• Economic and Environmental Geology
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• v.41 no.1
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• pp.15-32
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• 2008

The hydrochemical and isotopic (stable isotopes and noble gas isotopes) analyses for hot spring waters, cold groundwaters and surface water samples from the Seokmodo hot spring area of the Ganghwa province were carried out to characterize the hydrogeochemical characteristics of thermal waters and to interpret the source of thermal water and noble gases and the geochemical evolution of hot spring waters in the Seokmodo geothermal system. The hot spring waters and groundwaters show a weakly acidic condition with the pH values ranging from 6.42 to 6.77 and 6.01 to 7.71 respectively. The outflow temperature of the Seokmodo hot spring waters ranges from $43.3^{\circ}C\;to\;68.6^{\circ}C$. Relatively high values of the electrical conductivities which fall between 60,200 and $84,300{\mu}S/cm$ indicate that the hot spring waters were mixed with seawater in the subsurface geothermal system. The chemical compositions of the Seokmodo hot spring waters are characterized by Na-Ca-Cl water type. On the other hand, cold groundwaters and surface waters can be grouped into three types such as the Na(Ca)-$HCO_3$, Na(Ca)-$SO_4$ and Ca-$HCO_3$ types. The ${\delta}^{18}O\;and\;{\delta}D$ values of hot spring waters vary from -4.41 to -4.47%o and -32.0 to -33.5%o, respectively. Cold groundwaters range from -7.07 to -8.55%o in ${\delta}^{18}O$ and from -50.24 to -59.6%o in ${\delta}D$. The oxygen and hydrogen isotopic data indicate that the hot spring waters were originated from the local meteoric water source. The enrichments of heavy isotopes ($^{18}O\;and\;^2H$) in the Seokmodo hot spring waters imply that the thermal water was derived from the diffusion Bone between fresh and salt waters. The ${\delta}^{34}S$ values ranging from 23.1 to 23.5%o of dissolved sulfate are very close to the value of sea water sulfate of ${\delta}^{34}$S=20.2%o in this area, indicating the origin of sulfate in hot springs from sea water. The $^3H/^4He$ ratio of hot spring waters varies from $1.243{\times}10^{-6}\;to\;1.299{\times}10^{-6}cm^3STP/g$, which suggests that He gas in hot spring waters was partly originated from a mantle source. Argon isotopic ratio $(^{40}Ar/^{36}Ar=298{\times}10^{-6}cm^3STP/g)$ in hot spring waters corresponds to the atmospheric value.

• 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.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.441-455
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• 2003

The most common water types are found to be Ca-$HCO_3$, Ca-Na-$HCO_3$ and Ca-Na-$HCO_3$-Cl in Gwangju groundwater. Groundwater near the Gwangju stream are characterized Ca-Cl water type, with over 50 mg/L of C1- and 400 ${\mu}$S/cm of EC. The systematic variation of $Cl^-$, $HCO_3^-$,- EC and ${\gamma}^{18}O$ values in groundwater with distance away from drainages is caused by streamwater infiltration. Stable isotope data indicate that ${\gamma}$D and ${\gamma}^{18}O$ values of groundwaters near drainages were enriched by evaporation effect, showing a equation of ${\gamma}$D=7. 1${\times}{\gamma}^{18}O$-1. ${\gamma}^{18}O$ values over -6${\textperthansand}$ are anomalous in the unconfined groundwater zones, which are influenced by the local surface water enriched in $^{18}O$ composition. Groundwater in highland shows remarkably light ${\gamma}^{18}O$ values below -8$\textperthousand$. The infiltration of streamwater is dominant in unconfined alluvium aquifer near drainages. ${\gamma}^{13}$CDIC values (-17.6∼-15.2$\textperthousand$) of groundwaters near drainages revealed that dissolved inorganic carbon (DIC) is predominantly originated from natural soil-derived $CO_2$. ${\gamma}^{15}N$ and ${\gamma}^{18}O$ values of nitrate are 0∼17.0${\textperthansand}$ and 6.6∼17.4${\textperthansand}$, respectively. Relationship between ${\gamma}^{15}N$ and ${\gamma}^{18}O$ shows a systematic isotopic fractionation caused by denitrification of 40∼60%, suggesting that the major source of groundwater nitrate originated from nitrate of soils, and mixing nitrate of soil and sewage or manure.

• The Journal of Engineering Geology
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• v.18 no.4
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• pp.471-482
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• 2008

This study was carried out to investigate the contamination characteristics of surface water, soil water and groundwater around and in antimony waste landfill site in Wonsung-ri, Yeonki-kun, Chungnam. The waste disposed in the study was excavated and transported to the other site in several years ago. For this study, we collected 35 water samples including groundwater, soil water and surface in the study site and also collected 2 groundwater samples from a comparison site. The data of chemical analysis of soil water samples show the antimony concentration of $48.75{\sim}74.81\;ppb$, which is much higher than groundwater in a comparison site and is highly excess than regulation level for a drinking water of some advanced countries. A relatively high antimony concentration was detected in three stream water samples nearby landfill site and two groundwater samples. Fe and Mn contents in soil water and stream water were measured as maxium 6.5 mg/L and 7.3 mg/L, respectively. Although other heavy metals of water samples in the study site are higher concentration than water sample of comparison site, their absolute levels are lower than regulation level for a drinking water. The chemical data of water samples are plotted widely from Ca - $HCO_3$ type to Ca - ($Cl +SO_4+NO_3$) type. Some groundwater show high contents of potassium and nitrate, which would come from fertilizer and sewage. Conclusively, some heavy metals including antimony have been still remained under the soil surface of the landfill site in the past. These metals have leaked out into nearby stream and groundwater system, and threaten the ecology, crops and the health of residents in this site. Therefore, the government have to prepare the strategy to prevent the diffusion of heavy metals into aquatic environment and have to process the reclamation work for contaminated site. It is also necessary to make a regulation level of the antimony concentration for a drinking water and soil environment in Korea.

• Economic and Environmental Geology
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• v.31 no.3
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• pp.185-199
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• 1998

Hydrogeochemical and environmental isotope studies were undertaken for various kinds of water samples collected in 1995-1996 from the Bugok geothermal area. Physicochemical data indicate the occurrence of three distinct groups of natural water: Group I ($Na-S0_4$ type water with high temperatures up to $77^{\circ}C$, occurring from the central part of the geothermal area), Group II (warm $Na-HCO_{3}-SO_{4}$ type water, occurring from peripheral sites), Group III ($Ca-HCO_3$ type water, occurring as surface waters and/or shallow cold groundwaters). The Group I waters are further divided into two SUbtypes: Subgroup Ia and Subgroup lb. The general order of increasing degrees of hydrogeochemical evolution (due to the degrees of water-rock interaction) is: Group III$\rightarrow$Group II$\rightarrow$Group I. The Group II and III waters show smaller degrees of interaction with rocks (largely calcite and Na-plagioclase), whereas the Group I waters record the stronger interaction with plagioclase, K-feldspar, mica, chlorite and pyrite. The concentration and sulfur isotope composition of dissolved sulfate appear as a key parameter to understand the origin and evolution of geothermal waters. The sulfate was derived not only from oxidation of sedimentary pyrites in surrounding rocks (especially for the Subgroup Ib waters) but also from magmatic hydrothermal pyrites occurring in restricted fracture channels which extend down to a deep geothermal reservoir (typically for the Subgroup Ia waters). It is shown that the applicability of alkaliion geothermometer calculations for these waters is hampered by several processes (especially the mixing with Mg-rich near-surface waters) that modify the chemical composition. However, the multi-component mineral/water equilibria calculation and available fluid inclusion data indicate that geothermal waters of the Bugok area reach temperatures around $125^{\circ}C$ at deep geothermal reservoir (possibly a cooling pluton). Environmental isotope data (oxygen-18, deuterium and tritium) indicate the origin of all groups of waters from diverse meteoric waters. The Subgroup Ia waters are typically lower in O-H isotope values and tritium content, indicating their derivation from distinct meteoric waters. Combined with tritium isotope data, the Subgroup Ia waters likely represent the older (at least 45 years old) meteoric waters circuated down to the deep geothermal reservoir and record the lesser degrees of mixing with near-surface waters. We propose a model for the genesis and evolution of sulfate-rich geothermal waters.

• Journal of the Korean Society of Groundwater Environment
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• v.6 no.3
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• pp.140-151
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• 1999

Groundwater samples from the southern area composed of andesitic rocks and the northwestern area composed of granite in Pusan city, have been collected and analyzed. According to the Piper diagram. groundwater in the southern area belongs to Ca$\^$2＋/－HCO$_3$$\^$－/ and Ca$\^$2＋/－(Cl$\^$－/＋SO$_4$$\^$2－/) types, and that in the northwestern area mostly belongs to Ca$\^$2＋/－HCO$_3$$\^$－/ type and partly Na$\^$＋/－HCO$_3$$\^$－/ type. Two factors (factor 1 and factor 2) were obtained from the result of the factor analysis in the southern area. Factor 1, consisting of Mg$\^$2＋/, Ca$\^$2＋/, Cl$\^$－/, SO$_4$$\^$2－/, NH$_4$$\^$＋/, EC and NO$_3$$\^$－/ is represented by the dissolution of Ca-plagioclase and calcite, and the influence of anthropogenic sources. Factor 2, consisting of K$\^$＋/, Na$\^$＋/. SiO$_2$, SO$_4$$\^$2－/, and HCO$_3$$\^$－/ is mainly represented by the dissolution of feldspar. Three factors were obtained from the result of the factor analysis in the northwestern area Factor 1, consisting of Na$\^$＋/, K$\^$＋/, NH$_4$$\^$＋/, Cl$\^$－/, SO$_4$$\^$2－/ and NO$_3$$\^$－/ explains dissolution of plagioclase and mica, the influence of anthropogenic sources and salt water. Factor 2, consisting of Ca$\^$2＋/ and HCO$_3$$\^$－/ explains the dissolution of Ca-plagioclase. Factor 3, consisting of Mg$\^$2＋/ and SiO$_2$, explains the dissolution of silicate minces. and contaminants. Based on the phase stability diagrams, groundwater both in the southern and in the northwestern area is mostly in equilibrium with kaolinite. Cl$\^$－/ with respect to Na$\^$＋/, Ca$\^$2＋/, Mg$\^$2＋/, K$\^$＋/, SO$_4$$\^$2－/ and HCO$_3$$\^$－/ indicates that both the northwestern area and the southern area are influenced by the salt water.

• The Journal of Engineering Geology
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• v.28 no.4
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• pp.565-582
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• 2018

We investigated the hydrochemical properties of ChusanYongchulso Spring located in Buk-myeon, Ulleung Island, focusing on the formation and characteristics of aquifers in and around the Nari caldera. Abundant pumice with high permeability and numerous fractures (including faults and joints) that formed as a result of caldera subsidence are widely distributed in the subsurface, favoring the formation of aquifers. Because of the presence of porous pyroclastic rocks with a high internal surface area, the water type of the springs is characterized by $NaHCO_3$, with upper stream waters and the upper spring being characterized by $NaHCO_3$ and NaCl, respectively. Components with a high coefficient of determination with EC are $HCO_3$, Na, F, Ca, Mg, Cl, $SiO_2$, and $SO_4$. The high concentrations of Na and Cl might be attributable to the main lithologies in the area, given that alkaline volcanic rocks are distributed extensively across Ulleung Island. Eh and pH, which are considered to be important indicators of water-rock interaction, are unrelated to most components. According to the results obtained from factor analysis, the variance explained by factor 1 is 54% and by factor 2 is 25.8%. Components with a high loading on factor 1 are F, Na, EC, Cl, $HCO_3$, $SO_4$, $SiO_2$, Ca, $NO_3$, and Mg, whereas components with a high loading on factor 2 are Mg and Ca, along with K, $NO_3$, and DO with negative loadings. It is suggested that the high concentrations of Na, Cl, F, and $SO_4$ are closely related to the presence of fine-grained alkaline pyroclastic rocks with high permeability and porosity, which favorintensewater-rock interaction. However, a wide-ranging investigation that encompasses methods such as geophysical prospecting and geochemical analysis (including isotope, trace-element, and tracer techniques) will be necessary to gain a better understanding of the groundwater chemistry, aquifer distribution, and water cycling of Ulleung Island.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.729-744
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• 2023

The value of lithium has significantly increased due to the rising demand for electric cars and batteries. Lithium is primarily found in pegmatites, hydrothermally altered tuffaceous clays, and continental brines. Globally, groundwater-fed salt lakes and oil field brines are attracting attention as major sources of lithium in continental brines, accounting for about 70% of global lithium production. Recently, deep groundwater, especially geothermal water, is also studied for a potential source of lithium. Lithium concentrations in deep groundwater can increase through substantial water-rock reaction and mixing with brines. For the exploration of lithim in deep groundwater, it is important to understand its origin and behavior. Therefore, based on a nationwide preliminary study on the hydrogeochemical characteristics and evolution of thermal groundwater in South Korea, this study aims to investigate the distribution of lithium in the deep groundwater environment and understand the geochemical factors that affect its concentration. A total of 555 thermal groundwater samples were classified into five hydrochemical types showing distinct hydrogeochemical evolution. To investigate the enrichment mechanism, samples (n = 56) with lithium concentrations exceeding the 90th percentile (0.94 mg/L) were studied in detail. Lithium concentrations varied depending upon the type, with Na(Ca)-Cl type being the highest, followed by Ca(Na)-SO₄ type and low-pH Ca(Na)-HCO₃ type. In the Ca(Na)-Cl type, lithium enrichment is due to reverse cation exchange due to seawater intrusion. The enrichment of dissolved lithium in the Ca(Na)-SO₄ type groundwater occurring in Cretaceous volcanic sedimentary basins is related to the occurrence of hydrothermally altered clay minerals and volcanic activities, while enriched lithium in the low-pH Ca(Na)-HCO₃ type groundwater is due to enhanced weathering of basement rocks by ascending deep CO₂. This reconnaissance geochemical study provides valuable insights into hydrogeochemical evolution and economic lithium exploration in deep geologic environments.