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.
Clayey ores of the Jeonnam province mainly consist of pyrophyllite (monoclinic), kaolinite (1T), and minor amounts of quartz, muscovite, and feldspars. Mineralogical studies revealed that two kinds of clay minerals were mainly produced from the volcanic sediments with similar ages and compositions. Kaolinite deposits sometimes contain neither diaspore nor corundum, but alunites are often found in the upper portions of the kaolin ore bodies. On the other hand, corundum and diaspore are commoner in the pyrophyllite deposits than the kaolin deposits. As ages of rock formations are becoming younger, amounts of pyrophyllite and kaolinite are rather radically decreased, and finally disappeared. But muscovite, quartz, and plagioclase feldspars are inclined to be preserved because of weak alteration. Most of clay ore bodies contain purple tuff beds on the uppermost portion, and silicified beds, tuff, and lapillistone are found in an ascending order in the most of clay quarries. Chemical analyses show that higher contents of $Al_2O_3$ might not necessarily be due to the argillization, since some tuffs contain higher $Al_2O_3$ contents originated from feldspars. $SiO_2$ contents are fairly higher in the silicified beds than in those of adjacent formations, which might have been introduced from the ore bodies. And $K_2O$ contents are obviously lower than those of $Na_2O$ and CaO in the ores and their vicinities. Ignition losses of some of clays represent much higher contents than those of the ordinary ones because of the sporadic presence of alunite, diaspore and corundum which are accompanied with lots of $SO_4$ and $Al_2O_3$ contents. REE (rare earth element) abundances of most of volcanics and clay ores show rather higher LREE (light rare earth elements) contents, and represent small to moderately negative Eu anomalies. Though most of ores ususally show milky white color, fine-grained and well bedded formations which could be easily discernible in the most of outcrop. But more distinct characteristics are desirable where rather massive ore bodies exist. Purple tuffs and silicified beds above the ore bodies would be useful as marker horizons/key beds since they have rather obvious lithology, extension and mineralogy than those of other adjacent formations.
Some industrial minerals used in domestic industries such as monazite, apatite, bauxite, and ilmenite belong to NORM (Naturally Occurring Radioactive Materials) because they show a high radioactivity. Products, semi-products, wastes, and by-products which show higher radioactivity than NORM belong to TENORM (Technologically Enhanced Naturally Occurring Radioactive Materials). Apatite used for manufacturing phosphate fertilizer in Namhae Chemical company belongs to NORM, and its by-product, phospo-gypsum, belongs to TENORM. A geological investigation is needed for the future environmental impact assessment of the Namhae Chemical company's site. According to survey results of the Namhae Chemical company's site, soil mineral composition indicated the mixture of minerals derived from the country rock (quartz, feldspar, mica, $l4{\AA}$ mineral, kaolin and amphibole) and minerals from the gypsum open-air storage yard (gypsum and apatite). Soil samples showed average content of U 4.6 ppm and Th 10 ppm, which are similar to average crustal abundances. They also show average contents of $^{40}K$ 191-1,166 Bq/kg, $^{226}Ra$ 15.6-710 Bq/kg, and $^{232}Th$ 17.4-72.7 Bq/kg, which indicate moderate levels of radio nuclide. But $^{226}Ra$ anomaly in the gypsum open storage yard is clearly confirmed and $^{232}Th$ anomaly is also confirmed in the east road side of the factory and nearby mountain areas. Soil external hazard indices ranged 0.24-2.01 with the average 0.54. Although most external hazard indices were lower than 1, which means radiation hazard index to be negligible, 5 samples out of total 40 samples showed higher values than 1, and further detailed investigation is needed.
Bentonite layers are intercalated within the basal conglomerates in the Tertiary sedimentary basins of Kampo, Janggi and Pohang, southeastern Korea. Eighteen samples of the bentonites went through X-ray diffraction, scanning electron microscopy, heavy mineral analyses, chemical analyses and oxygen, hydrogen stable isotope analyses to define the mineralogical characters of the bentonites. Heavy minerals such as zircons, apatites, amphiboles and biotites separated from bentonites show clean and euhedral surfaces, which are the characteristic features of volcanic origin. But biotites from the Chunbook Conglomerate are found as altered and heavily broken flakes which implies longer transportation of these bentonites. $TiO_{2}/Al_{2}O_{3} ratios of <2 $\mu$m particle fractions (the Chunbook Conglomerate 0.031; Janggi 0.029; Kampo 0.025) suggest that those are originated from volcanic tuffs. That is, the higher the value is, the more mafic in chemical compositions of the original tuffs. Authigenic montmorillonite and zeolite minerals were observed by SEM, which indicates diagenesis origin of bentonites. But the samples from the Chunbook Conglomerate showed only chaotically packed clay flakes in the matrix of sands or conglomerates, which implies detrital influence, not authigenic origin. The structural formulae of montmorillonite from these basins reflects their environment of formation. Fe (Ⅵ) can show the redox condition of its past environment and much lower $Fe^{2+}(Ⅵ)/Fe^{3+}(Ⅵ)$ ratios in montmorillonite of the Chunbook Conglomerate imply the greater oxidizing influence. Calculated burial depths from oxygen stable isotope data of the samples from the Chunbook Conglomerate generally fall to the range of 929~963 m whereas the real burial depth of this area is only 530~580 m. This could be explained as the bentonites of the Chunbook conglomerate had not been formed in situ. Discriminant analyses with the data from chemical analyses and structural formulae of montmorillonites show that bentonites from three different basins could definitely be distinguished with each other. This result arises from the different chemical compositions of original volcanic ashes and the difference of sedimentary environments.
Kim, Yumi;Seo, Hyunhee;Jo, Kyoung-nam;Jung, Dayae;Shin, Seungwon;Huh, Min;Roh, Yul
Journal of the Mineralogical Society of Korea
/
v.31
no.2
/
pp.113-121
/
2018
Baekasan Acheon cave located in Hwasun-gun, Jeollanam-do is a natural limestone cave only found in this province. In this study, the mineralogical and geochemical characteristics of speleothems collected from Baekasan Acheon cave were identified and the capability of carbonate mineral formation by aerobic microorganisms enriched from the cave and the mineralogical and geochemical characteristics of carbonate minerals formed by the microorganisms were investigated. The samples of sediments (clay) and speleothems (shelfstone and cave coral) were collected at three sites in the cave. The samples of shelfstone and cave coral were identified mainly as carbonate mineral, Mg-rich calcite, and clay minerals were composed of quartz, muscovite, and vermiculite by X-ray diffraction (XRD) analysis. To cultivate the carbonate forming microorganisms, parts of the sediment and speleothems were placed in D-1 medium containing urea, respectively, and the growth of microorganisms was observed under the aerobic condition at room temperature. The capability of carbonate mineralization of the cultured Baekasan Acheon cave microorganisms was examined through adding 1% (v/v) of the cultured microorganisms and calcium sources, Ca-acetate or Ca-lactate, into the D-1 medium. XRD analysis showed that the microorganisms cultured in cave deposits formed calcium carbonate ($CaCO_3$) under all conditions, and these microbial carbonate minerals included calcite and vaterite. The morphological characteristics and chemical composition of biologically formed minerals were observed by SEM-EDS showed various crystal forms such as rhomboid, spherical, perforated surface with Ca, C, and O of major chemical components. The existence of such microorganisms in the cave can contribute the formation of carbonate minerals, and it is likely to affect the geochemical cycles of carbon and calcium in the cave.
To understand the characteristics of uranium distribution, and the correlation of the uranium content and major constituents in uraniferous black slates from the Jinsan area of Ogcheon Fold Terrain, forty representative specimens were analyzed by mineralogical and radiometric techniques. According to statistical analysis, the uranium has a positive correlation with organic carbon and limonite, but a negative relation to muscovite and other opaques. The relationship with the highest and meaningful correlation is between log uranium and organic carbon. The log uranium-organic carbon correlation coefficient is 0.845 and these two constituents have about 71.4% association. It suggests that the abundance of organic carbon controlled the uranium precipitation. The relationship of organic carbon to log uranium can be expressed by following regression equation log ($U_3O_8{\times}10^4+1$)=-1.3447+2.5599 log (organic carbon). The multiple regression equation of different major components to log uranium is log ($U_3O_8{\times}10^4+1$)=0.77396+ 0.04465 (organic carbon)+0.00574 (quartz)-0.00964 (muscovite)+0.37827 (biotite)-0.02286 (clay substance)+0.01268 (other silicates)+0.1032 (barite)-0.00224 (apatite)+0.01606 (calcite)+0.08258 (hematite)-0.02406 (limonite)-0.01715 (other opaques).
Syenite is not a common rock, unlike granitic rocks formed the major component of the continental crust. The aim of this study is to decipher the occurrences and detailed descriptive characteristics of the syenite distributed in Sancheong area, and to investigate the petrogenesis of the syenitic magma based on geochemical study. The dominant minerals in syenite are alkali feldspar (usually orthoclase and rarely microcline), plagioclase, amphibole, biotite, and quartz. Syenites are found in a wide variety of colors. The anhedral hornblende and biotite filling the boundary of feldspar and quartz indicate that the hydrous minerals were crystallized lately, and that water was insufficient at the beginning of crystallization in magma. According to the analysis of mineral composition, amphibole in syenite is mostly ferro-edenite, and the pressure is calculated as 3.3~4.9 kb with 11.9~17.3 km of emplacement depth. Biotite and pyroxene are plotted in the region of annite and hedenbergite, respectively. Based on petrochemical studies of major elements, syenite belongs to alkaline series, metaluminous, and I-type. On the other hand, the variation patterns of trace and rare earth elements of syenite differ from the patterns of diorite and granite. In the geochemical characteristics, syenite is different from gabbro-diorite spatially adjacent to syenite, as well as granite. These results suggest that each rock has been generated from the different sources of magma. Additionally, based on the experimental data, the syenitic magma can be formed (1) by the partial melting at a high pressure and dry system, (2) when the initial crystallization minerals to be residue with migration of the residual melts separated from the ascending cotectic magma (3) when fluorine compositions to be plentiful in the protolith and/or at depth of the magma. Based on the petrographic characteristics of the syenite, Sancheong syenitic magma may have been formed by partial melting in a dry system.
This study reports the results about the petrography and geochemical characteristics of 10 representative volacanic rocks. The Cretaceous volcanic rocks distributed in the vicinity of the Kageo island composed of andesitic rocks, dacitic welded tuff, and rhyolitic rocks in ascending order. Sedimentary rock is the basement in the study area covered with volcanic rocks. Andesitic rocks composed of pyroclastic volcanic breccia, lithic lapilli tuff and cryptocrystallin lava-flow. Most dacitic rocks are lapilli ash-flow welded tuff. Rhyolitic rocks consists of rhyolite tuff and rhyolite lava flow. Rhyolite tuff are lithic crystal ash-flow tuff and crystal vitric ash-flow tuff with somewhat accidental fragments of andesitic rocks, but dacitic rocks. The variation of major and trace element of the volcanic rocks show that contents of $Al_2O_3$, FeO, CaO, MgO, $TiO_2$ decrease with increasing of $SiO_2$. On the basis of Variation diagrams such as $Al_2O_3$ vs. CaO, Th/Yb vs. Ta/Yb, and $Ce_N/YB_N$ vs. $Ce_N$, these rocks represent mainly differentiation trend of calc-alkaline rock series. On the discriminant diagrams such as Ba/La and La/Th ratio, Rb vs. Y + Nb, the volcanic rocks in study area belongs to high-K Orogenic suites, with abundances of trace element and ternary diagram of K, Na, Ca. According to the tectonic discriminant diagram by Wood, these rocks falls into the diestructructive continental margin. K-Ar ages of whole rocks are from andesite to rhyolite $97.0{\pm}6.8~94.5{\pm}6.6,\68.9{\pm}4.8,\61.5{\pm}4.9~60.7{\pm}4.2$ Ma, repectively. Volcanic rocks in study area show well correlation to the Yucheon Group in terms of rock age dating and geochemcial data, and derived from andesitic calc-alkaline magma that undergone low pressure fractional crystallization dominated plagioclase at <30km.
The sediment collected from KODOS91-1 were studied using X-ray diffraction(SRD) analysis to clarify the composition and vertical distribution of clay minerals. Micropaleontological data(Radiolarians) was applied to identify the changes in post-depositional environment and chemical mechanism leading to the formation of authigenic minerals. The result show that the highest concentration of smectite is occurred in the lower part(Unit II, III) of sediment column and the lowest concentration in the upper part(Unit I) whereas terrestrial minerals, such as illite, kaolinite and quartz, indicate the opposite trends. Radiolarians in the upper part are composed entirely of Quaternary/Tertiary mixtures, whereas in lower sediment units generally revealed the middle Miocene to the Eocene. This may imply that the Quaternary and Tertiary sedimentary processes were continuously affected by reworking of older sediments and subsequent resegmentation. The changes of the sediment color, peak pattern of minerals and presence of reworked microfossils at the unit boundaries have been interpreted as evidence of authigenic formation. Mineralogical characteristics of the sediments in study area strongly indicates changes in paleoenvironments through geologic time, including changes in post-depositional conditions by physical processes and chemical mechanisms.
Late Cretaceous to early Tertiary volcanic rocks in the Kyongsang basin exhibit high-K calc-alkaline characteristics, and originated from the magmatism related genetically to subduction of Kula-Pacific plate. They represent HFSE depletion and LlLE enrichment characteristics as shown by magmas related to subduction. Early studies on the depth of magma generation has been estimated as 180-230 km based on K-h relation should be reevaluated, because the depth of peridotite partial melting with 0.4 wt. % water is 80-120 km at subduction zone, and subducting slab in premature arc can melted even lower than 70 km. Moreover the increase of potassium contents depends on either contamination of crustal material and fluids of subducting slab or low degree of partial melting. If the inclination of subduction zone is 30 degrees and the depth to the Benioff zone is 180-230 km, the calculated distance between the volcanic zone and trench axis would be 310-400 km. It is unlikely because the distance between the Kyongsang basin and trench during late Cretaceous to early Tertiary is closer than this value and not comparable with generally-accepted models in subduction zone magmatism. $K_{55}$ of the volcanics in the Kyongsang basin is 0.3-2.3 wt.% and the average indicate that the depth ranges between 80-170 km on the diagram of Marsh, Carmichael (1974). Fractionation from garnet lherzolite, assumed the depth of 180-230km, is not consistent with the REE patterns of the volcanoes in the Kyongsang basin. Futhermore, the range of depth suggested by many workers, who studied magmatism related to subduction, imply shallower than this depth. Crustal thickness calculated by the content of CaO and $Na_2O$ is about 30 km and about 35 km, respectively. Paleo-crustal thickness during late Cretaceous to early Tertiary times in the Kyongsang basin inferred about 30 km calculated by La/Sm versus LaJYb data, which is also supported by many previous studies.
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