• Economic and Environmental Geology
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• v.55 no.3
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• pp.261-271
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• 2022

Six gas samples were collected from coal and coaly shale from core AA-1, which was acquired from the Asem-Asem Basin, southeast Kalimantan, Indonesia. These coalbed gas samples were analyzed for the molecular composition, carbon isotope (δ¹³C_CH4, δ¹³C_C2, and δ¹³C_CO2), hydrogen isotope (δD_CH4), hydrocarbon index (C_HC), and carbon dioxide-methane index (CDMI) to document their origin and methanogenic pathways. Core AA-1 successively consists of lower clastic sedimentary rocks (Sedimentary Unit-1, SU-1) containing coal and coaly shale, and upper limestone (Sedimentary Unit-2, SU-2), unconformably underlain by serpentinized basement interpreted as part of the Cretaceous Meratus subduction complex (MSC). The coal and coaly shale (SU-1) were deposited in a marshes nearby a small-scale river. Compositions of coalbed gases show that methane ranges from 87.35 to 95.29% and ethane ranges from 3.65 to 9.97%. Carbon isotope of coalbed methane (δ¹³C_CH4) ranges from -60.3 to -58.8‰, while hydrogen isotope (δD_CH4) ranges from -252.9 to -252.1‰. Carbon isotope of coalbed ethane (δ¹³C_C2) ranges from -32.8 to -31.2‰, carbon isotope of coalbed carbon dioxide (δ¹³C_CO2) ranges from -8.6 to -6.2‰. The coalbed CO₂ is interpreted to be an abiogenic origin based on a combination of δ¹³C_CO2 and CDMI and could have been transported from underlying CO₂ bearing MSC through faults. The methanogenic pathways of coalbed gases are interpreted to have originated from primary methyl-type fermentation and mixed with CO₂ reduction, affecting thermogenic non-marine coal-type gases based on analyses of isotopic ratios and various indexes.

• Economic and Environmental Geology
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• v.42 no.4
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• pp.315-333
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• 2009

In this study, the hydrochemical and the isotopic characteristics of major streams in the Daejeon area were investigated during rainy and dry seasons. The stream water shows the electrical conductivity of the range of $37{\sim}527{\mu}s$/cm, and pH $6.21{\sim}9.83$. The chemical composition of stream waters can be grouped as three types: the upper streams of Ca(Mg)-$HCO_3$ type, Ca(Mg)-$SO_4(Cl)$ type of middle streams flowing through urban area, and Na(Ca)-$HCO_3$(Cl, $SO_4$) type of the down streams. Based on in-situ investigation, the high pH of stream waters flowing through urban area is likely to be caused by the inflow of a synthetic detergent discharging from the apartment complex. The electrical conductivity of stream waters at a dry season is higher than those of at a rainy season. We suggest that the hydro-chemical composition of stream waters in the Daejeon area was affected by the discharging water from the sewage treatment facilities and anthropogenic contaminants as well as the interaction with soil and rocks. ${\delta}D$ and ${\delta}^{18}O$ values of the stream waters show the relationship of ${\delta}D=6.45{\delta}^{18}O-7.4$, which is plotted at a lower area than global meteoric water line(GMWL) of Craig(1961). It is likely that this isotopic range results from the evaporation effect of stram waters and the change of an air mass. The isotope value shows an increasing trend from upper stream to lower stream, that reflects the isotopic altitude effect. The relationship between ${\delta}^{13}C$ and $EpCO_2$ indicates that the carbon as bicarbonate in stream water is mainly originated from $CO_2$ in the air and organic materials. The increasing trend of ${\delta}^{13}C$ value from upper stream waters to lower stream waters can be attributed to the following reasons: (1) an increasing dissolution of $CO_2$ gas from a contaminated air in downtown area of the Daejeon, and (2) the increment of an inorganic carbon of groundwater inflowed into stream by base flow. Based on the relationship between ${\delta}^{34}S$ and $SO_4$ of stream waters, the stream waters can be divided into four groups. $SO_4$ content increases as a following order: upper and middle Gab stream${\delta}^{34}S$ value decreases as above order. ${\delta}^{34}S$ value indicates that sulfur of stream waters is mainly originated from atmosphere, and is additionally supplied by pyrite source according to the increase of sulfate content. The sulfur isotope analysis of a synthetic detergent and sewage water as a potential source of the sulfur in stream waters is furtherly needed.

• Journal of the Korean earth science society
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• v.43 no.5
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• pp.569-578
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• 2022

Oceanic Anoxic Event 2 (OAE2) represents a period of mid-Cretaceous when black shale was deposited worldwide. This short period of perturbations in the global biogeochemical cycles spans the Cenomanian-Turonian boundary, marking the peak of the Cretaceous greenhouse, which is characterized by elevated atmospheric pCO₂, sealevel highstand, and expansion of oxygen minimum zone. Since the pioneering work in the 1970s, numerous studies have investigated the cause and consequences of the event based on geochemical and isotope proxies, and it is now widely accepted that the enhanced primary production and volcanism during the Cenomanian-Turonian boundary interval were the key environmental factors that triggered OAE2. This study briefly reviews previous OAE2 studies of the carbon, sulfur, and trace metal cycles for mechanistic understanding of the biogeochemical processes during the event.

• The Journal of the Petrological Society of Korea
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• v.10 no.3
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• pp.222-232
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• 2001

Secondary ion mass spectrometry (SIMS) uses focused high-speed primary ions to produce secondary ions from sample surface that are analyzed through a mass filter. SIMS is often called as ion microprobe, since it offers a micrometer-scale spatial resolution. Although the precision and accuracy of SIMS are not as good as many conventional mass spectrometers, it has several advantages such as small sample-size requirement, high spatial resolution and capability of in-situ analysis. In the field of geochemistry/cosmochemistry, SIMS is widely used for (1) stable isotope geochemistry of H, C, O, S, etc., (2) geochronology of U/Th-bearing minerals, (3) lateral distribution of trace elements in a mineral, and (4) discovery of presolar grains and investigation of their isotopic compositions.

• Economic and Environmental Geology
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• v.41 no.1
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• pp.1-14
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• 2008

The Bongsang gold-silver deposit consists of quartz veins that fill along the fault Bone within Cretaceous andesitic lapilli tuff. Mineralization is occurred within fault-breccia zones and can be divided into two stages. Stage I which can be subdivided into early and late depositional stages is main ore mineralization and stage II is barren. Stage I began with deposition of wall-rock alteration minerals and base-metal sulfides, and was deposited by later native silver, Ag-bearing tetrahedrite, polybasite and base-metal sulfides such like pyrite, sphalerite, chalcopyrite and galena. Fluid inclusion data indicate that homogenization temperatures and salinities of stage I range from 137 to $336^{\circ}C$ and from 0.0 to 10.6 wt.% NaCl, respectively. It suggests that ore forming fluids were cooled and diluted with the mixing of meteoric water. Also, temperature and sulfur fugacity deduced mineral assemblages of late stage I are $<210^{\circ}C\;and\;<10^{-15.4}$ atm, respectively. Sulfur(3.4%o) isotope composition indicates that ore sulfur was mainly derived from a magmatic source as well as the host rocks. The calculated oxygen{2.9%o, 10.3%o(quartz: 7.9%o, 8.9%o, calcite: 2.9%o, 10.3%o)}, hydrogen(-75%o) and carbon(-7.0%o, -5.9%o) isotope compositions indicate that hydrothermal fluids may be meteoric origin with some degree of mixing of another meteoric water for paragenetic time.

• Economic and Environmental Geology
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• v.32 no.2
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• pp.129-139
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• 1999

Hydrothermal gold deposits of the Trabong district in Vietnam occur as single-stage quartz $\pm$ calcite veins (0.3-1.2 m thick) which fill fault fractures in graphite-bearing gneiss and schist of the Chulai Complex and Kham Duc Formation of the Proterozoic age. Ore grades are 1.3 to 92.4 g/ton Au. Ore mineralogy is very simple, consisting mainly of pyrite with minor amounts of base-metal sulfides and electrum. Gold grains occur in two assemblages as follows: (1) early, Fe-rich (7.2-10.4 mole % FeS) sphalerite + electrum (50.4-64.3 atom % Au) assemblage occurring as inclusions in pyrite; (2) late, Fe-poor «4.7 mole % FeS) sphalerite + galena + electrum (47.6-81.7 atom % Au) assemblage occurring along fractures of pyrites. Based on fluid inclusion data and thermochemical considerations of ore mineral assemblages, ore minerals were formed at high temperatures (about $230^{\circ}C$ to $420^{\circ}C$) from $H_{2}O-CO_{2}(-CH_{4})$-NaCI fluids with the sulfur fugacity of about $10^{-6}$ to $10^{-10}$ atm. Fluid inclusion data also indicate that ore mineralization occurred mainly as a result of fluid unmixing accompanying $CO_2$ effervescence. Calculated oxygen and measured hydrogen isotope compositions of mineralizing waters (${\delta}^{18}O_{V-SMOW}$ values = 5.3 to 8.6$\textperthousand$, ${\delta}D_{V-SMOW}$ values = - 60 to - 52$\textperthousand$), along with the sulfur isotope compositions of vein sulfides (${\delta}^{34}S_{CDR}$ values = - 1.2 to 2.8$\textperthousand$) and carbon isotope compositions of inclusion $CO_2$ (${\delta}^{13}C_{PDB}$ values = - 4.7 to - 2.0$\textperthousand$) indicate that the high temperature (mesohypothermal) gold mineralization formed from a magmatic fluid.

• Economic and Environmental Geology
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• v.19 no.2
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• pp.109-122
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• 1986

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.

• Economic and Environmental Geology
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• v.24 no.2
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• pp.131-150
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• 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.

• Korean Journal of Ecology and Environment
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• v.47 no.2
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• pp.127-134
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• 2014

Organic carbon and nitrogen stable isotope ratios of particulate organic matter (POM) were determined at 7 stations (6 stations in Han river and Paldang dam outflow station) from May to October 2013, in order to understand the origin of POM at the Han river. ${\delta}^{13}C$ values of POM in four stations showed significant seasonal changes season, but ${\delta}^{15}N$ values were enriched in around Kyeongan stream (K). POC, PN and Chl-a concentration showed a similar seasonal pattern in Kyeongan stream, with an apparent decrease from July to August. POC and PN concentration has a higher correlation with Chl-a concentration in Kyeongan stream (K). ${\delta}^{13}C$ and ${\delta}^{15}N$ values of POM has a lighter value during lower Chl-a concentration peroid, compared to other seasons. Our results revealed that Kyeongan stream (K) seemed to be influenced by substantial amount of organic manure or fertilizer input in 2013, compared to the previous year (2012). These results suggest that the analysis of stable isotope ratios is a simple but useful tool for the identification of organic matter origin in aquatic environments.

• Journal of the Korean Society of Groundwater Environment
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• v.5 no.4
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• pp.177-191
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• 1998

For various kinds of waters including surface water, shallow groundwater (＜70 m deep) and deep groundwater (500∼810 m deep) from the Pungki area, an integrated study based on hydrochemical, multivariate statistical, thermodynamic, environmental isotopic (tritium, oxygen-hydrogen, carbon and sulfur), and mass-balance approaches was attempted to elucidate the hydrogeochemical and hydrologic characteristics of the groundwater system in the gneiss area. Shallow groundwaters are typified as the 'Ca-HCO$_3$'type with higher concentrations of Ca, Mg, SO$_4$and NO$_3$, whereas deep groundwaters are the 'Na-HCO$_3$'type with elevated concentrations of Na, Ba, Li, H$_2$S, F and Cl and are supersaturated with respect to calcite. The waters in the area are largely classified into two groups: 1) surface waters and most of shallow groundwaters, and 2) deep groundwaters and one sample of shallow groundwater. Seasonal compositional variations are recognized for the former. Multivariate statistical analysis indicates that three factors may explain about 86% of the compositional variations observed in deep groundwaters. These are: 1) plagioclase dissolution and calcite precipitation, 2) sulfate reduction, and 3) acid hydrolysis of hydroxyl-bearing minerals(mainly mica). By combining with results of thermodynamic calculation, four appropriate models of water/ rock interaction, each showing the dissolution of plagioclase, kaolinite and micas and the precipitation of calcite, illite, laumontite, chlorite and smectite, are proposed by mass balance modelling in order to explain the water quality of deep groundwaters. Oxygen-hydrogen isotope data indicate that deep groundwaters were originated from a local meteoric water recharged from distant, topograpically high mountainous region and underwent larger degrees of water/rock interaction during the regional deep circulation, whereas the shallow groundwaters were recharged from nearby, topograpically low region. Tritium data show that the recharge time was the pre-thermonuclear age for deep groundwaters (＜0.2 TU) but the post-thermonuclear age for shallow groundwaters (5.66∼7.79 TU). The $\delta$$\^$34/S values of dissolved sulfate indicate that high amounts of dissolved H$_2$S (up to 3.9 mg/1), a characteristic of deep groundwaters in this area, might be derived from the reduction of sulfate. The $\delta$$\^$13/C values of dissolved carbonates are controlled by not only the dissolution of carbonate minerals by dissolved soil CO$_2$(for shallow groundwaters) but also the reprecipitation of calcite (for deep groundwaters). An integrated model of the origin, flow and chemical evolution for the groundwaters in this area is proposed in this study.