong illite based on sales specifications, specifically examining the mineralogical composition, particle size, and chemical composition according to mesh size. The goal was to understand the characteristics of illite powder products and utilize them as a mineralogical database for exploring various applications. Commercial illite powder samples obtained from two mines were subjected to various experiments, including X-ray diffraction (XRD) analysis, laser diffraction particle size analysis, and scanning electron microscopy analysis, X-ray fluorescence analysis. The XRD analysis revealed that the illite powder products from the two mines mainly consisted of illite/muscovite, quartz, and feldspar, indicating similar constituent minerals matching with those of ores for each mine. Laser diffraction particle size analysis indicated the difference in particle size distribution depending on the product specifications, with particle size uniformity tending to increase with increasing mesh sizes. Scanning electron microscopy analysis showed variations in particle shape and size based on specifications. The size of illite particles did not vary significantly with product specifications, with noticeable changes observed mainly in the particle sizes of quartz and feldspar. Furthermore, although there were some differences in chemical composition among the samples from different mines, no significant variations were observed according to specifications. Based on these results, when considering the application of commercial illite powder, it is essential to carefully select it with the consideration of its specifications to account for characteristic variations. The findings of this study present support the great potential of various application fields of commercial illite powder, contributing to industrial utilization and the development of new technologies.

영동 일라이트, 분말, 입도, 광물학적 특성, 활용 분야, Yeongdong illite, Powder, Particle size, Mineralogical characteristics, Application fields

노세형 Sehyeong Roh , 이성근 Sung Keun Lee

DOI: Vol.36(No.4) 355-363, 2023

In this study, we explore the nature of clumped isotopes of H₂O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (¹⁶O, ¹⁷O, and ¹⁸O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H₂O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT¹⁸O), 1.16 times (HT¹⁷O), and 0.703 times (HD¹⁷O) relative to HD¹⁸O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H₂O including ¹⁷O and tritium. The current results help to account for diverse geochemical processes in earth’s surface environments. Future efforts include the calculations of isotope fractionations among various phases of H₂O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

안정 동위원소 분화, 동위원소 clumping, 동위원소 조합, 양자화학 계산, 진동 특성, Stable isotope fractionation, Isotope clumping, Isotopologues, Quantum chemical calculations, Vibrational properties

길영우 Youngwoo Kil

DOI: Vol.36(No.4) 365-376, 2023

Songaksan, formed about 3800 year ago, is one of the tuff rings in the Jeju Island. Mantle xenoliths, spinel peridotites, are enclosed in the Songaksan Trachybasalt. The spinel peridotites are less than 2 cm in size and are composed of olivine, orthopyroxene, clinopyroxene, and spinel. The uniform compositions of the minerals from core to rim indicate that equilibrium was reached in the spinel peridotites before these were enclosed in the host magma. The spinel peridotites originated at depths between 55 and 60 km with equilibrium temperatures ranging from 915 to 968℃. The spinel peridotites from Songaksan reveal porphyroclastic texture with a lot of neoblast minerals. Olivines display strong kink banding, indicating that the upper mantle of Songaksan has been deformed. The spinel peridotites from Songaksan have undergone about 5~7% fractional melting, and cryptic metasomatism by an silicate melt. The period of entrainment and transport of the spinel peridotites in the host magma is about 15 days.

송악산, 맨틀포획암, 스피넬 페리도타이트, 평형온도, Songaksan, Mantle xenolith, Spinel peridotite, Equilibrium temperature