Geochemical Journal, Vol. 36, pp.

155 to 171, 2002

Geochemistry of the Youngbogari deposit, Republic of Korea:

An unusual mesothermal goldsilver deposit of the Youngdong area

CHIL -SUP SO, 1 S EONG-T AEK YUN ,1* K EVIN L. S HELTON2 and D E-QUAN ZHANG 3
1

Department of Earth and Environmental Sciences, Korea University, Seoul 136-701, Korea
Department of Geological Sciences, University of Missouri-Columbia, Columbia, Missouri 65211, U.S.A.
3
Institute of Mineral Deposits, Chinese Academy of Geological Sciences, Beijing 100037, China
(Received June 11, 2001; Accepted January 7, 2002)
Mesothermal goldquartz veins of the Youngbogari deposit in the Youngdong area, South Korea, are
hosted in faulted shear zones in Precambrian gneiss of the Sobaegsan massif. The Youngbogari deposit
shares many features with other metamorphic rock-hosted gold deposits in the area, including a massive
single-stage nature of veins and a simple vein mineralogy. However, its ore mineralogy is unique in that
(1) arsenopyrite and pyrite occur dominantly with only minor pyrrhotite and (2) electrum grains are very
poor in gold content (<40 atom. % Au).
A variety of geochemical data indicate that deposition of the mesothermal goldsilver ores of the
Youngbogari deposit resulted mainly from cooling of ore fluids accompanying decreasing sulfur fugacity.
Fluid inclusion evidence indicates that gold deposition was not related to an early history of CO2 phase
separation (at temperatures of 300 to 420C), but rather was tied to a later history of cooling and dilution
of H2ONaCl ore fluids at temperatures of <300C. These temperature estimates for gold deposition agree
with those based on chlorite thermometry (270 to 320C) and sulfide mineral assemblages (<290C).
Measured and/or calculated, stable isotope compositions of hydrothermal fluids ( 18Owater = 5.8 to 8.0,
Dwater = 75 to 54) indicate an important role of rock-dominated (possibly magmatic) fluids in the
mesothermal goldsilver system.
The unusual arsenopyritepyrite-rich nature of the Youngbogari ores and their anomalously negative
34S values (2.9 to 5.1), compared to other mesothermal gold deposits of the Youngdong area, are
interpreted to reflect a more oxidizing nature of the Youngbogari ore fluids, likely due to less reaction with
graphite in wallrock gneiss.

display a consistent relationship among depth,

water-to-rock ratio (degree of meteoric water involvement), and Au/Ag ratio (So and Shelton,
1987; Shelton et al., 1988). These are:
(1) mesothermal-type gold-rich deposits, (2) Korean-type (~deep epithermal) goldsilver deposits (Tsuchida, 1944; Shikazono and Shimizu,
1986), and (3) more silver-rich, epithermal-type
deposits (So and Shelton, 1987; So et al., 1987a;
Shelton et al., 1990; Yun et al., 1993).
Among these, mesothermal-type deposits are
comparatively rare in Korea (Shelton et al., 1988;
So et al., 1995, 1999; So and Yun, 1997; Yun et

I NTRODUCTION
Goldsilver vein deposits in South Korea are
associated intimately with major periods of
Jurassic and Cretaceous granitic plutonism
(Shimazaki et al., 1981, 1986). Cretaceous granites have been shown to be higher level intrusions
(<23 km) than Jurassic granites (>5 km, Tsusue
et al., 1981; Watanabe, 1981), providing an opportunity to investigate the influence of magma
emplacement depth on the post-magmatic evolution of granite-related gold systems. Three major
types of deposits previously documented which
*Corresponding author (e-mail: styun@mail.korea.ac.kr)

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C.-S. So et al.

al., 2001), and therefore relatively little is known

about their genesis and fluid characteristics. They
appear to be associated genetically with Jurassic
(Daebo Series) granitoids (Lee, 1981) and are
characterized by high Au/Ag ratios (5:18:1).
Geochemical studies of these deposits indicate that
gold deposition occurred at temperatures of 300
to 370C in response to CO 2 separation of the fluids at depths of >4.5 km (Shelton et al., 1988; So
and Yun, 1997).
Korean-type deposits are associated with Late
JurassicEarly Cretaceous (Bulgugsa Series)
granitoids (Lee, 1981) and are characterized by
comparable Au/Ag ratios (1:52:1) and a general
paucity of sulfide minerals (Sugaki et al., 1986).
Geochemical studies of Korean-type goldsilver
deposits indicate that gold deposition occurred at
temperatures near 270C in response to boiling
and cooling at depths near 1.3 km (So and Shelton,
1987; So et al., 1987b).
The more silver-rich, epithermal deposits are
associated genetically with Late CretaceousTertiary granitoids and are characterized by lower Au/
Ag ratios (1:101:200) and more abundant and
complex sulfide mineralization. Geochemical
studies of these deposits indicate that goldsilver
deposition occurred at temperatures of <240C in
response to boiling and cooling at depths of <0.8
km (So and Shelton, 1987; So et al., 1987a;
Shelton et al., 1990).
The Youngdong area was historically one of
the important goldsilver producers in South Korea. Although accurate total production is not
known, available data show that at least 1.5 tons
of pure gold has been produced from twenty-five
goldsilver mines (KMPC, 1986). Various types
of gold(silver) deposits occur in the area, including metamorphic rock-hosted gold-rich deposits,
granite-hosted goldsilver deposits, and volcanic
rock-hosted silver-rich deposits (Choi et al., 1988;
Yun, 1991).
Metamorphic rock-hosted gold-rich deposits
share many common features: occurrence in fault
shear zones in Precambrian gneiss; a massive and
single-stage nature of quartz veins; weak and narrow wallrock alteration zones; volumetrically poor

and simple ore mineralogy dominantly comprising iron sulfides and base-metal sulfides; the
dominance of pyrrhotite among iron sulfides; the
gold-rich nature of ores and electrum grains; and
high temperature (up to 480C), low salinity (<10
wt. % eq. NaCl) and CO2-rich nature of fluid inclusions (Yun, 1991; So et al., 1995, 1999; So and
Yun, 1997). These features are similar to those of
worldwide Archean gold deposits, orogenic gold
deposits, and mesothermal gold deposits in the
eastern edge of Sino-Korean platform (Kerrich and
Cassidy, 1994; Pan and Fleet, 1995; Groves et al.,
1998; Yao et al., 1999; Goldfarb et al., 2001).
Mining of the Youngbogari deposit was intermittent between 1936 and 1990. Reported ore
grades range from 0.7 to 30.0 g/ton of gold and
from 20 to 204 g/ton of silver (KMPC, 1986).
Remaining reserves are an estimated 145,200
metric tons of ore. The Youngbogari deposit shares
many features with other metamorphic rockhosted gold deposits in the Youngdong area (Choi
et al., 1988; Yun, 1991). However, its ore mineralogy is unique in that (1) arsenopyrite and pyrite
occur dominantly with only minor pyrrhotite, and
(2) electrum grains are very poor in gold content
(<40 atom. % Au). Such mineralogical differences
may reflect different physicochemical conditions
(e.g., fugacities of sulfur and oxygen) during mineralization.
The main purpose of this study is to determine
what conditions caused formation of the unusual
Youngbogari deposit. Based on mineralogical,
fluid inclusion and stable isotope studies, we decipher the fluid composition and physicochemical conditions that led to deposition of unique
mesothermal ores at Youngbogari. There is special emphasis on sulfur isotope data of ore sulfurs
in various types of gold(silver) deposits in the
Youngdong area.
EXPERIMENTAL PROCEDURES
For this study, about eighty samples of vein
ore and wall-rocks were collected from underground ore stopes and surface outcrops of the
Youngbogari deposit. Among them, representative

Geochemistry of the Youngbogari deposit, Republic of Korea

samples were examined in detail by microscopy

in order to understand the mineralogy and
paragenesis of veins and wall-rock alteration
zones. X-ray diffraction analysis was also performed to identify the mineralogical characteristics in more details. The chemical compositions
of electrum, arsenopyrite, sphalerite, silver-bearing sulfosalts, and chlorite were analyzed with an
electron probe microanalyzer (JEOL JXA-8600
Superprobe) with energy-dispersion and wavelength-dispersion spectrometers at the Center for
Mineral Resources Research (CMR), Korea University.
Fifty-six samples of vein quartz among collected samples were prepared for fluid inclusion
study. Sphalerite was not suitable for the study
because of its opacity. Microthermometric data
were obtained using a FLUID Inc. gas-flow heatingfreezing stage calibrated with synthetic CO2
and H 2O inclusions and various organic solvents.
Before the microthermometric measurement, a
relative chronology of fluid inclusions was established using the criteria of Roedder (1984). During heating experiments, heating rates were maintained near 2C/min to avoid decrepitation of fluid
inclusions. A sequential technique described by
Haynes (1985) was employed during freezing experiments in order to obtain accurate temperatures
of phase change in fluid inclusions. Temperatures
of total homogenization (Thtot) have standard
error of 2C. The melting temperatures of the
carbonic phase (TmCO2 ), ice (Tmice) and clathrate (Tmclath) and the homogenization temperatures of the carbonic phase (ThCO 2) have
standard errors of 0.2C.
We have examined the sulfur isotope compositions of 20 sulfides (pyrite, sphalerite, galena,
arsenopyrite) separated by hand-picking from
sulfide bands, the oxygen isotope compositions of
8 vein quartz, the carbon isotope compositions of
4 samples of CO 2 gas extracted from fluid inclusions, and the hydrogen isotope compositions of
8 samples of inclusion waters. Mineral separates
used for analysis were at least 99% pure. For the
preparation of vein sulfides to extract SO2 for
sulfur isotopic analysis, the conventional tech-

157

nique described by Grinenko (1962) was used.

Oxygen isotope analysis of vein quartz was carried out with conventional fluorination techniques
(Hall and Friedman, 1963). Inclusion-hosted fluids were also extracted in a line that was designed
to separate H2 O, CO2 , and CH4 from vein quartz
samples for measurement of their hydrogen isotope (for water) and carbon isotope (for CO2 ) ratios. The method of crushing in a vacuum was used
to extract the fluids. Before the crushing of quartz
samples for hydrogen isotope analysis, detailed
fluid inclusion petrology of each sample was carefully examined to select the samples to minimize
the percentage of obvious secondary inclusions.
Careful monitoring of the CO2 /H2 O ratios in the
extracted fluids also allowed us to affirm that the
extracted fluids from quartz and their hydrogen
isotope compositions are representative of the
typical mineralizing fluids, because primary inclusions typically contain high proportions of liquid CO 2-bearing fluid inclusions. The stable isotopic compositions were analyzed with gas-isotope ratio mass spectrometers at the Institute of
Mineral Deposits, Beijing, China, the Stable Isotope and Fluid Inclusion Laboratories of MissouriColumbia, U.S.A., and the Krueger Enterprises,
U.S.A. Isotope data are reported in standard
notation relative to the CDT standard for sulfur,
the PDB standard for carbon, and the V-SMOW
standard for oxygen and hydrogen. The standard
error of each analysis is about 0.1 for S, C and
O, and 2 for H.
G EOLOGIC S ETTING AND O RE DEPOSIT
Geologic setting
As shown in Fig. 1, the Youngdong area is located approximately 170 km SSE of Seoul between the Okchon Fold Belt (a NE-trending fold
and thrust belt comprising mainly Late
Precambrian to Paleozoic metasedimentary rocks)
and the Sobaegsan Massif (a metamorphic terrane
comprising mainly Late Archean to Early
Proterozoic gneisses and schists). The basement
rocks of the Sobaegsan Massif experienced
amphibolite- to granulite-facies metamorphism

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C.-S. So et al.

of 1,810 10 Ma was obtained for the granite

gneiss by Choo and Kim (1985). Amphibolitegrade metamorphic mineral assemblages in the
gneisses have been overprinted by greenschist
facies assemblages, especially along mineralized
fault planes. A late Jurassic granodiorite batholith
intrudes these metamorphic rocks in the eastern
part of the study area. So and Yun (1997) obtained
a RbSr age of 171 10 Ma for the granodiorite,
and have suggested that it was genetically related
to mesothermal-type gold mineralization in the
Youngdong area.

Fig. 1. Simplified geologic map of South Korea (after

Chough et al., 2000), showing the location of
Yongbogari (YB) AuAg deposit in the Youngdong area
(shown as a box). Tectonic provinces: IB = Imjingang
Belt, KB = Kyonggi Massif, OFB = Okchon Fold Belt,
SM = Sobaegsan Massif, KB = Kyongsang Basin. Age
of granites: Older Granite = Permian to Jurassic,
Younger Granite = Cretaceous to Early Tertiary.

during the late Paleozoic to early Mesozoic collision process between the North and South China
crustal blocks (Na and Kim, 1987; Ree et al., 1996;
Chough et al., 2000) and were intruded by foliated or massive granites of Permian to Jurassic
age (Fig. 1). Numerous hydrothermal quartz veins
in the Youngdong area mostly occur in
Precambrian basement rocks.
Precambrian basement rocks in the
Youngbogari deposit area consist of banded biotite
gneiss, granitic gneiss and small lenses of schist
within the gneisses (Fig. 2). Banded biotite gneiss
and granitic gneiss have a gradational contact and
are locally migmatitic. A whole-rock RbSr age

Ore deposit
The Youngbogari deposit comprises two major quartz veins with strike and dip directions of
N2068E and 7080SE, respectively (Fig. 2).
The veins extend up to 1 km along strike direction and vary in thickness from 0.6 to 1.0 m. Weak
alteration of wall-rock gneiss occurs along mineralized fault planes as narrow (<0.2 m thick), pale
green zones consisting of quartz, sericite, chlorite,
carbonates (calcite, dolomite) and pyrite. No economic gold concentration occurs in the alteration
zones. Mineralogical characteristics and chemical composition of electrum and sphalerite from
Youngbogari ores have been briefly described in
Choi et al. (1988). However, most data in this section were collected by this study.
Ore mineralization occurs in massive quartz
veins whose ore mineralogy is relatively simple,
consisting mainly of iron sulfides (dominantly
arsenopyrite and pyrite) and base-metal sulfides
(sphalerite and galena). The veins contain variable amounts of sulfides (generally <10 vol %,
but locally up to 50 vol % of the vein) in massive
gray to milky quartz and locally show crude
sulfide bands in the following sequence, from vein
margins to center: arsenopyrite + pyrite +
sphalerite; sphalerite + chalcopyrite + pyrite
pyrrhotite; sphalerite + galena + pyrite + AuAg
minerals (electrum, argentite, pyrargyrite). Mineralogy and paragenesis of veins are summarized
in Fig. 3.
Arsenopyrite (31.433.4 atom. % As) is the
most abundant sulfide mineral (>40 vol % of ore

Geochemistry of the Youngbogari deposit, Republic of Korea

159

Fig. 2. Geologic map of the Youngbogari deposit area.

minerals in veins) and occurs mainly as large,

euhedral to subhedral aggregates (up to 5 mm in
size) in marginal to intermediate portions of the
veins. Along vein margins, arsenopyrite and pyrite form a crude band. Pyrite in association with
arsenopyrite rarely contains tiny grains of
pyrrhotite. Pyrrhotite also occurs as a rare sulfide
intergrown with or included in sphalerite.
Arsenopyrite is commonly fractured and healed
by later quartz, sulfides (mainly galena and
sphalerite) and electrum grains (Fig. 4A).
Sphalerite (X FeS = 0.040.18) is also abundant and
occurs typically as anhedral grains intergrown
with pyrite, chalcopyrite, galena and tetrahedrite.
Late sphalerite (X FeS = 0.040.10) occurs in microscopic veinlets cutting arsenopyrite and pyrite,
and is associated with late quartz, chlorite, galena,
electrum and argentite (Figs. 4B and C). Gold in
the Youngbogari ores occurs as silver-rich electrum (60.387.6 atom. % Ag) which is intergrown
with galena that fills fractures in arsenopyrite. Due
to the intimate association of electrum grains
within arsenopyrite fractures, the Youngbogari
ores have been undervalued in spite of high gold
grades (up to 30 g/ton Au), because refining of
arsenopyrite-rich ores has been avoided due to
environmental problem.

Fig. 3. Generalized paragenetic sequence of minerals

from veins of the Youngbogari AuAg deposit. Thickness of lines is proportional to abundance.

Compared with other Jurassic, mesothermaltype gold deposits in the Youngdong area (Choi
et al., 1988; Yun, 1991; So et al., 1995, 1999; So
and Yun, 1997), the Youngbogari deposit shows

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C.-S. So et al.

many common features: (1) occurrence within

Precambrian gneiss; (2) massive and single-stage
quartz veins; (3) simple vein mineralogy. However, some characteristics of the Youngbogari ores
are unique: (1) arsenopyrite is the most abundant
sulfide mineral (other deposits do not contain significant arsenopyrite); (2) pyrrhotite is rare among
the iron sulfides (pyrrhotite is the most abundant
sulfide in other deposits); (3) the electrum has very
high silver contents (up to 87.6 atom. % Ag),
whereas electrum from other deposits are goldrich (mostly >70 atom. % Au).
DEPOSITIONAL C ONDITIONS OF
ORE MINERALIZATION
Chlorite thermometry
Cathelineau (1988) suggested that the Al(IV)
content of chlorite can be used to estimate the temperature of geothermal fluids. The suggested equation is T (C) = 322Al(IV) 62 for chlorites converted to the formula 8Si + Al(IV), and can be
used to reconstruct temperatures within the error
of 10C. Following the correction of increase in
Al(IV) content with Fe/(Fe + Mg), the compositions of chlorites (N = 18) in association with galena, sphalerite, electrum and argentite (Fig. 4C)
in late periods of hydrothermal mineralization
were used to estimate the temperatures of hydrothermal fluids. Calculated temperatures of formation range from 270 to 320C. These temperatures likely reflect the depositional conditions of
gold and silver.

Fig. 4. Reflected light photomicrographs showing the

occurrence of electrum and chlorite. A and B: Electrum grains (el) intergrown with late quartz (qz), galena (gn) and iron-poor (59 mole % FeS) sphalerite
(sp), which fill fractures in arsenopyrite (apy).
C: Chlorite (chl) intergrown with late quartz, sphalerite
and galena. Scale bars are 0.1 mm.

Temperature and fugacity of sulfur conditions

based on sulfide mineral assemblages
Temperatures and fugacities of sulfur of the
ore-forming fluids can be estimated based on the
available ore mineral assemblages and their compositions. In marginal portions of veins,
arsenopyrite (31.433.4 atom. % As) coexists with
pyrite as a crude bimineralic band. This assemblage indicates temperature and fugacity of sulfur
conditions of approximately >380C and >108
bars, respectively (Fig. 5; Kretschmar and Scott,
1976). Electrum grains (Ag content = 60.387.6

Geochemistry of the Youngbogari deposit, Republic of Korea

161

Fig. 5. Sulfur fugacity versus temperature diagram showing the depositional conditions of ore mineral assemblages in the Youngbogari ores. Hatched area indicates deposition of arsenopyrite + pyrite pyrrhotite (early;
pre-gold); shaded area, deposition of electrum + iron-poor (410 mole % FeS) sphalerite argentite (late; golddepositing). The sources of stability curves are: isopleths (atom. fraction of Ag; NAg) of electrum from Barton and
Toulmin (1964); isopleths (mole % FeS) of sphalerite from Barton and Skinner (1979); and isopleths (atom. % As;
numbers 31, 32 and 33) of arsenopyrite from Kretchmar and Scott (1976).

atom. %) are associated with chlorite, galena, late

iron-poor sphalerite (X FeS = 0.040.10) and
argentite, which fill fractures in arsenopyrite. This
late assemblage indicates a fugacity of sulfur of
about <1010 bars at temperatures of <290C (Fig.
5; Barton and Toulmin, 1964; Barton and
Skinner, 1979). These data indicate that the ore
fluids evolved progressively toward lower temperatures and sulfur fugacities with time.
F LUID I NCLUSIONS
Occurrence and compositional types of fluid inclusions
Vein quartz is typically inclusion-rich, due to
repeated fracturing and healing events both during and after quartz deposition. The size of fluid
inclusions ranges from <3 to 30 m. Two main
types of fluid inclusions were identified based on
their phase relations at 20C and their behavior
on cooling to 15C: liquid-rich, aqueous inclusions and liquid CO2-bearing inclusions.

Liquid-rich, aqueous inclusions consist of an

aqueous liquid and vapor. The vapor bubble comprises 10 to 45 vol %. These inclusions homogenize to liquid phase upon heating. Upon cooling,
CO 2-clathrate formed in some aqueous inclusions.
These clathrate-forming inclusions appear to be
primary, as they do not show obvious fracture control, and are classified herein as type a aqueous
inclusions. Most aqueous inclusions are relatively
small (mostly <10 m) and irregular in shape, and
occur along fractures cutting across individual
quartz grains. These inclusions do not nucleate
clathrate on cooling and are classified as type b
aqueous inclusions.
Carbonic, liquid CO2 -bearing inclusions contain liquid CO2 , vapor CO2 and aqueous liquid.
Based on the relative abundances of CO2 and H2O,
they are classified into two subtypes: type a
carbonic (H 2 O > CO 2 ) and type b carbonic
(H2 O < CO2). The volume proportions of CO2 (liquid + vapor) are about 10 to 35% for type a carbonic inclusions and 55 to 90% for type b. The

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C.-S. So et al.

Fig. 7. Frequency diagrams of total homogenization

temperature (Thtot) of fluid inclusions in vein quartz
from the Youngbogari AuAg deposit.

Fig. 6. Frequency diagrams of estimated salinity of

fluid inclusions in vein quartz from the Youngbogari
AuAg deposit. P + PS = primary and
pseudosecondary, S = secondary.

entire range of CO2 volume is typically observed

within a single grain. Carbonic inclusions appear
mostly to be primary in origin, as they occur as
regular-shaped and isolated inclusions with no
obvious fracture control. Upon heating, most carbonic inclusions decrepitated prior to homogenization. Therefore, we could obtain only a small
number of Thtot data. When the thermal decrepitation occurred slightly before anticipated homogenization, the decrepitation temperature was used
as a minimum estimate of the real homogenization temperature.
Microthermometric data
Microthermometric data of 301 fluid inclusions
(260 primary and pseudosecondary, and 41 secondary) in vein quartz were obtained by freezing
and heating experiments. The salinity data reported for 131 fluid inclusions are based on freezing point depression in the system H2 ONaCl
(Bodnar, 1993) for aqueous inclusions and on clathrate melting temperatures (Bozzo et al., 1975;
Diamond, 1992) for liquid CO2 -bearing inclusions.
Aqueous inclusions The first ice melting of
liquid-rich, aqueous inclusions was recognized at

temperatures near 21C, indicating the dominance of NaCl among dissolved salts (Crawford,
1981). Final melting of ice (Tmice) occurred at
temperatures between 6.1 and 1.6C. If we
neglect the effect of a small amount of clathrate
formation by which ice melting temperatures can
be depressed (Collins, 1979; Hedenquist and
Henley, 1985), the Tmice values correspond to
salinities of 9.3 to 2.7 wt. % eq. NaCl (Fig. 6).
Aqueous inclusions homogenized to the liquid
phase at temperatures of 232 to 418C (Fig. 7).
Tmclath data of type a aqueous inclusions were
very difficult to obtain because of their small size,
but fall in the range of 5.9 to 8.6C (corresponding to salinities of 2.8 to 7.6 wt. % eq. NaCl, within
the range estimated from Tmice data).
The salinity and homogenization temperature
data obtained for obvious secondary aqueous inclusions (type b) fall in the range 1.2 to 10.4
wt. % eq. NaCl (corresponding to Tmice values
of 0.7 to 6.9C) and 163 to 228C, respectively (Figs. 6 and 7).
Carbonic inclusions Melting temperatures of
the CO2-bearing phase (TmCO2) in type a carbonic inclusions range between 60.4 and
56.6C (Fig. 8A), indicating the presence of small
amounts of CH4 in the carbonic phase (Burruss,
1981). Homogenization of the CO2-rich portion
(ThCO2) in type a carbonic inclusions to the
liquid CO2 phase occurred at temperatures of 19.2
to 29.6C (Fig. 8B). Within a single quartz grain,

Geochemistry of the Youngbogari deposit, Republic of Korea

163

Fig. 8. Temperatures of melting (TmCO 2) and homogenization (ThCO 2) of carbonic phase, and temperatures of clathrate melting (Tmclath) in liquid CO2bearing inclusions in vein quartz from the Youngbogari
AuAg deposit.
Fig. 9. Total homogenization temperature versus salinity diagram for fluid inclusions in vein quartz from
the Youngbogari AuAg deposit.

ThCO2 values range widely, indicating that the

density of the CO2 -rich phase was highly variable
during the fluids entrapment. Tmclath values of
type a carbonic inclusions range from 7.1 to
11.0C (Fig. 8C). Tmclath values above 10C
indicate the presence of CH 4 (Hollister and
Burruss, 1976; Burruss, 1981; Diamond, 1992).
If we neglect the presence of CH 4 clathrate, which
acts to raise the clathrate melting temperature, the
Tmclath values correspond to salinities of less
than 5.6 wt. % eq. NaCl. The Thtot values of
these inclusions (to the aqueous phase) range from
257 to 367C (Fig. 7).
Type b carbonic inclusions have TmCO2
and ThCO2 (to the liquid) values of 61.4 to
56.6C and 18.3 to 28.4C, respectively (Figs.
8A and B). Tmclath values of these inclusions
range from 8.0 to 9.7C (Fig. 8C), corresponding to salinities of 0.6 to 3.9 wt. % eq. NaCl if we
neglect the presence of CH4 clathrate. A total of
88 Th-tot (to the CO2-rich phase) values obtained
for type b carbonic inclusions range from 253
to 353C, similar to the range for type a carbonic inclusions (Fig. 7).
Fluid immiscibility and mineral precipitation
As described earlier, hydrothermal fluids
trapped as apparent primary inclusions in vein
quartz are composed of three types: (1) a low to
moderate-salinity (<9.3 wt. % eq. NaCl) aqueous

fluid with the ability to form CO 2 clathrate;

(2) an H 2O-rich, H 2OCO2 fluid with low salinity
(<5.6 wt. % eq. NaCl); (3) a CO 2-rich, H 2OCO2
fluid with low salinity (<3.9 wt. % eq. NaCl).
The entire range of CO 2 concentration is observed within single quartz grains. Total homogenization temperatures of type a and b carbonic inclusions are similar (253 to 367C, with
the peak at 280320C in their distribution, Fig.
7). These observations likely indicate CO2 phase
separation of hydrothermal fluids during deposition of vein quartz. The wide range of total homogenization temperatures (232 to 418C) is
thought to reflect several episodes of CO2 phase
separation during vein formation, as indicated by
textural evidence of repeated fracturing and filling of the veins.
The relationship between Thtotal values and
salinities of fluid inclusions (Fig. 9) may also
record a history of CO2 separation over a temperature range of approximately 250 to 370C. Within
this temperature range, data for aqueous and carbonic inclusions are quite variable, but show recognizable systematic trends: (1) liquid CO2 -bearing inclusions generally have lower salinities than
aqueous inclusions; (2) more CO 2-rich, type b
carbonic inclusions have lower salinities than type
a carbonic inclusions; (3) above temperature of

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C.-S. So et al.

300C, aqueous inclusions tend to display a trend

of increasing salinity with decreasing temperature.
All of these trends can be interpreted to indicate
CO2 phase separation, because phase separation
of a relatively low-salinity, H2OCO2 fluid produces both a high-salinity H2 O-rich fluid and a
low-salinity CO 2 -rich fluid, owing to the
fractionation of nearly all of the salt into the H2Orich liquid phase (Bowers and Helgeson, 1983).
If this interpretation is true, secondary aqueous
inclusions with low homogenization temperatures
(<200C) and high salinities (>9 wt. % eq. NaCl;
Fig. 9) may represent the continued trapping of
remnant fluids evolved through CO2 separation.
Precipitation of most sulfides occurring
intergrown with vein quartz may have resulted
from this early history of CO2 separation, which
would have resulted in increase in pH of the aqueous fluid and the escape of H2S to vapor phase.
The two processes could effectively result in precipitation of sulfides (e.g., Bowers, 1986). The

separated CO2 could have reacted with adjacent

wall rocks, forming carbonates in alteration zones.
Goldsilver deposition
As described earlier, electrum and other silver-bearing minerals (argentite, argentian
tetrahedrite and pyrargyrite) occur along fractures
cutting earlier sulfides and quartz. This indicates
that gold and silver mineralization occurred late
in the history of vein formation. We consider that
gold deposition was related temporally to the fluids
trapped
as
lower
temperature,
pseudosecondary and/or secondary inclusions in
vein quartz. Thus, gold deposition at Youngbogari
likely occurred from aqueous fluids with lower
Thtotal values (<300C), not from higher temperature carbonic fluids.
It is important to recognize the fact that lower
temperature (<300C) aqueous inclusions tend to
show a trend of decreasing salinity with decreasing temperature (Fig. 9). This trend likely records

Table 1. Sulfur isotope data of sulfide minerals from goldquartz veins of the Youngbogari deposit
Sample No.

Mineral

YB-2-1
YB-2-2
YB-2-3
YB-5
YB-5-1
YB-5-2
YB-6-1
YB-6-2
YB-15-1
YB-15-2
YB-16
YB-20-1
YB-20-2
YB-21-1
YB-21-2
YB-21-3
YB-25
YB-26
YB-27-1
YB-27-2

Sphalerite
Galena
Arsenopyrite
Galena
Arsenopyrite
Pyrite
Sphalerite
Galena
Sphalerite
Galena
Arsenopyrite
Sphalerite
Arsenopyrite
Sphalerite
Galena
Pyrite
Chalcopyrite
Galena
Sphalerite
Galena

3 4 S ()

and Temp.1 )

T (C) 2 )

34 S H 2S () 3 )

2.6
4.9
3.4
6.6
2.5
3.6
4.1
6.4
4.4
6.4
2.4
4.8
2.7
2.8
5.2
2.8
4.4
5.4
5.4
5.9

spgn 2.3 (287 45C)

285
285
380
270
370
370
285
285
320
320
370
360
370
275
275
290
310
280
310
310

2.9
2.9

4.5

4.6
4.4
4.4
4.7
4.6

5.0

3.1
3.1
4.1
4.3
3.1
5.1
4.0

spgn 2.3 (287 45C)

spgn 2.0 (328 50C)

spgn 2.4 (276 42C)

Remarks
middle; sp + gn band
middle; sp + gn band
early; apy + py band
late; gn-rich band
early; apy + py band
early; apy + py band
middle; sp + gn band
middle; sp + gn band
middle; sp + gn band
middle; sp + gn band
early; apy + py band
early; apy + py + sp band
early; apy + py + sp band
late; sp + gn + py band
late; sp + gn + py band
late; sp + gn + py band
middle; sp + cp band
late; gn-rich band
middle; sp + gn band
middle; sp + gn band

Abbreviations: apy = arsenopyrite, cp = chalcopyrite, gn = galena, py = pyrite, sp = sphalerite.

1)
Sulfur isotope fractionation between two minerals, and the calculated isotope temperature in parenthesis (Ohmoto and Rye,
1979).
2)
Based on the average fluid inclusion and/or sulfur isotope temperatures and paragenetic constraints.
3)
Using the sulfur isotope fractionation equation in Ohmoto and Rye (1979).

Geochemistry of the Youngbogari deposit, Republic of Korea

the simple cooling and dilution of hydrothermal

fluids. The temperatures (<300C) suggested for
gold deposition agree with temperature estimates
based on chlorite thermometry (270 to 320C)
and sulfide mineral assemblages (<290C). Therefore, we consider that gold deposition at
Youngbogari was not directly related to the early
history of CO 2 separation (at temperatures of
>300C), but rather was tied to a late history of
cooling and dilution of ore fluids. As discussed
earlier, decreasing sulfur activity accompanying
sulfide precipitation also may have acted to precipitate gold.
STABLE I SOTOPES
Sulfur isotope study
The sulfur isotope compositions of twenty
samples of vein sulfides are summarized in Table
1. Within the range of 34S values (6.6 to 2.4),
the 34S values generally increase in the order of
galena < sphalerite < pyrite (~arsenopyrite). This
order agrees with the theoretical 34S enrichment
order (Ohmoto and Rye, 1979), likely indicating
the approach toward isotopic equilibrium between
sulfide minerals and hydrothermal fluids.
Four sphaleritegalena pairs with textures indicating possible coprecipitation were obtained
from middle sulfide bands and were analyzed to
determine equilibrium isotope temperatures (Table 1). The sphaleritegalena pairs yield calculated

165

temperatures of 276 42C to 328 50C

(Ohmoto and Rye, 1979). These sulfur isotope
temperatures are in fair agreement with temperature estimates from homogenization temperatures
of fluid inclusions in adjacent quartz. Assuming
appropriate depositional temperatures of >350C,
280 to 350C, and <280C for early, middle, and
late sulfides, respectively, based on fluid inclusion data, sulfur isotope temperatures, thermodynamic considerations of chlorite and sulfide mineral assemblages, and paragenetic constraint, the
34S values of H 2S in hydrothermal fluids were
determined (Table 1). Calculated 34 SH 2 S values
fall in the range of 5.1 to 2.0 (Ohmoto and
Rye, 1979).
Carbon, oxygen, and hydrogen isotope studies
The carbon, oxygen, and hydrogen isotope data
are summarized in Table 2. The 13C values of CO2
in inclusion fluids extracted from quartz range
from 10.4 to 7.4, suggesting a well-mixed
crustal or igneous carbon source (Field and
Fifarek, 1986; Chivas et al., 1987). The 18O values of vein quartz have a narrow range from 11.7
to 13.8. Based on average total homogenization
temperatures of primary fluid inclusions in each
sample and/or on sulfur isotope temperatures, 18O
values of water in equilibrium with quartz were
calculated using the fractionation equation of
Matsuhisa et al. (1979). The calculated 18O H 2 O

Table 2. Oxygen isotope data of vein quartz, and hydrogen and carbon isotope data of inclusion fluids extracted from quartz, Youngbogari deposit
Sample No.
YB-1
YB-2
YB-5
YB-6
YB-9
YB-10
YB-15
YB-20

1 8 Oq z ()

Dwater ()

13 C CO2 ()

T (C) 1 )

1 8 Owater () 2 )

12.1
13.6
12.8
13.8
12.6
11.7
13.1
11.8

67
71
71
72
75
54
61
67

7.5
7.4

8.9
10.4

330
285
370
300
320
330
320
360

6.2
6.2
8.0
6.9
6.4
5.8
6.9
6.8

qz = quartz.
1)
Based on the average fluid inclusion and/or sulfur isotope temperatures and paragenetic constraints.
2)
Calculated water-isotope composition based on quartzwater oxygen isotope fractionation equation in Matsuhisa et al. (1979).

166

C.-S. So et al.

values range from 5.8 to 8.0 (Table 2). The D

values of inclusion waters range from 54 to
75, and with the exception of sample YB-10,
the range is 61 to 75. The 18O and D values (Table 2) significantly overlap the magmatic
water box of Taylor (1979). These isotope values of the Youngbogari ore fluids could represent
magmatic fluids, or fluids from meteoric or metamorphic sources that equilibrated isotopically with
nearby Jurassic granodiorite at high temperatures
and low water : rock ratios. A similar fluid source
was suggested for other mesothermal-type gold
deposits in the Youngdong area (So and Yun, 1997;
So et al., 1995, 1999).
COMPARISON OF SULFUR I SOTOPE DATA
The 34S values for Youngbogari ores (6.6 to
2.4) are the lowest among those reported from
Korean metallic ore deposits (e.g., Shelton et al.,
1990; So and Shelton, 1987; So et al., 1987a, 1999;
Ishihara et al., 2000). Sulfide minerals from Korean metallic ore deposits predominantly have 34S
values in the range of 3 to 7 (>80% of measured samples). This may indicate that igneous
sulfur was predominant in hydrothermal systems
formed in the Korean Peninsula.
Typical mesothermal and epithermal ores in the
Youngdong area
Various types of goldsilver deposits occur
together in the Youngdong area, therefore providing a unique opportunity to examine sulfur isotope systematics in relation to depth and fluid
chemistry. Figure 10 shows frequency diagrams
of 34S values (N = 109) obtained from hydrothermal goldsilver deposits in the Youngdong
area. Deposit types represented are: (1) the unusual Youngbogari goldsilver deposit; (2) goldrich, mesothermal-type deposits (e.g.,
Samhwanghak, Samdong, Heungdeok, Daewon,
and Ilsaeng deposits), which are more typical of
the Youngdong area (So et al., 1995, 1999; So and
Yun, 1997); (3) epithermal-type goldsilver deposits (e.g., Wolyu, Keumryeong, Namkwang, and
Taesung deposits; Yun et al., 1993; So et al.,

Fig. 10. Frequency diagrams of 34S values (CDT) of

sulfide minerals from hydrothermal Au(Ag) deposits
in the Youngdong area, Korea.

1994a, b).
Mesothermal-type gold deposits occur in
graphite-bearing, Precambrian gneisses and
formed at high-temperatures (up to 480C) and
relatively high pressures (up to 2 kbar), from
CO2(CH4)-rich fluids that were genetically related to Jurassic Daebo granitoids (around 166
Ma; So and Yun, 1997). These deposits are commonly simple in ore mineralogy and contain large
amounts of pyrrhotite, suggesting relatively low
fO2 conditions of ore fluids. Based on fluid chemistry, So and Yun (1997) suggested that the
mesothermal auriferous fluids were evolved under reducing conditions that were defined by both
graphitefluid interactions and the QFM buffer.

Geochemistry of the Youngbogari deposit, Republic of Korea

By contrast, epithermal-type deposits are hosted

in diverse rock types (Precambrian gneiss, Cretaceous volcanic and sedimentary rocks), and commonly show a multi-stage, complex silver-rich ore
mineralogy containing various As-Sb-Ge-bearing
silver sulfosalts. Epithermal-type goldsilver deposits formed with CO 2 -poor fluids at shallow
depths <600 m from lower temperature (generally
200 to 300C). The ore fluids were evolved meteoric waters whose circulation resulted from intrusion of late Cretaceous granitic rocks such as
quartz porphyry (around 80 Ma; Yun et al., 1993;
So et al., 1994a). Both the predominance of pyrite (without pyrrhotite) and the occurrence of
hematite indicate more oxidizing conditions for
epithermal fluids than for mesothermal fluids.
Careful examination of the data in Fig. 10
shows that the 34S values of sulfide minerals from
each deposit generally follow the theoretical order of 34S enrichment (galena < chalcopyrite <
sphalerite ~ pyrrhotite < pyrite; Ohmoto and Rye,
1979), suggesting general attainment of isotopic
equilibrium between sulfide minerals and hydrothermal fluids. Compared to the 34S values from
epithermal-type goldsilver deposits (~0 to 8,
but mostly between 4 and 7) in the Youngdong
area, those of mesothermal-type gold deposits are
clearly lower and fall mostly in the range of 4 to
2 (Fig. 10). Except for one pyrite sample from
an alteration zone (~5), sulfide minerals from
the Samdong deposit tend to have 34S values below 0. It is noteworthy that the mesothermal
Samdong ores contain only small amounts of
pyrrhotite, whereas ores from the mesothermal
Samhwanghak, Heungdeok, Daewon, and Ilsaeng
deposits are characteristically pyrrhotite-rich.
The pyrrhotite-rich nature of the ores from the
Samhwanghak, Heungdeok, Daewon, and Ilsaeng
deposits indicates the predominance of reduced
species (H2S and HS) among the dissolved sulfur
species in their hydrothermal fluids (Ohmoto and
34
Rye, 1979). Therefore, the SH 2 S values (0
2; So and Yun, 1997; So et al., 1999) calculated
for those deposits may be taken as an approximation of the sulfur isotopic composition of the entire hydrothermal fluids ( 34 S S ). This 34 S S

167

value (0 2) obtained from pyrrhotite-rich,

mesothermal-type deposits is considered to reflect
the derivation of sulfur from Jurassic granitic
rocks. It should be noted that the 34SS values
obtained from Jurassic mesothermal-type deposits are lower (by about 4) than those obtained
from late Cretaceous epithermal-type deposits
(around 4; Yun et al., 1993; So et al., 1994a, b).
Our sulfur isotope data from the Youngdong
areas hydrothermal deposits (Fig. 10) indicate
isotopically distinct sulfur reservoirs for the hydrothermal systems that formed Jurassic
mesothermal and late Cretaceous epithermal deposits. We speculate that the Jurassic granitic hydrothermal system incorporated 32 S-enriched
sulfur (possibly, sedimentary sulfur in basement
rocks) during magma generation (Sasaki and
Ishihara, 1979; Ishihara et al., 1996). Jurassic
granitoids in South Korea generally belong to the
ilmenite-series, whereas Cretaceous granitoids
belong mostly to the magnetite-series. Similarly,
ilmenite-series granitoids and associated ore
sulfides in Japan typically have more negative 34S
values (average 5), than magnetite-series
granitoids and their related sulfide ores (Sasaki
and Ishihara, 1979).
Low 34S values in the Youngbogari ores
The 34S values for the Youngbogari ores are
remarkably negative (Fig. 10). Although we could
not obtain a reliable age for the Youngbogari deposit because of the absence of appropriate minerals for absolute age dating, the geologic setting
and oxygenhydrogen isotope data suggest a
mesothermal origin for the Youngbogari deposit,
likely associated with nearby Jurassic granitic
rocks. If that is true, the difference in 34S values
between the Youngbogari deposit and other
mesothermal deposits of the area (Samhwanghak,
Heungdeok, Daewon, and Ilsaeng) can be caused
by either of the following mechanisms: (1) the
presence of at least two distinct reservoirs (both
igneous, with 34S values of <5 and 0 2)
for Jurassic mesothermal-type, goldsilver deposits in the Youngdong area; (2) different degrees
of the mixing (assimilation) of 32 S-enriched sulfur

168

C.-S. So et al.

(possibly sulfur in Precambrian pelitic basement

rocks) during the generation and/or subsequent
ascent of magma (cf., Sasaki and Ishihara, 1979);
and/or (3) different degrees of the oxidation of an
H 2 S-rich, magmatically derived sulfur source
(34S = 0 2) during ascent to mineralization
sites (cf., Ishihara et al., 1996). We consider that
the first and second mechanisms cannot be successfully applied to the Youngdong area, because
the geologic setting (especially the host rock petrology) is the same for all of the mesothermaltype deposits in the Youngdong area. Therefore,
we prefer the third mechanism.
If we pay attention to the observed differences
in ore mineralogy (especially, iron-bearing ore
minerals) in the mesothermal-type deposits, as described earlier, ores from the Samhwanghak,
Heungdeok, Daewon, and Ilsaeng deposits are predominantly pyrrhotite-rich with rare amounts of
pyrite, whereas ores from the Samdong and
Youngbogari deposits are characteristically
pyrrhotite-poor. Though the Samdong and
Youngbogari ores are both rich in pyrite, the
Youngbogari ores also contain large amounts of
arsenopyrite and base-metal sulfides. Such mineralogical differences among the mesothermaltype deposits reflect differences in oxygen fugacity of hydrothermal fluids: the pyrrhotite-rich deposits formed from relatively lower fO 2 fluids
which were evolved near the QFM buffer condition (So and Yun, 1997) than pyrite-rich deposits,
and the Youngbogari deposit formed from comparably higher fO2 fluids. The different fO2 conditions were possibly the results of varying degrees of reduction of the ascending magmatic fluids by the reaction with graphite in wallrock gneiss
(So and Yun, 1997). According to So and Yun
(1997), fluid inclusions in quartz from pyrrhotiterich, mesothermal-type deposits in the Youngdong
area contain variable, but high concentrations of
CH4 (6 to 48 mole %, average ~15 mole %). By
contrast, fluid inclusions from the pyrite-rich
Samdong deposit are lower in CH4 content (up to
20 mole %, but mostly <10 mole %; So et al.,
1995). Similarly, microthermometric data for fluid
inclusions from the Youngbogari deposit also in-

dicate low concentrations of CH4 in fluid. The difference in CH4 concentrations in inclusion fluids
may be taken as an estimation of the extent of both
graphitefluid interaction and resultant reduction
of hydrothermal fluids during mineralization. Nevertheless, we conclude that pyrrhotite-rich deposits formed from higher temperature (up to 480C)
and more reducing fluids than did pyrite-rich deposits.
We speculate that the Youngbogari deposit
possibly formed from the most oxidized fluids.
Higher oxygen fugacity of ascending hydrothermal fluids would have formed sulfate from reduced sulfur species (H2S and HS). Sulfate preferentially incorporates 34S, resulting in lower 34S
values of H2S (Ohmoto, 1986) and the observed
lower values of precipitated sulfides in the
Youngbogari deposit.
SUMMARY
A variety of types of geochemical data indicate that deposition of mesothermal, goldsilver
ores of the Youngbogari deposit resulted mainly
from cooling of ore fluids accompanying decreasing sulfur fugacity. Fluid inclusion evidence indicates that gold deposition was not related to an
early history of CO2 separation (at temperatures
of >300C), but rather was tied to a later history
of cooling and dilution of H2ONaCl ore fluids at
temperatures of <300C. These temperature estimates for gold deposition agree with those based
on chlorite thermometry (270 to 320C) and
sulfide mineral assemblages (<290C). The unusual arsenopyritepyrite-rich nature of the
Youngbogari ores and their anomalously negative
34S values, compared to other mesothermal gold
deposits of the Youngdong area, are interpreted
to reflect more oxidizing nature of the
Youngbogari ore fluids, likely due to less reaction with graphite in wallrock gneiss.
AcknowledgmentsThis study was supported by the
Non-Directed Research Fund of the Korea Research
Foundation. We also acknowledge partial support from
the Center for Mineral Resources Research at Korea
University.

Geochemistry of the Youngbogari deposit, Republic of Korea

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