• Economic and Environmental Geology
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• v.56 no.5
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• pp.515-532
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• 2023

Bentonite, predominantly consists of expandable clay minerals, is considered to be the suitable buffering material in high-level radioactive waste disposal repository due to its large swelling property and low permeability. Additionally, the bentonite has large cation exchange capacity and specific surface area, and thus, it effectively retards the transport of leaked radionuclides to surrounding environments. This study aims to review the thermodynamic sorption models for four radionuclides (U, Am, Se, and Eu) and eight bentonites. Then, the thermodynamic sorption models and optimized sorption parameters were precisely analyzed by considering the experimental conditions in previous study. Here, the optimized sorption parameters showed that thermodynamic sorption models were related to experimental conditions such as types and concentrations of radionuclides, ionic strength, major competing cation, temperature, solid-to-liquid ratio, carbonate species, and mineralogical properties of bentonite. These results implied that the thermodynamic sorption models suggested by the optimization at specific experimental conditions had large uncertainty for application to various environmental conditions.

• Economic and Environmental Geology
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• v.39 no.3 s.178
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• pp.213-227
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• 2006

The geochemical evolution of mine drainage and leachate from waste rock dumps and stream water in Pb-As-rich abandoned Sechang mine area was investigated to elucidate mechanisms of trace metals. Total and sequential extractions were applied to estimate the distribution of trace metals in constituent phases of the waste rocks and to assess the mobility of trace metals according to physicochemical conditions. These discharged waters varied largely in chemical composition both spatially and temporally, and included cases with significant]y low pH (in the range 2.1-3.3), and extremely sulphate (up to 661 mg/l and metal contents (e.g. up to 169 mg/l for Zn, 27 mg/l for As, 3.97 mg/l for Pb, 2.99 mg/l for Cu, and 1.88 mg/l for Cd). Arsenic and heavy metal concentrations at the down-stream of Sechang mine have been decreased nearly to the background level in downstream sites (sites 8 and 16) without any artificial treatments. The oxidation of Fe-sulfides and the subsequent hydrolysis, of Fe(II), with precipitation of poorly crystallized minerals, constituted an efficient mechanism of natural attenuation which reduces considerably the transference of trace metals (i.e. Fe and As) to rivers. The dilution of drainage by mixing with pristine waters provoked an additional decrease of trace metal concentrations and a progressive pH increase. On the other hand, the most soluble cations (i.e. Zn) remained significantly as dissolved solutes until the pH was raised to approximately neutral values. With respect to ecotoxicity, it is likely that the Zn pollution is of particular concern in Sechang mine area. This was confirmed by the sequential extraction experiment, where Zn in wet waste-rock samples occurred predominantly in the exchangeable fraction (65-89% of total), while Pb was the highest in the reducible and carbonate fractions, and Cd, Cu and As in the residual fraction. Pb concentration in the readily available exchangeable fraction (34-48% of total) was dominated for dried waste rock samples. Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreased in the order of Zn>Pb>Cd>As=Cu.

• Economic and Environmental Geology
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• v.38 no.4 s.173
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• pp.435-450
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• 2005

The purpose of the study is to analyze the hydrogeochemical characteristics by multivariate statistical method, to interpret the hydrogeochemical processes for the new variables calculated from principal components analysis (PCA), and to infer the groundwater flow and circulation mechanism by applying the geostatistical methods for each element and principal component. Chloride and nitrate are the most influencing components for groundwater quality, and the contents of $NO_3$ increased by the input of agricultural activities show the largest variation. The results of PCA, a multivariate statistical method, show that the first three principal components explain $73.9\%$ of the total variance. PC1 indicates the increase of dissolved ions, PC2 is related with the dissolution of carbonate minerals and nitrate contamination, and PC3 shows the effect of cation exchange process and silicate mineral dissolution. From the results of experimental semivariogram, the components of groundwater are divided into two groups: one group includes electrical conductivity (EC), Cl, Na, and $NO_3$, and the other includes $HCO_3,\;SiO_2,$ Ca, and Sr. The results for spatial distribution of groundwater components showed that EC, Cl, and Na increased with approaching the coastal line and nitrate has close relationship with the presence of agricultural land. These components are also correlated with the topographic features reflecting the groundwater recharge effect. The kriging analysis by using principal components shows that PC 1 has the different spatial distribution of Cl, Na, and EC, possibly due to the influence of pH, Ca, Sr, and $HCO_3$ for PC1. It was considered that the linear anomaly zone of PC2 in western area was caused by the dissolution of carbonate mineral. Consequently, the application of multivariate and geostatistical methods for groundwater in the study area is very useful for determining the quantitative analysis of water quality data and the characteristics of spatial distribution.

• Economic and Environmental Geology
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• v.47 no.4
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• pp.363-379
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• 2014

The Haenam Pb-Zn skarn deposit is located at the Hwawon peninsula in the southwestern part of the Ogcheon Metamorphic Belt. The deposit is developed along the contact between limestone of the Ogcheon group and Cretaceous quartz porphyry. Petrography of ore samples, chemical composition of skarn and ore minerals, and geochemistry of the related igneous rocks were investigated to understand the characteristics of the skarn mineralization. Skarn zonation consists of garnet${\pm}$pyroxene${\pm}$calcite${\pm}$quartz zone, pyroxene+garnet+quartz${\pm}$calcite zone, calcite+pyroxene${\pm}$garnet zone, quartz+calcite${\pm}$pyroxene zone, and calcite${\pm}$chlorite zone in succession toward carbonate rock. Garnet commonly shows zonal texture comprised of andradite and grossular. Pyroxene varies from Mn-hedenbergite to diopside as away from the intrusive rock. Chalcopyrite occurs as major ore mineral near the intrusive rock, and sphalerite and galena tend to increase as going away. Electron probe microanalyses revealed that FeS contents of sphalerite become decreased from 5.17 mole % for garnet${\pm}$pyroxene${\pm}$calcite${\pm}$quartz zone to 2.93 mole %, and to 0.40 mole % for calcite+pyroxene${\pm}$garnet zone, gradually. Ag and Bi contents also decreased from 0.72 wt.% and 1.62 wt.% to <0.01 wt.% and 0.11 wt.%, respectively. Thus, the Haenam deposit shows systematic variation of species and chemical compositions of ore minerals with skarn zoned texture. The related intrusive rock, quartz porphyry, expresses more differentiated characteristics than Zn-skarn deposit of Meinert(1995), and has relatively high$SiO_2$ concentration of 72.76~75.38 wt.% and shows geochemical features classified as calc-alkaline, peraluminous igneous rock and volcanic arc tectonic setting.

• Economic and Environmental Geology
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• v.30 no.6
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• pp.505-517
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• 1997

Lead and zinc mineralization of the Kwangsin mine was formed in quartz and carbonate veins that filled fault-related fractures in the limestone-rich Samtaesan Formation of the Chosun Supergroup and the phyllite-rich Suchangni Formation of unknown age. A K-Ar date of alteration sericite indicates that the Pb-Zn mineralization took place during Late Cretaceous (83.5 Ma), genetically in relation to the cooling of the nearby Muamsa Granite (83~87 Ma). Mineral paragenesis can be divided into three stages (I, II, III): (I) the deposition of barren massive white quartz, (II) the main Pb-Zn mineralization with deposition of white crystalline quartz and/or carbonates (rhodochrosite and dolomite), and (III) the deposition of post-ore barren calcite. Mineralogic and fluid inclusion data indicate that lead-zinc minerals in middle stage II (IIb) were deposited at temperatures between $182^{\circ}$ and $276^{\circ}C$ from fluids with salinities of 2.7 to 5.4 wt. % equiv. NaCl and with log $fs_2$ values of -15.5 to -11.8 atm. The relationship between homogenization temperature and salinity data indicates that lead-zinc deposition was a result of fluid boiling and later meteoric water mixing. Ore mineralization occurred at depths of about 600 to 700 m. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S_{CDT}=9.0{\sim}14.5$ ‰) indicate a relatively high ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids (up to 14 ‰), likely indicating an igneous source of sulfur largely mixed with an isotopically heavier sulfur source (possibly sulfates in surrounding sedimentary rocks). There is a remarkable decrease of calculated ${\delta}^{18}O$ value of water in hydrothermal fluids with increasing paragenetic time: stage I, 14.6~10.1 ‰; stage IIa, 5.8~2.2 ‰; stage IIb, 0.8~2.0 ‰; stage IIc, -6.1~-6.8 ‰, This indicates a progressive increase of meteoric water influx in the hydrothermal system at Kwangsin. Measured and calculated hydrogen and oxygen isotope values indicate that the Kwangsin hydrothermal fluids was formed from a circulating (due to intrusion of the Muamsa Granite) meteoric waters which evolved through interaction mainly with the Samtaesan Formation (${\delta}^{18}O=20.1$ to 24.9 ‰) under low water/rock ratios.

• Economic and Environmental Geology
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• v.32 no.5
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• pp.435-444
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• 1999

The antimony deposits of the Hyundong mine, located in the northeastern part of the Sobaegsan massif, occur as hydrothermal quartz+carbonate veins and stockworks which fill the fault fractures developed in Precambrian metamOlphic rocks (mainly, granitic gneiss). Hydrothermal alteration occurs commonly in the vicinity of mineralized veins and is characterized by sericitization and silicification. A K-Ar age of alteration sericite is 139.2$\pm$ 4.4 Ma, implying the early Cretaceous age of mineralization, possibly in association with intrusion of nearby acidic dikes (mainly, quartz porphyry). The hydrothermal mineralization occurred in five mineralization stages. These are: (I) stage I, characterized by deposition of chalcedonic quartz; (2) stage II, deposition of quartz with base-metal sulfides and stibnite; (3) stage III, deposition of quartz and carbonates (calcite, dolomite, ankerite, rhodochrosite) with various antimony-bearing minerals such as stibnite, polybasite, berthierite, native antimony, gudmundite and ullmannite; (4) stage IV, deposition of calcite with stibnite; and (5) stage V, deposition of barren calcite. Antimony occurs mostly as stibnite within stages II to IV veins, which has various habits including disseminated, veinlets and euhedral coarse crystals. Fluid inclusion studies indicate that hydrothermal mineralization at Hyundong occurred from the fluids with temperature and salinity of $330^{\circ}$C to 120 and 5.3 wI. % equiv. NaCI. The temperature and salinity of ore fluids systematically decreased with elapsed time in the course of mineralization, possibly due to the influx of larger amounts of meteoric groundwater. The deposition of antimony-bearing minerals occurred at low temperatures «$250^{\circ}$C), mainly due to the cooling and dilution of fluids. Based on the evidence of fluid boiling during the early stage II mineralization, the mineralization occurred under low pressure conditions (about 80 bars, corresponding to depths of about 350 m under hydrostatic pressure regime). Thermodynamic considerations of ore . mineral assemblages indicate that antimony deposition also occurred as the results of decreases in temperature and sulfur fugacity of hydrothermal fluids. Calculated sulfur isotope composition of ore fluids ($\delta^{34}S_{\Sigma s}$=5.4 to 7.8$\textperthousand$) indicates an igneous source of sulfur.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.4
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• pp.177-191
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• 1998

For various kinds of waters including surface water, shallow groundwater (＜70 m deep) and deep groundwater (500∼810 m deep) from the Pungki area, an integrated study based on hydrochemical, multivariate statistical, thermodynamic, environmental isotopic (tritium, oxygen-hydrogen, carbon and sulfur), and mass-balance approaches was attempted to elucidate the hydrogeochemical and hydrologic characteristics of the groundwater system in the gneiss area. Shallow groundwaters are typified as the 'Ca-HCO$_3$'type with higher concentrations of Ca, Mg, SO$_4$and NO$_3$, whereas deep groundwaters are the 'Na-HCO$_3$'type with elevated concentrations of Na, Ba, Li, H$_2$S, F and Cl and are supersaturated with respect to calcite. The waters in the area are largely classified into two groups: 1) surface waters and most of shallow groundwaters, and 2) deep groundwaters and one sample of shallow groundwater. Seasonal compositional variations are recognized for the former. Multivariate statistical analysis indicates that three factors may explain about 86% of the compositional variations observed in deep groundwaters. These are: 1) plagioclase dissolution and calcite precipitation, 2) sulfate reduction, and 3) acid hydrolysis of hydroxyl-bearing minerals(mainly mica). By combining with results of thermodynamic calculation, four appropriate models of water/ rock interaction, each showing the dissolution of plagioclase, kaolinite and micas and the precipitation of calcite, illite, laumontite, chlorite and smectite, are proposed by mass balance modelling in order to explain the water quality of deep groundwaters. Oxygen-hydrogen isotope data indicate that deep groundwaters were originated from a local meteoric water recharged from distant, topograpically high mountainous region and underwent larger degrees of water/rock interaction during the regional deep circulation, whereas the shallow groundwaters were recharged from nearby, topograpically low region. Tritium data show that the recharge time was the pre-thermonuclear age for deep groundwaters (＜0.2 TU) but the post-thermonuclear age for shallow groundwaters (5.66∼7.79 TU). The $\delta$$\^$34/S values of dissolved sulfate indicate that high amounts of dissolved H$_2$S (up to 3.9 mg/1), a characteristic of deep groundwaters in this area, might be derived from the reduction of sulfate. The $\delta$$\^$13/C values of dissolved carbonates are controlled by not only the dissolution of carbonate minerals by dissolved soil CO$_2$(for shallow groundwaters) but also the reprecipitation of calcite (for deep groundwaters). An integrated model of the origin, flow and chemical evolution for the groundwaters in this area is proposed in this study.

• 한국해양학회지
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• v.22 no.3
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• pp.130-142
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• 1987

Sedimentological characteristics of the surface sediments in the southern sea off Cheju Island are described from analyses of bottom sediments. The sediments are subdivided into seven textural classes, muddy sand, slightly gravelly muddy sand, sand, clayey sand, sandy clay, sandymud, silty sand. Sand-size sediments are distributed in the southeastern part and/or around the Island, whereas sandy and muddy sediments are mainly distributed in the central and southern parts of the study area. A small portion of mud patch is located in the southwestern part of the area. According to the textural parameters analysis, sediments in the study area are poorly sorted(av.2.52 ), positive skewed(av.1.61 ), leptokurtic(av.1.74 ), transported by saltation and/or suspension, and roundness of quartz is varied from angular to surrounded, which suggesting that the depositional environment is not simple. The calcium carbonate content is on the average 26.99%, and commonly abundant in sand-size sediments, whereas organic matter content in the bulk sediment is on the average 6.70% and usually dominant in fine-grained sediments.Light minerals consist of quartz(av56.01%),Na-Ca feldspar(av.6.15%),K-feldspar(av.9.22%) and rock fragments(av28.11%).The contect onquartz and K-feldspar increases continuously away from the Cheju Island. As a result of geochemical analysis,concentrations of the elements are as follow:Zn:19.42-43.52 ppm (av.30.67ppm),Mn:50-304 ppm(av139.39ppm),Cr:3.54-10.68ppm(av6.50ppm),Pb:5.52-41.68ppm(av.15.60ppm), Co:7.08-14.68ppm (av.10.78ppm),Ni:19.70-42.42ppm(av.29.57ppm),Cu:3.14-9.12ppm(av.5.14ppm),Fe:0.48-2.08% (av1.22%),Ca:0.32-13.16%(av6.60%),Al:0.06-0.08%(av.0.27%),Mg:0.12-0.76%(av.0.53%)na:0.11-0.51%(av.0.36%) Ag:0.48-4.08ppm(av.1.22ppm).Among these elements,the content of Zn,Cu,Cr,Mn,Fe,Al,Mg,Pb and Na increase toward the southwestern area,while the content of Ca and Ag SHOWS the reversed distribution trend.Such a distribution pattern seems to imply that spatial distrivution of heavy metals is closely related to the variation in grain size. X-ray diffractogram show that the minerals in clay from the southwestern mud patch are illite ,chlorite, kaolinte,feldspar and calcite.The bulk of illite in th mud zone is believed to be originated from Huanghe and Yangytze River.The mud patch in this region contains the diagnostic calcite peak,and the concentration of Ca,ni,Pb,Ag are similar to Huanghe type,which indicates that the greater part of these clay fractions may have been derived from the Huanghe River.

• Economic and Environmental Geology
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• v.34 no.6
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• pp.507-522
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• 2001

At the Tongyeong mine, quartz, rhodochrosite (kutnahorite), muscovite, illite, pyrite, galena, chalcopyrite. sphalerite, acanthite, and hessite are the principal vein minerals. They were deposited under epithermal conditions in two stages. Ore mineral assemblages and associated gangue phases in stage can be clearly divided into two general associations: an early cycle (band) that appeared with introduction of most of the sulfides and electrum, and a later cycle in which base metal and carbonate-bearing assemblages (mostly rhodochrosite) became dominant. Tellurides and some electrum occur as small rounded grains within subhedral-to euhedral pyrite or anhedral galena in stageII. Sulfide mineralization is zoned from pyrite to galena and sphalerite. We have used computer modeling to simulate formation of four stages of vein genesis. The reaction of a single fluid with andesite host rock at 28$0^{\circ}C$, isobaric cooling of a single fluid from 26$0^{\circ}C$ to 12$0^{\circ}C$, and boiling and mixing of a fluid with both decreasing pressure and temperature were studied using the CHILLER program. Calculations show that the precipitation of alteration minerals is due to fluid-andesite interaction as temperature drops. Speciation calculations confirm that the hydrothermal fluids with moderately high salinities and pH 5.7 (acid), were capable of transporting significant quantities of base metals. The abundance of gold in fluid depends critically on the ratio of total base metals and iron to sulfide in the aqueous phase because gold is transported as an Au(HS)$_2$- complex, which is sensitive to sulfide activity. Modeling results for Tongyeong mineralization show strong influence of shallow hydrogenic processes such as boiling and fluid mixing. The variable handing in stageII mineralization is best explained by maltiple boilings of hydrothermal fluid followed by lateral mixing of the fluid with overlying diluted, steam-heated ground water. The degree of similarity of calculated mineral assemblages and observed electrum composition and field relationships shows the utility of the numerical simulation method in identifying chemical processes that accompany boiling and mixing in Te-bearing Au-Ag system. This has been applied in models to narrow the search area for epithermal ores.

• Economic and Environmental Geology
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• v.49 no.1
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• pp.13-22
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• 2016

The objectives of this study were to recover silica and iron oxides and $CO_2$ sequestration using serpentine via various acid dissolution and pH swing processes. Serpentine collected from Guhang-myeon in S. Korea were mainly composed of antigorite and magnetite consisting of $SiO_2$ (45.3 wt.%), MgO (41.3 wt.%), $Fe_2O_3$ (12.2 wt.%). Serpentine pulverized ($${\leq_-}75{\mu}m$$) and then dissolved in 3 different acids, HCl, $H_2SO_4$, $HNO_3$. Residues treated with acidic solution were recovered from the solution (step 1). And then the residual solution containing dissolved serpentine was titrated using $NH_4OH$. And pH of the solution increased up to pH=8.6 to obtain reddish precipitates (step 2). After recovery of the precipitates, the residual solution reacted with $CO_2$ and then pH increased up to pH=9.5 to precipitate white materials (step 3). The mineralogical characteristics of the original sample and harvested precipitates were examined by XRD, and TEM-EDS analyses. ICP-AES analysis was also used to investigate solution chemistry. The dissolved ions were Mg, Si, and Fe. The antigorite became noncrystralline silica after acid treatment (step 1). The precipitate at pH=8.6 was mainly amorphous iron oxide, of which size ranged from 2 to 10 nm and mainly consisting of Fe, O, and Si (step 2). At pH=9.5, nesquehonite [$Mg(HCO_3)(OH){\cdot}2(H_2O)$] and lasfordite [$MgCO_3{\cdot}H_2O$] were formed after reaction with $CO_2$ (step 3). The size of carbonated minerals was ranged from 1 to $6{\mu}m$. These results indicated that the acid treatment of serpentine and pH swing processes for the serpentine can be used for synthesis of other materials such as silica, iron oxides and magnesium carbonate. Also, This process may be useful for the precursor synthesis and $CO_2$ sequestration via mineral carbonation.