The present paper summerizes the studies on clay mineralogical characteristics of Korean soil, relationship between potassium and clay minerals, potassium release pattern of clay minerals and utilization of clay minerals for soil conditioner and fertilizers, which have been carried out in this laboratory. 1. The red yellow podzolic soil is mostly abundant in the upland of Korea and mainly consists of halloysite and weathered intermediates of mica such as illite and vermiculite. 2. With regard to soil parent material, kaolin mineral occurs abundant in soils derived from granite and granite gneiss. Mica is dominant in basaltic soil. The main clay mineral of the soil, originated from the Tertiary, is found montmorillonite and the volcanic soil of Jeju Island has plenty of allophane as its main clay mineral. 3. It is confirmed that the soil fertility depends on the composition of clay minerals. The red yellow podzolic soil, containing lot of kaolin, shows low productivity while the montmorillonite soil has higher productivity. 4. The release rate of solid phase potassium (micas and fixed potassium) follows the 1st order reaction equation in the equilibrium solution of $IN-NH_4OAc$. The potassium release constant is positively correlated with the mica content of the clay but negatively correlated with the content of $14.5{\AA}$ minerals. On the other hand, the potassium release constant has very high correlation with the ratio(Kex/Kt) of exchangeable potassium(Kex) to total potassium(Kt). 5. It is also found that Kex/Kt has rather high correlation with the content of mica and $14.5{\AA}$ minerals existed in the clay as well as the mica content of the soil.
Acid sulfate soils occur extensively in Gimhae area where they have been formed from the brackish alluvial sediments along the sea coast and river estuary. The strong acid environment enhances silicate weathering and thus affects the soil clay minerals. The minerals were identified through chemical, X-ray diffraction and thermal methods. The ratio of $SiO_2$ and $Al_2O_3$ in the clay fractions ranged from 3.14 to 3.77, indicating that the distribution of the clay minerals were 1 : 1 and 2 : 1 minerals. Cation exchange capacity in the clay fractions was low due to high contents of 1 : 1 minerals and hydroxy interlayered vermiculite(HIV). The B and C horizon rich in jarosite have large amounts of yellow streaks which reflect high content of $Fe_2O_3$ and $K_2O$. Vermiculite and illite were quantified from thermogravimetry(TG), kaolin minerals from both TG and differential thermal analysis(DTA), and HIV from X-ray diffraction analysis. The dominant clay minerals were kaolin minerals, vermiculite, illite and HIV. HIV considered to be formed, especially, in acid soil environments. The minor minerals were quarts, feldspar, jarosite, pyrite, hematite and goethite. Kaolin minerals were the most abundant clay minerals throughout the acid sulfate soil. Kaolin minerals, however, increased towards the top of horizons throughout the soils and HIV decreased towards the top of horizons in the soil of Gimhae series and Haecheog series. Alteration of HIV to kaolin minerals during weathering of low pH condition in deep soil horizons may explain the high quantities of kaolin minerals and the relatively low quantities of HIV in the soil at top horizons.
Lee, Chan Hee;Jin, Hong Ju;Choi, Ji Soo;Na, Geon Ju
Journal of Conservation Science
/
v.32
no.2
/
pp.273-291
/
2016
Some ceramic artifacts representing time-wise from comb pattern pottery in the Neolithic Age to white porcelain in Joseon Dynasty were selected from 7 sites in the north and south area of Charyeong Mountain Range in order to making techniques interpretation and development process of ancient ceramics through physicochemical and mineralogical quantitative analysis. Studied pottery samples in the Prehistoric times showed trace of ring piling in soft-type, and pottery in the Three Kingdoms Period had both soft and hard-type but kettle-ware and storage-ware were made with ring piling, but table-ware was made by wheel spinning. Different from pottery after the Three Kingdom Period when refinement of source clay was high, pottery in the Neolithic Age and in the Bronze Age exhibited highly mineral content in sandy source clay, which showed a lot of larger temper than source clay. Groundmass of celadon and white porcelain almost did not reveal primary minerals but had high content of minerals by high temperature firing. Ceramic samples showed some different in major and minor elements according to sites irrespective of times. Geochemical behaviors are very similar indicating similar basic characteristics of source clay. However, loss-on-ignition showed 0.01 to 12.59wt.% range with a large deviation but it rapidly decreased moving from the Prehistoric times to the Three Kingdom Period. They have correlation with the weight loss due to firings, according to burning degree of source clay and detection of high temperature minerals, estimated firing temperatures are classified into 5 groups. Pottery in the Neolithic Age and in the Bronze Age belongs from 750 to $850^{\circ}C$ group; pottery in the Three Kingdom Period are variously found in 750 to $1,100^{\circ}C$ range of firing temperature; and it is believed celadon and white porcelain were baked in high temperature of 1,150 to $1,250^{\circ}C$. It seems difference between refinement of source clay and firing temperature based on production times resulted from change in raw material supply and firing method pursuant to development of production skill. However, there was difference in production methods even at the same period and it is thought that they were utilized according to use purpose and needs instead of evolved development simply to one direction.
This study focuses on identification of mineralogical and geochemical characteristics and interpretation of raw material sources for prehistoric chlorite beads excavated from Geoseokri site in Boseong and Buntori site in Haenam, Korea. These prehistoric beads consist of three grayish blue ring-shaped beads, one dark green tubular bead and one greenish black tubular bead that show acicular-columnar and fibrous microtexture. The beads are composed of $SiO_2$, $Al_2O_3$, MgO and FeO as majors and a trace amount of $K_2O$, CaO and Na_2O$. Mineral species is mostly chlorite with a small amount of quartz and feldspar. Quantitative analysis indicates that the grayish blue ring-shaped beads and the dark green tubular bead belong to clinochlore and the greenish black tubular bead does to the boundary between clinochlore and sheridantie. Chlorite is a hydrous phyllosilicate mineral and it shows various microtexture of acicular, sheeted, earthy, granular andfibrous shapes. As its hardness is 2, chlorite is easily engraved due to its softness. It has aesthetic worthy as it shows green, black and greenish gray colors and pearly to greasy luster as well. These factors would lead to the extensive use of chloritic beads as ornaments from prehistoric times. Though the mineral sources of the chlorite beads can be found in central western region of Chungnam and Iwon of Hamnam, those areas are too distant from the two relic sites. Instead, chlorite ores commonly occur as altered products in wall rock alteration zone of every hydrothermal deposit. Therefore, it is probable that raw materials of chlorite were supplied from neighboring hydrothermal environment rather than far deposits. The result needs further study to verify raw material provenance interpretation, supply, manufacture and distribution on the basis of archaeological points of view.
The Samgwang deposit has been one of the largest deposits in Korea. The deposit consists of series of host rocks including Precambrian metasedimentary rocks and Jurassic Baegunsa formation, which unconformably overlies the Precambrian metasedimentary rocks. The deposit consists of eight lens-shaped quartz veins which filled fractures along fault zones in Precambrian metasedimentary rock, which feature suggest that it is an orogenic-type deposit. Laminated quartz veins are common in the deposit which contain minerals including quartz, ankerite, white mica, chlorite, apatite, rutile, arsenopyrite, sphalerite, chalcopyrite and galena. The structural formulars of white micas from laminated quartz vein and wallrock alteration are determined to be (K1.02-0.82Na0.02-0.00Ca0.00)(Al1.73-1.58Mg0.26-0.16Fe0.23-0.10Mn0.00Ti0.03-0.01Cr0.01-0.00)(Si3.35-3.22Al0.79-0.65)O10(OH)2 and (K0.75-0.67Na0.01Ca0.00) (Al1.78-1.74Mg0.16-0.15Fe0.15-0.13Mn0.00Ti0.04-0.02Cr0.01-0.00)(Si3.33-3.26Al0.74-0.67)O10(OH)2, respectively. It suggest that white mica from laminated quartz vein has higher interlayer cation (K+Na+Ca) and Fe+Mg+Mn+Ti content in octahedral site compared to the white mica from the wallrock alteration. Compositional variations in white mica from laminated quartz vein can be caused by phengitic or Tschermark substitution ((Al3+)VI+(Al3+)IV <-> (Fe2+ or Mg2+)VI)+(Si4+)IV) and (Fe3+)VI <-> (Al3+)VI substitution. Ankerite from laminated quartz vein has compositional variations of FeO and MgO contents along crystal growth direction. The geochemical and textural features suggest that laminated quartz vein from the Samgwang gold-silver deposit was formed during ductile shear stage, which is an important main gold-silver ore-forming event in orogeinc deposit.
The purpose of this study was to investigate the possibility of eco-friendly/efficient recovery of valuable resources, such as Au from mine tailings, which are environmental pollutants in the Mongolian mine sector. For this purpose, this study selected 4 place of mine tailings of the Mongolian mines sector and carried out mineralogy evaluation of the valuable resources in the tailings. In this study, flotation was performed to separate and concentrate valuable resources in the tailings. Microwave nitric acid leaching was used to leach the valuable resources contained in the sample and to improve the Au grade. Chloride leaching attempted to leach Au from the leaching residues. XRD analysis of the tailings samples showed that most of the samples consisted of silicate minerals. As a result of confirming the content of the element through XRF analysis, the SiO2 content was very high, the Fe2O3 content was 2.32-4.23%, and the content of PbO, CuO and ZnO components were all within 2%. As a result of flotation for the tailings samples, the recovery of Au was the highest in Bayanairag sample (95.38%). As a result of microwave nitric solution experiment on Au concentrate sample obtained by flotation, the content of Au in the microwave nitrate leaching residue increased by 12.15% from 192.72 g/ton to 216.14g/ton in Khamo sample, the highest increase was 57.58% in Bayanairag sample. TCLP tests on tailings generated after flotation showed dissolution characteristics within EPA. Chloride leaching test was performed to recover Au from solid residues. The leaching rate was 87.43-89.35% within 10 minutes. For Khamo sample, 100% Au was leached after 60 minutes of leaching time. Therefore, in order to process the tailings continuously generated in Mongolia, applying the same process as the present study is expected to effectively recover the valuable resources contained in the tailings.
The atomic structures of silicate liquids at high pressure provide insights into the transport properties including thermal conductivities or elemental partitioning behavior between rocks and magmas in Earth's interior. Whereas the local electronic structure around silicon may vary with the arrangement of the nearby oxygens, the detailed nature of such relationship remains to be established. Here, we explored the atomic origin of the pressure-induced changes in the electronic structure around silicon by calculating the partial electronic density of states and L3-edge X-ray absorption spectra of SiO2 polymorphs. The result showed that the Si PDOS at the conduction band varies with the crystal structure and local atomic environments. Particularly, d-orbital showed the distinct features at 108 and 130 eV upon the changes in the coordination number of Si. Calculated Si XAS spectra showed features due to the s,d-orbitals at the conduction band and varied similarly with those observed in s,d-orbitals upon changes in the crystal structures. The calculated Si XAS spectrum for α-quartz was analogous to the experimental Si XRS spectrum for SiO2 glass, implying the overall similarities in the local atomic environments around the Si. The edge energies at the center of gravity of XAS spectra were closely related to the Si-O distance, thus showing the systematic changes upon densification. Current results suggest that the Si L2,3-edge XRS, sensitive probe of the Si-O distance, would be useful in unveiling the densification mechanism of silicate glasses and melts at high pressure.
The Shinri area near the Yedang Lake, the eastern part of the Hongseong area in SW Gyeonggi Massif, consists of the Neoproterozoic Duckjeongri granodiorite-tonalite, mylonitized amphibole-bearing orthogneiss and impure marble with lens-shaped garnet-bearing metabasites. In this paper, we report mineralogical and geochemical data of Neoproterozoic lens-shaped garnet-bearing metabasites within marble of the Shinri area. The $SiO_2$ contents of garnet-bearing metabasites in marble vary between ~46.98 and 51.17 wt%, and the $Na_2O$ + $K_2O$ contents fall between ~1.95 and 2.85 wt%, similar to the tholeiitic sub-alkaline basaltic rocks. In the Zr/Y vs. Zr diagram, garnet-bearing metabasites also plot in the subalkaline basaltic rocks. The chondrite-normalized REE patterns for Shinri garnet-bearing metabasites show relatively flat patterns to that of chondrite. They show slight LREE-enriched and depleted patterns. The major and trace element data from lens-shaped garnet-bearing metabasites in marble of the Shinri area suggest that these rocks were formed in within plate. In contrast, previous major and trace element data of high pressure type garnet-bearing metabasites from the mafic-ultramafic complex in the Baekdong and Bibong areas suggest that these rocks were formed in a nascent arc to backarc spreading center within subduction zone setting. Based on mineral assemblage and mineral chemistry, P-T estimates for Shinri garnet-bearing metabasites are 9.6-12.7 kb, $695-840^{\circ}C$ for inclusions in the core, and 9.6-13.6 kb, $630-755^{\circ}C$ for those in the rim. These P-T estimates are distinct from those of the Baekdong and Bibong garnet-bearing metabasites with isothermal decompressional retrograde P-T path. In addition to Triassic tectonic activity previously reported in the Shinri area of Hongseong, the details of metamorphic history such as protolith age and Neo-Proterozoic metamorphic episode need to be solved.
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.
A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.
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