이서영 Lee Seoyoung , 이성근 Lee Sung Keun

DOI: Vol.34(No.3) 157-167, 2021

Lead (Pb) is one of the key trace elements, exhibiting a peculiar partitioning behavior into silicate melts in contact with minerals. Partitioning behaviors of Pb between silicate mineral and melt have been known to depend on melt composition and thus, the atomic structures of corresponding silicate liquids. Despite the importance, detailed structural studies of Pb-bearing silicate melts are still lacking due to experimental difficulties. Here, we explored the effect of lead content on the atomic structures, particularly the evolution of silicate networks in Pb-bearing sodium metasilicate ([(PbO)_x(Na₂O)_1-x] · SiO₂) glasses as a model system for trace metal bearing natural silicate melts, using ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy. As the PbO content increases, the ²⁹Si peak widths increase, and the maximum peak positions shift from -76.2, -77.8, -80.3, -81.5, -84.6, to -87.7 ppm with increasing PbO contents of 0, 0.25, 0.5, 0.67, 0.86, and 1, respectively. The ²⁹Si MAS NMR spectra for the glasses were simulated with Gaussian functions for Qⁿ species (SiO₄ tetrahedra with n BOs) for providing quantitative resolution. The simulation results reveal the evolution of each Qⁿ species with varying PbO content. Na-endmember Na₂SiO₃ glass consists of predominant Q² species together with equal proportions of Q¹ and Q³. As Pb replaces Na, the fraction of Q² species tends to decrease, while those for Q¹ and Q³ species increase indicating an increase in disproportionation among Qⁿ species. Simulation results on the ²⁹Si NMR spectrum showed increases in structural disorder and chemical disorder as evidenced by an increase in disproportionation factor with an increase in average cation field strengths of the network modifying cations. Changes in the topological and configurational disorder of the model silicate melt by Pb imply an intrinsic origin of macroscopic properties such as element partitioning behavior.

비정질 Pb-Na 규산염, 고상 핵자기 공명 분광분석, 29Si MAS NMR, 원자 구조, 무질서도, Lead sodium silicate glasses, solid-state NMR spectroscopy, atomic structure, degree of disorder

성동훈 Donghoon Seoung , 김현수 Hyeonsu Kim , 김표상 Pyosang Kim , 이용문 Yongmoon Lee

DOI: Vol.34(No.3) 169-176, 2021

This study aimed to fundamentally understand structural changes of zeolite under pressure and in the presence of different pressure-transmitting media (PTM) for application studies such as immobilization of heavy metal cation or CO₂ storage using pressure. High-pressure X-ray powder diffraction study was conducted on the zeolite-W (K_6.4Al_6.5Si_25.8O₆₄× 15.3H₂O, K-MER) to understand linear compressibility and the bulk moduli in different PTM conditions. Zeolite-w is a synthetic material having the same framework as natural zeolite merlinoite ((K, Ca_0.5, Ba_0.5, Na)₁₀ Al₁₀Si₂₂O₆₄× 22H₂O). The space group of the sample was identified as I4/mmm belonging to the tetragonal crystal system. Water, carbon dioxide, and silicone-oil were used as pressure-transmitting media. The mixture of sample and each PTM was mounted in a diamond anvil cell (DAC) and then pressurized up to 3 GPa with an increment of ca. 0.5 GPa. Pressure-induced changes of powder diffraction patterns were measured using a synchrotron X-ray light source. Lattice constants, and bulk moduli were calculated using the Le-Bail method and the Birch-Murnaghan equation. In all PTM conditions, linear compressibility of c-axis (β_c) was 0.006(1) GPa_-1 or 0.007(1) GPa_-1. On the other hand, the linear compressibility of a(b)-axis (β_a) was 0.013(1) GPa_-1 in silicone-oil run, which is twice more compressible than the a(b)-axis in water and carbon dioxide runs, β_a= 0.006(1) GPa_-1. The bulk moduli were measured as 50(3) GPa, 52(3) GPa, and 29(2) GPa in water, carbon dioxide, and silicone-oil run, respectively. The orthorhombicities of ac-plane in the water, and carbon dioxide runs were comparatively constant, near 0.350~0.353, whereas the value decreased abruptly in the silicone-oil run following formula, y = -0.005(1)x + 0.351(1) by non-penetrating pressure fluid condition.

제올라이트, 멜리노이트, 고압분말회절, 선형압축률, 체적탄성률, zeolite, merlinoite, high-pressure powder diffraction, linear compressibility, bulk modulus

유봉철 Bong Chul Yoo

DOI: Vol.34(No.3) 177-191, 2021

The Zhenzigou Pb-Zn deposit, 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 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. Based on mineral petrography and paragenesis, dolomites from this deposit are classified three type (1. dolomite (D₀) as hostrock, 2. dolomite (D₁) in layer ore associated with white mica, quartz, K-feldspar, sphalerite, galena, pyrite, arsenopyrite from greenschist facies, 3. dolomite (D₂) in vein ore associated with quartz, apatite and pyrite from quartz vein). The structural formulars of dolomites are determined to be Ca_1.00-1.03Mg_0.94-0.98Fe_0.00-0.06As_0.00-0.01(CO₃)₂(D₀), Ca_0.97-1.16Mg_0.32-0.83 Fe_0.10-0.50Mn_0.01-0.12Zn_0.00-0.01Pb_0.00-0.03As_0.00-0.01(CO₃)₂(D₁), Ca_1.00-1.01Mg_0.85-0.92Fe_0.06-0.11 Mn_0.01-0.03As_0.01(CO₃)₂(D₂), respectively. It means that dolomites from the Zhenzigou deposit have higher content of trace elements compared to the theoretical composition of dolomite. Feo and MnO contents of these dolomites (D₀, D₁ and D₂) contain 0.05∼2.06 wt.%, 0.00∼0.08 wt.% (D₀), 3.53∼17.22 wt.%, 0.49∼3.71 wt.% (D₁) and 2.32∼3.91 wt.%, 0.43∼0.95 wt.% (D₂), respectively. The dolomite (D₁) from layer ore has higher content of these trace elements (FeO, MnO, ZnO and PbO) than dolomite (D₀) from hostrock and dolomite (D₂) from quartz vein. Dolomites correspond to Ferroan dolomite (D₀ and D₂), and ankerite and Ferroan dolomite (D₁), respectively. Therefore, 1) dolomite (D₀) from hostrock is a Ferroan dolomite formed by marine evaporative lagoon environment in Paleoproterozoic Jiao Liao Ji basin. 2) Dolomite (D₁) from layer ore is a ankerite and Ferroan dolomite formed by hydrothermal metasomatism origined metamorphism (greenschist facies) associated with Paleoproterozoic intrusion. 3) Dolomte (D₂) from quartz vein is a Ferroan dolomite formed by hydrothermal fluid origined Mesozoic intrusion.

젠지고우 연-아연 광상, 돌로마이트, 산상, 화학조성, Zhenzigou Pb-Zn deposit, Dolomite, Occurrence, Chemical composition

박덕원 Deok-won Park

DOI: Vol.34(No.3) 193-208, 2021

Abstract: The characteristics of the microcrack lengths(①), microcrack spacings(②) and Brazilian tensile strengths(③) related to the six directions of rock cleavages(H2~R1) in Geochang granite were analyzed. First, the 18 cumulative graphs for the above three major factors representing unique characteristics of the rock cleavages were made. Through the general chart for these graphs classified into three planes and three rock cleavages, the 28 parameters on the length, spacing and Brazilian tensile strength have been determined. The results of correlation analysis among these parameters are summarized as follows. Second, the above parameters were classified into six groups(I~VI) according to the sorting order on the magnitude of parameter values among three rock cleavages and three planes. The values of parameters belonging to group I and II are in order of R(rift) < G(grain) < H(hardway) and H < G < R. The values of the 8 parameters on the length of line(os₂, Δs, ΔL and oS^mean), the exponent(λ_L ^mean and λ_S ^mean), the slope(a^mean) and the anisotropy coefficient (An^mean) are in order of R < G < H and H'(hardway plane) < G'(grain plane) < R'(rift plane). Third, the noticeable differences in distribution patterns among the six types of charts for three planes and three rock cleavages are as follows. From the chart for three planes, the values of ΔL, ΔS and Δσ_t, corresponding to the distance between two points where the two fitting lines meet on the X-axis, increase in the order of R' < H' < G'. In particular, the two graphs of R2 and G2 related to the length and Brazilian tensile strength are almost parallel to each other and show the distribution characteristics of hardway plane. Among the graphs related to the Brazilian tensile strength, the overall shape for hardway plane is similar to that for grain. From the chart for three rock cleavages, the slopes of the graphs related to the length increase in the order of R < G < H, while those of the graphs related to the spacing and Brazilian tensile strength decrease in the order of R

미세균열의 길이, 미세균열의 간격, 압열인장강도, 결, 화강암, 파라미터, 상관도, Microcrack lengths, Microcrack spacings, Brazilian tensile strengths, Rock cleavages, Granite, Parameters, Correlation chart