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.
Jaehoon Choi;SunJu Park;Hyunsoo Seo;Hyun Tai Ahn;Jeong-Hwan Lee;Junghoon Park;Seong-Taek Yun
Economic and Environmental Geology
/
v.56
no.6
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pp.847-870
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2023
The safe disposal of high-level radioactive waste requires accurate predictions of the long-term geochemical behavior of radionuclides. To achieve this, the present study was conducted to model geochemical behaviors of uranium (U), plutonium (Pu), and palladium (Pd) under different hydrogeochemical conditions that represent deep groundwater in Korea. Geochemical modeling was performed for five types of South Korean deep groundwater environment: high-TDS saline groundwater (G1), low-pH CO2-rich groundwater (G2), high-pH alkaline groundwater (G3), sulfate-rich groundwater (G4), and dilute (fresh) groundwater (G5). Under the pH and Eh (redox potential) ranges of 3 to 12 and ±0.2 V, respectively, the solubility and speciation of U, Pu, and Pd in deep groundwater were predicted. The result reveals that U(IV) exhibits high solubility within the neutral to alkaline pH range, even in reducing environment with Eh down to -0.2 V. Such high solubility of U is primarily attributed to the formation of Ca-U-CO3 complexes, which is important in both G2 located along fault zones and G3 occurring in granitic bedrocks. On the other hand, the solubility of Pu is found to be highly dependent on pH, with the lowest solubility in neutral to alkaline conditions. The predominant species are Pu(IV) and Pu(III) and their removal is predicted to occur by sorption. Considering the migration by colloids, however, the role of colloid formation and migration are expected to promote the Pu mobility, especially in deep groundwater of G3 and G5 which have low ionic strengths. Palladium (Pd) exhibits the low solubility due to the precipitation as sulfides in reducing conditions. In oxidizing condition, anionic complexes such as Pd(OH)3-, PdCl3(OH)2-, PdCl42-, and Pd(CO3)22- would be removed by sorption onto metal (hydro)oxides. This study will improve the understanding of the fate and transport of radionuclides in deep groundwater conditions of South Korea and therefore contributes to develop strategies for safe high-level radioactive waste disposal.
This study was carried out to investigate distribution of epilithic algal and chemical contents of irrigation water influencing in the Seomjin River from March to October in 1996 and 1997. In the water quality of the Seomjin River, the monthly average contents of $NH^+\;_4-N,\;SO_4\;^{2-}$ and $Cl^-$ showed the lowest peak in July and August while that of $NO_3-N$ showed the highest peak in June. The water quality of the Seomjin River was deteriorated by inflow of Yo-cheon and Sosi-cheon in the middle stream. The concentration of anions and cations of the Seomjin River was $Cl^->SO_4\;^{2-}>NO_3\;^->PO_4\;^{3-}\;and\;Ca^{2+}>Na^+>Mg^{2+}>K^+>NH_4\;^+$, respectively. The epilithic algal community identified 339 taxa consisting of 7 forma, 42 varieties and 290 species in 6 classes. In species composition, green algae and diatoms were heavily dominated which were evaluated 50.4% and 31.3% of total classification, respectively. In seasonal distribution, 219 species presented in summer but, 147 species were in winter. In this study, dominant species were Cocconeis placentula var. euglypta and Cosmarium furcatospermum in spering. Cyclotella meneghinasa and Synedra ulna, Scenedesmus ecornis in summer. Melosira varians, Achnathes minutissima in autumn and Gomphonema parvulum in winter were dominated. Finally, the dominant indices in this study have ranged 0.10-0.43.
Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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v.10
no.3
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pp.189-197
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2012
Geochemical composition of fracture filling minerals and groundwater was investigated to characterize geochemical characteristics of groundwater system at the KURT site. Minerals such as calcite, illite, laumontite, chlorite, epidote, montmorillonite, and kaolinite, as well as I/S mixed layer minerals were detected in the minerals extracted from the fracture surfaces of the core samples. The groundwater from the DB-1, YS-1 and YS-4 boreholes showed alkaline conditions with pH of higher than 8. The electrical conductivity (EC) values of the groundwater samples were around $200{\mu}S/cm$, except for the YS-1 borehole. Dissolved oxygen was almost zero in the DB-1 borehole indicating highly reduced conditions. The Cl- concentration was estimated around 5 mg/L and showed homogeneous distribution along depths at the KURT site. It might indicate the mixing between shallow groundwater and deep groundwater. The shallow groundwater from boreholes showed $Ca-HCO_3$ type, whereas deep groundwater below 300 m from the surface indicated $Na-HCO_3$ type. The isotopic values observed in the groundwater ranged from -10.4 to -8.2‰ for ${\delta}^{18}O$ and from -71.3 to -55.0‰for ${\delta}D$. In addition, the isotope-depleted water contained higher fluoride concentration. The oxygen and hydrogen isotopic values of deep groundwater were more depleted compared to the shallow groundwater. The results from age dating analysis using $^{14}C$ indicated relatively younger (2000~6000yr old) groundwater compared to other european granitic groundwaters such as Stripa (Sweden).
To investigate the increased acid tolerance of a acid-resistant mutant Leuconostoc mesenteroides M-100 improved as a kimchi starter, proton permeability, ATPase acitivity, glycolysis activity, $Mg^{2+}$ releasement, and membrane fatty acid composition were studied and comprised with its wild type Leuconostoc mesenteroides Mw. In the proton permeability experiment, the mininum values of the average half time ($t_{1/2}$) of pH equilibration through the cell membrane of the Mw and the M-100 were about 8.6 min and 9.2 min in 150 mM KCI solution, respectivily. In the 3% NaCl solution, the $t_{1/2}$ values of the Mw and the M-100 were 6min and 8.6 min, respectivily. The values and pHs of maximal specific activities of ATPase originated from the Mw and the M-100 were 0.6U at pH 5.5 and 0.8U at pH 5.5, respectivily. The result of pH dependence of glycolysis showed that the M-100 had higher activities than that of Mw except at pH 5.0. The releases of magnesium from the Mw and the M-100 were observed about 36.5% and 13% at pH 4.0 after 2 hours, respectivily. The results of comparison of membrane fatty acid composition of the Mw with the M-100 showed that $C_{12}$, $C_{14}$, $C_{18:1}$, and $C_{19:0cyclo}$ were major different fatty acids between two strains and the content of $C_{18:1}$, and $C_{19:0cyclo}$ were 23.4%, 10.2% in the Mw and 15.1%, 12.2% in the M-100. These results indicated that acid tolerance of the M-100 was significantly improved in comparison with its wild type Mw.
To get the basic information for the improvement of the optimum levels of upland soil fertility and fertilizer application, the soil samples in two hundred fifteen site were collected from the major condiment vegetable cultivation areas such as red pepper, garlic and onion fields. Physico-chemical properties of the soil samples were investigated. Soil texture distribution of soil samples in red pepper, garlic and onion cultivation areas was in order of loam (L), sandy loam (SL), silt loam (SiL) and clay loam (CL) (35.4, 31.6, 14.9 and 7.0%, respectively). The average pH of soil in garlic and onion cultivation areas were over pH 6.0, whereas in red pepper was under pH 5.5. The frequency distribution of soil pH in total sampling sites were 58.7% in under pH 6.0 and 21.4% in below pH 5.0, in contrast to 10.3% in over pH 7.0. The organic matter contents were in the range of $20{\sim}30g\;kg^{-1}$, and the onion field soils was a little higher than those in red pepper or garlic. The available phosphate contents were in the range of $719{\sim}746mg\;kg^{-1}$ and were not different among in red pepper, garlic and onion. The frequency distribution of available phosphate in total sampling sites were found 62.8% of above $600mg\;kg^{-1}$, which was over the standard level for upland soil improvement, and then 22.3% was exceeded $1,000mg\;kg^{-1}$, especially. In the exchangeable cations, the K and Ca contents in garlic (1.27 and $9.11cmol\;kg^{-1}$) and onion (1.20 and $8.39cmol\;kg^{-1}$) were higher than in red pepper (0.96 and $5.87cmol\;kg^{-1}$), respectively. The Mg contents in garlic field soils ($2.17cmol\;kg^{-1}$) were higher than those in red pepper and onion (1.51 and $1.80cmol\;kg^{-1}$). This exchangeable K, Ca and Mg contents were higher than the standard level for upland soil improvement. The contents of microelement were ranged in $54.3{\sim}60.1mg\;kg^{-1}$ for Fe, $31.3{\sim}42.3mg\;kg^{-1}$ for Mn, $1.7{\sim}2.3mg\;kg^{-1}$ for Cu and $4.8{\sim}5.5mg\;kg^{-1}$ for Zn, respectively.
To investigate the increased acid tolerance of a acid-resistant mutant Leuconostoc paramesenteroides P-100 improved as a kimchi starter, proton permeability, ATPase acitivity, glycolysis activity, $Mg^2$sup +/ releasement, and membrane fatty acid composition were studied and comprised with its wild type Leuconostoc paramesenteroides Pw. In the proton permeability experiment, the maximum values of the average half time (t$\_$1/2/) of pH equilibration through the cell membrane of the Pw and the P-100 were about 6.4 min and 7.8 min in 150 mM KCI solution, respectively. In the 3% NaCl solution, the t$\_$1/2/ values of the Pw and the P-100 were 5.5 min and 6.9 min, respectively. The values and pHs of maximal specific activities of ATPase originated from the Pw and the P-100 were 0.5 unit/mg protein and 0.78 unit/mg protein at pH 6.0, respectively. The result of pH dependence of glycolysis showed that the P-100 had higher activities than that of Pw except at pH 7.0. The releases of magnesium from the Pw and the P-100 were observed about 54.5% and 23.2% at pH 4.0 after 2 hours, respectively. The results of comparison of membrane fatty acid composition of the Pw with the P-100 showed that C$\_$8:0/, C$\_$9:0/, C$\_$10:0/, C$\_$11:0/, C$\_$18:0/, and C$\_$19:0,cyclo/ were major different fatty acids between two strains and the content of C$\_$18:1/, and C$\_$19:0,cyclo/ were 2.8%, N.D (not detected) in the Pw and 0.4%, 2.3% in the P-100. These results indicated that acid tolerance of the P-100 was significantly improved in comparison with its wild type Pw.
Water shortages are expected to be a major impact of climate change. This study examined the growth of Chinese cabbage seedling using reclaimed wastewater and waste nutrient solution as alternative irrigation resources. Generally, the concentration of nutrients, such as $K^+$, $NH_4^+$, $Mg^{2+}$, $Ca^{2+}$, $Cl^-$,$NO_3^-$, $PO_4^-$ and $SO_4^{2-}$, in waste nutrient solution was higher than that in wastewater. However, Chinese cabbage seedling irrigated with wastewater was supplied a higher concentration of $Na^+$ and $Cl^-$ than waste nutrient solution. The growth of Chinese cabbage seedling irrigated with waste nutrient solution was similar or higher than those irrigated with groundwater as control, while the growth of those irrigated with wastewater was similar to those irrigated with groundwater. The total nitrogen uptake in Chinese cabbage seedling irrigated with groundwater, waste nutrient solution from organic and inorganic hydroponic cultures, and wastewater was 5.47, 10.02, 5.20, and 4.59 mg/plant, respectively. The nitrogen uptake of Chinese cabbage seedling irrigated with waste nutrient solution from organic hydroponic substrates in a 50% lower dose than recommended was 8.34 mg/plant, which is higher than that of the cabbage irrigated with groundwater. Overall, the results suggest that waste nutrient solution and wastewater can be used as alternate water resources, and can allow a reduction in the amount of fertilizer needed to raise Chinese cabbage seedling.
In this study, the evaluation of performance of AORFB using methyl viologen and TEMPOL as organic active materials in neutral supporting electrolyte (NaCl) with various membrane types was performed. Using methyl viologen and TEMPOL as active materials in neutral electrolyte solution, the cell voltage is 1.37V which is relatively high value for AORFB. Two types of membranes were examined for performance comparison. First, when using Nafion 117 membrane which is commercial cation exchange membrane, only the charge process occurred in the first cycle and the single cell couldn't work because of its high resistance. However, when using Fumasep anion exchange membrane (FAA-3-50) instead of Nafion 117 membrane, the result was obtained as the totally different charge-discharge graphs. When current density was $40mA{\cdot}cm^{-2}$ and cut off voltage range was from 0.55 V to 1.7 V, the charge efficiency (CE) was 97% and voltage efficiency (VE) was 78%. In addition, the discharge capacity was $1.44Ah{\cdot}L^{-1}$ which was 54% of theoretical capacity ($2.68Ah{\cdot}L^{-1}$) at $10^{th}$ cycle and the capacity loss rate was $0.0015Ah{\cdot}L^{-1}$ per cycle during 50 cycles. Through cyclic voltammetry test, it seems that this difference in the performance between the full cell using Nafion 117 membrane and Fumasep anion exchange membrane came from increasing resistance due to chemical reaction between membrane and active material, not the capacity loss due to cross-over of active material through membrane.
In this study, conductive polymers and the enzyme tyrosinase (Tyr) were deposited on the surface of a screen printed carbon electrode (SPCE), which can be fabricated as a disposable sensor chip, and applied to the detection of bisphenol F (BPF), an endocrine disruptor with proven links to male diseases and thyroid disorders, using electrochemical methods. On the surface of the SPCE working electrode, which was negatively charged by oxygen plasma treatment, a positively charged conductive polymer, poly(diallyldimethyl ammonium chloride) (PDDA), a negatively charged polymer compound, poly(sodium 4-styrenesulfonate) (PSS), and another layer of PDDA were layered by electrostatic attraction in the order of PDDA, PSS, and finally PDDA. Then, a layer of Tyr, which was negatively charged due to pH adjustment to 7.0, was added to create a PDDA-PSS-PDDA-Tyr sensor for BPF. When the electrode sensor is exposed to a BPF solution, which is the substrate and target analyte, 4,4'-methylenebis(cyclohexa-3,5-diene-1,2-dione) is generated by an oxidation reaction with the Tyr enzyme on the electrode surface. The reduction process of the product at 0.1 V (vs. Ag/AgCl) generating 4,4'-methylenebis(benzene-1,2-diol) was measured using cyclic and differential pulse voltammetries, resulting in a change in the peak current with respect to the concentration of BPF. In addition, we compared the detection performance of BPF using an ionic liquid electrolyte as an alternative to phosphate-buffered saline, which has been used in many previous sensing studies. Furthermore, the selectivity of bisphenol S, which acts as an interfering substance with a similar structure to BPF, was investigated. Finally, we demonstrated the practical applicability of the sensor by applying it to analyze the concentration of BPF in real samples prepared in the laboratory.
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