One piece of Haedong-Tongue(해동통보) minted at 1,102 A.D. was excavated from No.20 wooden coffin, Sinbong-dong, Cheongju. It was analyzed by micro-XRF and ICP and determined the concentrations of ten elements such as Cu, Pb, Sn, Zn, Fe, Mn, Sb, Co, As, Ag and Ni. The measurement of lead isotope ratios was also carried out in order to predict the provenance of raw materials used for minting of Haedong-Tongbo. It was found that Haedong-Tongbo was minted with three compositions of $Cu\;75.5\%,\;Pb\;13.3\%\;and\;Sn\;6.0\%$, which were different from the typical composition of Chosen-Tongbo and Sangpyung-Tongbo used in Chosen dynasty. Lead isotope ratios of Haedong-Tongbo showed that the provenance of lead used for minting of it suggested the possibility to be originated from Southern part of Korea.
Mn-Pb-Zn-Ag deposits of the Janggun mine are hosted in the Cambro-Ordovician Janggun limestone mostly along the contacts of the Jurassic Chunyang granite. The deposits are represented by several ore pipes and steeply dipping lenticular bodies consisting of lower Pb-Zn-Ag sulfide ores and upper manganese carbonate and oxide ores. The former consists mainly of arsenic, antimony, silver, manganese, and tin-bearing sulfides, whereas the latter are characterized by hypogene rhodochrosite, and superficial manganese oxides including todorokite, nsutite, pyrolusite, cryptomelane, birnesite and janggunite. Origin of the upper manganese ore deposits has been a controversial subject among geologists for this mine: hydrothermal metasomatic vs. syngenetic sedimentary origin. Syngenetic advocators have proposed a new sedimentary rock, rhodochrostone, which is composed mainly of rhodochrosite in mineralogy. In the present study, carbon, oxygen and sulfur isotopic compositions were analayzed obtaining results as follows: Rhodochrosite minerals, (Mn, Ca, Mg, Fe) $CO_3$, from hydrothermal veins, massive sulfide ores and replacement ores in dolomitic limestone range in isotopic value from -4.2 to -6.3‰ in ${\delta}^{13}C$(PDB) and +7.6 to +12.9‰ in ${\delta}^{18}O$(SMOW) with a mean value of -5.3‰ in ${\delta}^{13}C$ and +10.7‰ in ${\delta}^{18}O$. The rhodochrosite bearing limestone and dolomitic limestone show average isotopic values of -1.5‰ in ${\delta}^{13}C$ and +17.5‰ in ${\delta}^{18}O$, which differ from those of the rhodochrosite mentioned above. This implies that the carbon and oxygen in ore fluids and host limestone were not derived from an identical source. ${\delta}^{34}S$ values of sulfide minerals exhibit a narrow range, +2.0 to +5.0‰ and isotopic temperature appeared to be about $288{\sim}343^{\circ}C$. Calculated initial isotopic values of rhodochrosite minerals, ${\delta}^{18}O_{H_2O}=+6.6$ to +10.6‰ and ${\delta}^{13}C_{CO_2}=-4.0$ to -5.1 ‰, strongly suggest that carbonate waters should be deep seated in origin. Isotopic data of manganese oxide ores derived from hypogene rhodochrosites suggest that the oxygen of the limestone host rock rather than those of meteoric waters contribute to form manganese oxide ores above the water table.
Ore mineralization of the Hwanghak copper deposit in the Ogsan area occurred in three stages of quartz (stage I and II) and calcite (stage III) veining along fissures in Early Cretaceous sedimentary rocks. Ore minerals are pyrite, pyrrhotite, chalcopyrite (dominant), sphalerite, hematite, galena, and Ag-, Pb-, and Bi-sulfosalts. These were deposited during the first stage at temperatures between $370^{\circ}C$ and < $200^{\circ}C$ from fluids with salinities between 0.5 and 7.6 equiv. wt. % NaCl. There is evidence of boiling and this suggests pressures of less than 180 bars during the first stage. Equilibrium thermodynamic interpretation accompanying with mineral paragenesis and fluid inclusion data indicates that copper precipitation in the hydrothermal system occurred due to cooling and changing in chemical conditions ($fs_2$, $fo_2$, pH). Gradual temperature decrease from $350^{\circ}$ to $250^{\circ}C$ of ore fluids by boiling and mixing with less-evolved meteoric waters mainly led to copper deposition through destabilization of copper chloride complexes. Sulfur isotope values of sulfide minerals decrease systematically with paragenetic time from calculated ${\delta}^{34}S_{H_2S}$ values of 8.2 to 4.7‰. These values, together with the observed change from sulfide-only to sulfide-hematite assemblages and fluid inclusion data, suggest progressively more oxidizing conditions, with a corresponding increase of the $sulfate/H_2S$ ratio of hydrothermal fluids. Measured and calculated hydrogen and oxygen isotope valutls of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values.
No, Sang-gun;Lee, Seung-han;Park, Ki-woong;Jeong, Hyeon-guk;Yun, Ji-seong;Kim, Sun-ok;Park, Maeng-eon
Economic and Environmental Geology
/
v.51
no.3
/
pp.213-222
/
2018
Metasediment-hosted Pb-Zn mineralized zone has been found in Dyusembay of Kazakhstan. Its petrological properties, metal index, alteration index and redox-sensitivity are compared with those of SEDEX type deposit. Mineralization is developed along foliation of host rock (graphitic phyllite) and controlled by folds and faults; major ore minerals including pyrite, pyrrhotite, sphalerite, and galena are disseminated or interlayered with fine-grained quartz. The margin of the mineralized zone is metamorphosed accompanying sericite and chlorite. Hydrothermal brecciation and Pb-Zn mineralization formed in quartz-calcite stockworks are confirmed at the around of Maytyubin granitoid intrusions. The mineralization is classified into three types according to those of occurrence, paragenesis, chemical composition and isotopic characteristics. Type 1 whose fine-grained pyrite, pyrrhotite and sphalerite are formed in parallel yet discontinuous to well-developed foliations of the host rock; its geochemistry is similar to those of the earlier stage in SEDEX-type mineralization. In case of type 2, the ore minerals of which are concentrated being parallel to a foliation by regional metamorphism, and most of them associated with quartz and muscovite (${\pm}$ biotite) paragenetically. Type 3 is formed in the hydrothermal breccia zone whose ore minerals are controlled by foliation and breccia and developed in quartz ${\pm}$ calcite veins having a form such as stratification, stockwork or veinlets. Host rocks in the mineralized zone indicate homogeneous metamorphic grade and there is no specific alteration zonation. Also, all types (type 1, type 2, and type 3) represent similar REEs patterns, it can be interpreted that these are originated from a same source. Sulphides occurred in mineralized zone indicate a limited range of sulphur isotope values (type 2, ${\delta}^{34}S=-13.3{\sim}-11.7$‰; type 3, ${\delta}^{34}S=-13.9{\sim}-8.2$‰), and a result of geothermometry presents different temperature ranges: type 2($251{\pm}38^{\circ}C{\sim}277{\pm}40^{\circ}C$); type 3($360{\pm}2^{\circ}C$ to $537{\pm}29^{\circ}C$). It is estimated to be due to the effect of metamorphism and Maytyubin granitoid intrusions, respectively. In addition, ternary chart of thorium, scandium, and zircon for discrimination of tectonic setting and redox sensitivity using V/Mo values indicate that hydrothermal sediments put on reduction environment after precipitation, before being affected by metamorphism and intrusion activity. Geochemical data are plotted on a distal trend of SEDEX-type with discrimination plot using SEDEX index. As a result, petrological-geochemical properties demonstrate that Dyusembay Pb-Zn mineralized zone is comparable to distal-type of SEDEX deposit.
Vibrio sp. S-1-2 was isolated from seawater in the Masan bay and its bacterial characteristics and bioaccumulation of $CdCl_2$ in the cell were investigated. As the result of microscopic and biochemical test, the S-1-2 strain was identified to Vibrio sp. and this strain can be tolerated even in 200 ppm $CdCl_2$ media, however its growth was inhibited. In 25 ppm $ZnCl_2$ media, the growth of Cd resistant Vibrio sp. S-1-2 was promoted at later stage of growth. The growth of Vibrio sp. S-1-2 was inhibited on 25 ppm $CuCl_2$ and $PbCl_2$ media and was not able to grow in 25 ppm $HgCl_2$ media at all. The uptake of cadium in the cells was increased exponentially with increasing concentration of $CdCl_2$ in media. But the uptake rate of cadmium was suddenly inhibited at 50 ppm $CdCl_2$ media. Optimal pH and NaCl concentration for bioaccumulation of $CdCl_2$ were 8-9 and 1-2%, respectively. In the case of pH, maximum dpm value was found at pH 7 after 96 hours culture and in the case of NaCl concentration, it was detected in 2% NaCl media after 36 hours culture.
We carried out the U-Pb age dating of zircon from basement rocks in the southern part of the Danyang National Geopark. Two migmatitic gneisses composed of biotite±sillimanite±garnet+feldspar+quartz were dated. Leucosomes in the samples were clearly distinguished from their melanosomes. The U-Pb isotopic compositions of zircon from sillimanite- and garnet-bearing migmatitic samples were measured using a secondary ion microprobe, yielding metamorphic ages, 1870±10 Ma (2σ)와 1863±6 Ma (2σ), respectively. 1.87~1.86 Ga metamorphic ages are consistent with those of the Paleoproterozoic low-P and high-T regional metamorphism (1.87~1.85 Ga) in the Yeongnam Massif. The maximum depositional age based upon the apparent 207Pb/206Pb ages of detrital zircon in the samples was estimated as 2.06 Ga, and thus sedimentation age of the protolith of the migmatitic gneisses ranges between 2.06 and 1.87 Ga.
An experiment was performed for zone refined Re-filament and normal (nonzone refined) Re-filament to reduce the background effect on the measurement of low level uranium samples. From both filaments, the signals which seemed to come from a cluster of light alkali elements, $(^{39}K_6)^+$, $(^{39}K_5+^{41}K)^+$ and $PbO_2$ were identified as the isobaric effect of the uranium isotopes. The isobaric effect signal was completely disappeared by heating the filament about $2000^{\circ}C$ at < $10^{-7}$ torr of vacuum for more than 1.5 hour in zone refined Refilaments, while that from the normal Re-filaments was not disappeared completely and was still remained as 3 pg. of uranium as the impurities after the degassing treatment was performed for more than 5 hours at the same condition of zone refined filaments. A threshold condition eliminating impurities were proved to be at 5 A and 30 minutes of degassing time. The uranium content as an impurity in rhenium filament was checked with a filament degassing treatment using the U-233 spike by isotope dilution mass spectrometry. A 0.31 ng of U was detected in rhenium filament without degassing, while only 3 pg of U was detected with baking treatment at a current of 5.5 A for 1 hr. Using normal Re-filaments for the ultra trace of uranium sample analysis had something problem because uranium remains to be 3 pg on the filament even though degassed for long hours. If the 1 ng uranium were measured, 0.3% error occurred basically. It was also conformed that ionization filament current was recommended not to be increased over 5.5 A to reduce the background. Finally, the contents of uranium isotopes in uranium standard materials (KRISS standard material and NIST standard materials, U-005 and U-030) were measured and compared with certified values. The differences between them showed 0.04% for U-235, 2% for U-234 and 2% for U-236, respectively.
Park, Ki-Hwa;Park, Hee-In;Eastoe, Christopher J.;Choi, Suck-Won
Economic and Environmental Geology
/
v.24
no.2
/
pp.131-150
/
1991
The Weolseong diatreme was temporally and spatially related to the intrusion of the Gadaeri granite, and was -mineralized by meteoric aqueous fluids. In the Nokdong As-Zn deposit, pyrite, aresenopyrite and sphalerite are the most abundant sulfide minerals. They are associated with minor amount of magnetite, pyrrhotite, chalcopyrite and cassiterite, and trace amounts of Pb-Sb-Bi-Ag sulphosalts. The AsZn ore probably occurred at about $350^{\circ}C$ according to fluid inclusion and compositional data estimated from the arsenic content of arsenopyrite and iron content of sphalerite intergrown with pyrrhotite + chalcopyrite + cubanite. Heating studies of fluid inclusions in quartz indicate a temperature range between 180 and $360^{\circ}C$, and freezing data indicate a salinity range from 0.8 to 4.1 eq.wt % NaCl. The coexisting assemblage pyrite + pyrrhotite + arsenopyrite suggests that $H_2S$ was the dominate reduced sulfur species, and defines fluid parameter thus: $10^{-34.5}$ < ${\alpha}_{S_2}$ < $10^{-33}$, $10^{-11}$ < $f_{S_2}$ < $10^{-8}$, -2.4 < ${\alpha}_{S_2}$ < -1.6 atm and pH= 5.2 (sericte stable) at $300^{\circ}C$. The sulfur isotope values ranged from 1.8 to 5.5% and indicate that the sulfur in the sulfides is of magmatic in origin. The carbon isotope values range from -7.8 to -11.6%, and the oxygen isotope values from the carbonates in mineralized wall rock range from 2 to 11.4%. The oxygen isotope compositions of water coexisting with calcite require an input of meteoric water. The geochemical data indicate that the ore-forming fluid probably was generated by a variety of mechanisms, including deep circulation of meteoric water driven by magmatic heat, with possible input of magniatic water and ore component.
Composition analysis and lead isotope ratio analysis were conducted to determine the coloring machanism on lead glaze used in Gyeongbokgung Palace and the provenance of the lead used as a flux. 31 blue tiles were classified into green, blue, and yellow. The chemical analysis of lead glazes on the blue tiles revealed that Pb, Si, and Cu were the main components, and trace amounts of Fe, Ca, Mg, and Al were detected. The Cu content was high in blue lead glaze, while Cu was not detected in yellow or brown lead glaze which instead had high Fe content. Therefore, it was found that lead was used as a flux and copper oxide as a coloring agent in the production of lead glaze. In addition, the lead isotope ratios of the lead glaze used in the blue tiles of Gyeongbokgung palace were plotted in zone 3 on the distribution map of lead isotope ratios on the Korean Peninsula, which includes Chungcheong-do and Jeolla-do. It is presumed that the flux for the lead glaze was sourced from galena found in these regions. The lead isotope ratios of the green glaze from the Three Kingdoms and Unified Silla period were mostly located outside the Korean Peninsula, showing that the provenance of lead had changed. In particular, the lead isotope ratios of the green glaze from the Three Kingdoms and Unified Silla period suggest exchange with neighboring countries. Also the lead isotope ratios of the green glazes from the same temple are different, so it is believed that they were made at different times or in different workshops.
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.
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