• Journal of the Mineralogical Society of Korea
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• v.29 no.4
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• pp.221-227
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• 2016

Copper is an essential transition metal involving in various biogeochemical processes. With the recent advances in analytical techniques and mass spectrometry, such as MC-ICP-MS, it is possible to measure Cu isotopes, which allows us to understand various biogeochemical processes in detail. Nonetheless, few studies have been performed in South Korea. In this study, we compared two purification methods previously reported using an anion exchange resin ($AG^{(R)}$ MP-1M), developed the best method in our lab environment, and then verified it by measuring Cu isotopic compositions in two USGS geological reference materials (BHVO-2 and BIR-1a). Although all matrix cations causing mass bias were effectively removed through both two methods with the yield of better than 95%, the method using the mixture of HCl and $H_2O_2$ only displays Cu isotopic compositions, in excellent agreement with reported values within the error. The method developed in this study is expected to be commonly applied to earth and environmental sciences.

• Analytical Science and Technology
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• v.26 no.5
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• pp.333-339
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• 2013

This study was conducted to build up the inventories of Pb isotopic compositions of major Pb pollution sources in South Korea. Since non-ferrous metal smelters are one of major anthropogenic sources, two smelters for zinc, each one of smelter for lead and copper were selected for the study. The Pb concentrations and isotopic compositions of metal ores, wastewater, sludge, metal rod and produced sulfuric acid were analysed to understand the Pb isotopic patterns in environment. The isotopic ratio, $^{206}Pb/^{207}Pb$, of zinc ores from zinc smelter were in the range of 1.179~1.198 and the ratio of waste, flue gas and products samples were 1.105~1.147. This results implied that the isotopic patterns of output samples showed mixing patterns between two distinct metal ore soerces. In 2011, major importing countries of zinc ore were Australia, Peru and Mexico. Thus Pb isotopic patterns from zinc smelter is originated from the mixing patterns between less radiogenic Australian ores and more radiogenic South America's ores. Lead smelters also showed the same mixing patterns with those of zinc smelters. However copper smelter showed same Pb isotopic patterns with more radiogenic South America's ores.

• Economic and Environmental Geology
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• v.38 no.4 s.173
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• pp.421-434
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• 2005

Abstract Based onthe characteristics of Carlin-type gold deposit in Nevada district, a potential in Korea is evaluated to the Yemi area where is structurally controlled by folds and trust fault. The fault of high angles are combined with a more permeable rocks such as the Yemi breccia and laminated silty limestone. The pattern of enrichment factors for Tl, Sb, As, Ag, Pb, Zn, Cu, Mo and W of limestones in the southern area are geochemically similar with those reported from the Carlin-type Bold deposit. Moreover, the oxygen and carbon isotopes show a hydrothermal alteration is widely developed in this area. According to the result of geophysical interpretation, stable isotope, alteration mineralogy, geochemical study, and geological structure, this mineralized zone may be extended to the M direction, so a detailed systematic exploration is required to identify this alteration zone.

• Korean Journal of Heritage: History & Science
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• v.49 no.3
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• pp.4-11
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• 2016

This study compares eight bronze spoons in the Goryeo Dynasty and analyzes their components and lead isotopes in order to confirm the relationship between their production sites and excavation sites. Most of the excavated spoons have elliptical heads, and their handles are categorized into two types. Bronze spoons are made of binary Cu-Sn alloys, but Pb is not added. The same artifacts can have different trace elements depending on location, and the spoons had high Ag content. According to an analysis of their lead isotopic ratio, they were made with raw materials produced in Zone 3 of the South Korean galena map. If the data of the trace elements in the raw ores of the bronze is accumulated, it can be used to indicate the provenance of the artifacts.

• Economic and Environmental Geology
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• v.56 no.4
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• pp.475-499
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• 2023

To infer the provenance of raw iron materials utilized in iron production at the archaeological sites in Gyeongsang province, petrographic and geochemical analyses were conducted for smelting samples and major iron ores sourced from ore deposits. The smelting samples excavated from various iron archaeological sites were classified into different types according to their refining processes, such as iron bloom, iron bloom slag, pig iron, pig iron slag, forging iron flake, smithery iron, iron flake, and arrowhead. These samples exhibited discernable differences in their mineralogical components and texture. The enrichments of major elements such as aluminum and calcium in silicate minerals of the residual slags and the high contents of trace elements such as nickel and copper in some iron-making relics reflect the characteristics of raw iron ores, and thus can be regarded as potential indicators for inferring the provenance of source materials. In particular, the compositional ranges of Pb-Sr isotope ratios for the iron smelting samples were classified into three categories: 1) those exhibiting similar ratios to those of the raw iron ores, 2) those enriched in strontium isotope ratio, and 3) those enriched in both lead and strontium isotope ratios. The observed distinct Pb-Sr isotope characteristics in the iron smelting samples suggest the potential contribution of specific additives being introduced during the high-temperature refining process. These results provide a new perspective on the interpretation of the provenance study of the iron archaeological samples in Gyeongsang province, particularly in terms of the potential contribution of additives on the refining process.

• Analytical Science and Technology
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• v.13 no.3
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• pp.297-303
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• 2000

Isotope-dilution inductively coupled plasma mass spectrometry was used to determine trace amounts of Cd, Cu, Pb, Ni and Zn in sediment. Sediment samples were dissolved by microwave digestion with addition of mixed acid ($HNO_3$, HF and $HClO_4$). Lead was determined after separation of alkaline and alkaline earth metals by an ammonium pyrrolidenedithiocarbarmate (APDC) solvent extraction. The other elements were determined after separation of iron, tin and titanium by hydroxide precipitation. Recovery efficiency of the analyte elements was not satisfactory, but most of matrix elements causing the isobaric interference could be effectively eliminated by the separation. Good agreement was achieved with the certified values in the analysis of the two sediment reference materials.

• Analytical Science and Technology
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• v.31 no.6
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• pp.240-246
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• 2018

The present study analyzed standard samples of three types of aluminum matrix certified reference materials (CRM) using GD-MS. Calibration curves were constructed for 13 elements (Mg, Si, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Sn, and Pb), with the slope representing the relative sensitivity factor (RSF). The x- and y-axes of the calibration curve represented ion beam ratio (IBR) and the authenticated value of the standard sample, respectively. In order to evaluate precision and linearity of the calibration curve, RSD and the coefficient of determination were calculated. Curve RSD for every element reflected high precision (within 10 %). For most elements, the coefficient of determination was ${\geq}0.99$, indicating excellent linearity. However, vanadium, nickel, and gallium curves exhibited relatively low linearity (0.90~0.95), likely due to their narrow concentration ranges. Standard RSF was calculated using the slope of the curve generated for three types of CRM. Despite vanadium, nickel, and gallium exhibiting low coefficients of determination, their standard RSF resembled that of the three types of CRM. Therefore, the RSF method may be used for element quantitation. Standard iron matrix samples were analyzed to verify the applicability of the aluminum matrix standard RSF, as well as to calculate the RSD-estimated error of the measured value relative to the actual standard value. Six elements (Al, Si, V, Cr, Mn, and Ni) exhibited an RSD of approximately 30 %, while the RSD of Cu was 77 %. In general, Cu isotopes are subject to interference: $^{63}Cu$ to $^{54}Fe^{2+}-^{36}Ar$ and $^{65}Cu$ to $^{56}Fe-Al^{3+}$ interference. Thus, the influence of these impurities may have contributed to the high RSD value observed for Cu. To reliably identify copper, the resolution should be set at ${\geq}8000$. However, high resolutions are inappropriate for analyzing trace elements, as it lowers ion permeability. In conclusion, quantitation of even relatively low amounts of six elements (Al, Si, V, Cr, Mn, and Ni) is possible using this method.

• Korean Journal of Mineralogy and Petrology
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• v.34 no.4
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• pp.219-226
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• 2021

We examined component analysis and lead isotope ratio analysis to find out the relationship between the excavation and the production site of 25 bronze weapons from prehistoric ages. All 25 bronze weapons are ternary alloys of copper-tin-lead and lead is artificially added. The lead isotope ratios of 25 bronze weapons show that bronze are made by raw materials in the southern regions of the Korean Peninsula, including northern China. The raw materials of narrow-shaped bronze dagger are supplied in zone 1-3 and northern China. In addition, provenance of lead for bronze halberd and pearhead are the rest of the region except for zone 1 and zone 4. Silver are enriched in most samples and zinc and cobalt are deficient. Arsenic and antimony detected only specific samples and can be used as critical parameter for provenance study. Lead isotopes and trace elements of archaeological bronzes will provide conservation scientist with useful tool to study the provenance of raw materials

• Economic and Environmental Geology
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• v.44 no.3
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• pp.193-201
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• 2011

The Geopung Cu deposit consists of two subparallel quartz veins that till the NE-trending fissures in Triassic Cheongsan granite. The quartz veins occur mainly massive with partially cavity and breccia. They can be followed along strike for about 500 m and varies in thickness from 0.2 to 2.2 m. Based on the mineralogy and paragenesis of veins, mineralization of quartz veins can be divided into hypogene and supergene stages. Hypogene stage is associated with hydrothermal alteration minerals such as sericite, pyrite, quartz, chlorite, clay minerals and sulfides such as pyrite, arsenopyrite, pyrrhotite, marcasite, sphalerite, stannite, chalcopyrite and galena. Supergene stage is composed of geothite. Fluid inclusion data from quartz indicate that homogenization temperatures and salinity of hypogene stage range from 163 to $356^{\circ}C$ and from 0.2 to 7.2 wt.% eq. NaCl, respectively. They suggest that ore forming fluids were progressively cooled and diluted from mixing with meteoric water. Sulfur (${\delta}^{34}S$: 4.3~9.2‰) isotope composition indicates that ore sulfur was derived from mainly magmatic source although there is a partial derivation from the host rocks. The calculated oxygen (${\delta}^{18}O$: 0.9~4.0‰) and hydrogen (${\delta}D$: -86~-69‰) isotope compositions suggest that magmatic and meteoric ore fluids were equally important for the formation of the Geopung Cu deposit and then overlapped to some degree with another type of meteoric water during mineralization.

• Journal of Conservation Science
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• v.30 no.4
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• pp.345-351
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• 2014

Chemical and Pb isotope analysis were performed in order to determine the origin of bronze artefacts excavated from the Inyongsaji site in South Korea. The result of ICP-MS shows that they are tin bronzes in which lead was not intentionally added during production. Pb isotope data analyzed by TIMS are plotted in the southern region of Korea and China of the distribution map drawn by Mabuchi(1985). On the other hand, the identical isotope data are plotted in the Taebaek basin and the Olcheon metamorphic belt correspondent to zone2 and zone3 respectively. It is believed that the isotope data on the tin bronzes which have very low lead content can be used to trace the origin of copper ore rather than those of either lead or tin ore. Pb istope analysis allows diverse interpretation as it can be applied to any object containing trace amounts of lead. In addition, accumulation of isotope data as well as further studies will improve reliability of the provenance studies.