Magnetite and Scheelite-Bearing Skarns in Ulsan Mine, Korea

최선규,이마이 나오야,Choi, Seon-Gyu,Imai, Naoya The Korean Society of Economic and Environmental G 1993 자원환경지질 Vol.26 No.1

경상분지 남동부에 위치한 울산광산은 석회암을 교대한 전형적인 calcareous skarn강상으로 Fe W광화작용 이외에도 Cu, Pb, Zn, As, Bi, Ni, Co, Cr, Ag, Sn, In, Te, Sb 등이 수반되는 다금속광화작용의 특성을 보여주고 있다. 본 광상은 직립에 가까운 파이프상 광체로 산출되며, 자철석과 함께 북측의 혼펠스와의 경계부근에 회중석이 부분적으로 광염되어 있다. 본 광상의 스카른대는 석회암 및 혼펠스를 교대한 괴상 스카른과 양자를 각기 절단하는 맥상스카른으로 구분된다. 괴상스카른은 석회암 기원의 스카른이 주체를 이루며, 이러한 스카른대는 규회석 스카른, 석류석 스카른, 단사휘석-석류석 스카른, 단사휘석 스카른으로 분류되며, 부분적으로 스카른대 주변부를 따라 거정질 방해석대가 존재하고 있다. 스카른 진화과정은 초기스카른 및 후기스카른의 두 시기로 분류되며, 초기스카른은 prograde한 스카른 생성시기로 초기에는 규회석, Mg-rich 단사휘석, Al-rich garnet가 주로 정출되며 광석광물은 거의 불모한 시기이나, 초기스카른의 말기로 진행됨에 따라 자철석과 회중석이 정출된다. 그리고, 후기스카른의 전반기까지는 Fe-rich 단사휘석, Fe-rich garnet와 함께 자철석 회중석이 연속적으로 정출되었으나, 후기스카른의 중기부터는 Ni, Co, As, Cu, Zn, Fe, Bi 등의 황화광물이 정출되는 다금속광화 작용의 특정을 보인다. 또한, 최후기 열수작용시기에는 섬아연석과 방연석 등의 Base-metal 황화광물이 주로 정출되는 연 아연 광화작용의 양상을 나타낸다. 이러한 각 광화시기별 스카른 광물과 광석광물의 변화양상은 고온의 열수용액이 천부로 유출되는 과정에서 광화용액의 온도가 급격히 떨어진 결과 (telescope)에 기인된 것으로 사료된다. The Ulsan Fe-W deposit, which can be classified as a calcareous skarn deposit, is represented by ore pipe consisting principally of magnetite and lesser amounts of scheelite with minor sulphides, sulphosaits, arsenides, sulpharsenides, etc. At Ulsan mine, metasomatic processes of skarn growth may be divided broadly into two stages based on the paragenetic sequence of calc-silicate minerals and their chemical composition; early and late skarn stages. Early stage has started with the formation of highly calcic assemblages of wollastonite, diopsidic clinopyroxene and nearly pure grossular, which are followed by the formation of clinopyroxenes with salite to ferrosalite composition and grandite garnets with intermediate composition. Based on these calc-silicate assemblages, the temperatures of early skarn formations have been in the ranges of $550^{\circ}$ to $450^{\circ}$. The calc-silicate assemblages formed during the earlier half period of late skarn stage show the enrichment of notable iron and slight manganese, and the depletion of magnesium; clinopyroxenes are hedenbergitic, and grandite garnets are andraditic. The formation temperatures during this skarn stage are inferred to have been in the range of $430^{\circ}$ to $470^{\circ}C$ at low $X_{CO_2}$ by data from fluid inclusions of late andraditic garnets. The later half period of late skarn stage is characterized by the hydrous alteration of pre-existing minerals and the formation of hydrous silicates. The main iron-tungsten mineralization representing prominent deposition of magnetite immediately followed by minor scheelite impregnation has taken place at the middle of early skarn stage, while complex polymetallic mineralization has proceeded during and after the late skarn stage. Various metals and semimetals of Fe, Ni, Co, Cu, Zn, As, Mo, Ag, In, Sn, Sb, Te, Pb and Bi have been in various states such as native metal, sulphides, arsenides, sulphosaits, sulpharsenides and tellurides.

한국(韓國) 장군광산(將軍鑛山)의 황석석(黃錫石)에 대(對)하여 -장군(將軍) 연(鉛)·아연(亞鉛)·은(銀) 광석광물(鑛石鑛物)의 지식(知識)에의 기여(寄與) (3)-

이현구,이마이 나오야,Lee, Hyun Koo,Imai, Naoya 대한자원환경지질학회 1986 자원환경지질 Vol.19 No.no.spc

In the Janggun mine, stannite occurs as anhedral grains, up to 500 micrometer in long dimension, closely associated with sphalerite, chalcopyrite, arsenopyrite, pyrrhotite, galena and rhodochrosite in the periphery of the South ore body. In reflected light, stannite is grayish yellow green in color and exhibits moderate bireflectance and strong anisotropism without any intenal reflections. Reflection; Rmax. =29.0, Rmin. =27.8 percent at a wavelength of 560nm, and VHN; 219~244kg/mm at a 50g load. The chemical composition on the average from 35 spot analyses by electron microprobe is, Cu 28.0, Fe 12.7, Zn 2.9, Mn 0.2, Sn 25.8, S 30.3, sum 99.9 (all in weight percent); the corresponding chemical formula as calculated on the basis of total atoms=8 is, Cu 1.88 Fe 0.97 Zn 0.19 Mn 0.02 Sn 0.93 S 4.01, which fulfills approximately the ideal formula of $Cu_2FeSnS_4$. The strongest reflections on the X-ray diffraction patterns are; $3.10{\AA}$ (10) (112), $2.72{\AA}$ (5) (020, 004), $1.922{\AA}$ (5) (024), $1.642{\AA}$ (3) (132), $1.244{\AA}$ (3) (143, 136, 235), $1.111{\AA}$(3) (244), $0.958{\AA}$ (1) (048, 422), the patterns are identical with those of literature. From the textural evidence of the microscopic observation, the mineral is considered to have been formed at the middle stage of hydrothermal lead-zinc-silver mineralization.

한국·장군광산산 보울란저라이트에 대하여; 장군 연·아연·은 구성광물의 지식에 대한 기여 (2)

이현구,이마이 나오야,Lee, Hyun Koo,Imai, Naoya The Korean Society of Economic and Environmental G 1993 자원환경지질 Vol.26 No.2

장군광산산 보울란저라이트는 침상이나 불규칙한 형태로 방연석, 차골석, 함은 사면동석과 밀접하게 공생하여 남광상에서 산출되며, 특히 남광상 A광체와 B광체 주변의 능망간석대에 그 산출이 뚜렷하다. 어떤 장소, 특히 남광상 B광체 상부에는 방연석, 황철석, 유비철석, 함망간 방해석, 석영 등과 공생하여 작은 정동중에 "머리털"이나 "깃털"모양의 보울 란저라이트 집합체를 형성하기도 한다. 이광물의 반사색은 녹회색을 띠고, 반사다색성은 차골석보다 강하고 이방성이 명료하다. 반사율은 공기중에서 파장이 560nm 일 때 $R_{max.}=42.3%$, $R_{min.}=35.7%$이고, 비커스경도 (VHN)는 50g의 하중에서 $146{\sim}173kg/mm^2$이다. 표준시약 (Short, 1941)에 의한 반응에서는 HN03에서는 즉시 흑색으로 변하지만, 그외의 시약과는 거의 반응하지 않는다. 8개 시료 23개 입자에 대하여 EPMA로 분석한 결과 $Pb_{56.1}Sb_{25.1}S_{18.5}$, Total 99.6 wt.%이고, S= 11로해 계산된 화학식은 $Pb_{5.16}Sb_{3.94}S_{11}$로서 거의 보울란저라이트의 이상적인 화학식 $Pb_5Sb_4S_{11}$을 만족하고 있다. X-선 회절분석에 의해 얻어진 X-선 회절패턴에 나타나는 주요한 회절선은 $3.73\;{\AA}\;(10)$, $3.22\;{\AA}\;(5)$, $3.03\;{\AA}\;(4)$, $2.82\;{\AA}\;(5)$로서 공간군 $C^5_{2h}-P2_{1/a}$ 과 잘 일치한다. 이상의 장군광산산 보울란저라이트는 그 산출상태와 광물의 공생관계로부터 열수성 연-아연-은광화작용의 최후기에 생성된 광물로 판단된다. At the Janggun mine, boulangerite usually occurs as needles or irregularly-shaped grains, up to $500{{\mu}m}$ in longer dimensions, closely associated with galena, minerals of a tetrahedrite-freibergite series and bournonite in the peripheries of South A and B orebodies and the zone of manganoan carbonates surrounding them. In some places, especially at the top of South B orebody, it occures as "feather ore" consisting of its fine needles or "hairs" in small drusy cavities together with fine-grained euhedral galena, pyrite, manganoan carbonates, quartz, etc. In reflected light, it is bluish grey in colour exhibiting moderate bireflectance and is strongly anisotropic without any internal reflections. Reflectance in air is $R_{max}=43.2$, $R_{min}=35.7$ percent at wavelength of 580 nm, and VHN: $146-173\;kg/mm^2$ at a 50 g-load. The chemical composition on the average from 23 complete spot analyses by electron microprobe is, Pb 56.1, Sb 25.1, S 18.5, Total 99.6 (all in weight percent); the corresponding chemical formula calculated on the basis of S=11 is; $Pb_{5.16}Sb_{3.93}S_{11.0}$ which fulfils approximately the ideal formula $Pb_5Sb_4S_{11}$. The strongest reflections on the X-ray diffraction pattern are; $3.73\;{\AA}\;(10)$, $3.22\;{\AA}\;(5)$, $3.03\;{\AA}\;(4)$ and $2.82\;{\AA}\;(5)$ and the pattern is in harmonic with space group $C^5_{2h}-P2_1/a$. From the textural evidence of the microscopic observations, the mineral is considered to have been formed at the latest stage of hydrothermal lead-zinc-silver mineralization.

장군광산(將軍鑛山)의 연(鉛)·아연(亞鉛)·은(銀) 및 철(鐵) 광상(鑛床)의 성인(成因)과 지질구조(地質構造)와의 관계(關係) - 광상(鑛床) 생성(生成)의 지질구조(地質構造) 규제(規制)와 모암(母岩)의 변질(變質) -

이현구,고석주,나오야 이마이,Lee, Hyun Koo,Ko, Suck Jin,Naoya, Imai 대한자원환경지질학회 1990 자원환경지질 Vol.23 No.2

The lead-zinc-silver-iron deposits from the Janggun mine are of hydrothermal-metasomatic origin, characterized by the marked hydrothermal alteration of the wallrocks, such as hydrothermal manganese enrichment of carbonate rocks, silicification, chloritization, sericitization, montmorillonitization and argillic alteration. The ore deposits have been emplaced within the Janggun Limestone of Cambro-Ordovician age at the immediate contacts with apophyses injected from the Chunyang Granite plutons of Late Jurrasic age. They have been structurally controlled by fractures in the carbonate rocks and the irregular intrusive contacts of granitic rocks, and are closely associated with hypogene manganese carbonate deposits. In the mine nine seperate orebodies are being mined. On the basis of the petrological study, hydrothermal alteration zone of this mine may be divided into the following four zones from wallrock to orebody. (I) Primary calcite and dolomite zone${\rightarrow}$(II) dolomitic limestone zone${\rightarrow}$(III) dolomitic zone${\rightarrow}$(IV) rhodochrosite zone${\rightarrow}$ orebody. There was not recongnized Mn and Fe elements in the primary calcite and dolomite zone. But, in the dolomitic limestone and dolomite zone, calcite and dolomite were subjected to weak hydrothermal manganese enrichment and the grade of the manganese enrichment increase oreward. By means of electron probe microanalysis, it was found that manganoan dolomite occured between primary dolomite grains, cross the cleavage of the primary dolomite and around the dolomite grains. Above these result supports that the Janggun manganese carbonate deposits are of hydrothermal metasomatic origin.

Compositional Variation of Arsenopyrites in Arsenic and Polymetallic Ores from the Ulsan Mine, Republic of Korea, and their Application to a Geothermometer

최선규,정재일,이마이 나오야,Choi, Seon-Gyu,Chung, Jae-Ill,Imai, Naoya The Korean Society of Economic and Environmental G 1986 자원환경지질 Vol.19 No.3

울산(蔚山)의 철 중석 스카른광상에서 산출되는 유비철석(硫砒鐵石)은 그의 산출상태(産出狀態) 광물공생관계(鑛物共生關係) 화학조성(化學組成)을 근거로 세 가지 유형으로 구분된다. 유비철석(硫砒鐵石) I 은 다금속광화작용(多金屬鑛化作用) 초기에 정출된 것으로 주로 스카른대 내에서 산점상으로 분포하며, Ni-Fe-Co계 유화물과 밀접한 공생관계를 보여준다. 유비철석(硫砒鐵石) I 의 화학조성은 Ni, Co의 함량이 현저하게 높고 As/S(원자비(原子比))>1으로 과잉(過剩)의 비소를 함유한다. 유비철석(硫砒鐵石) II는 Cu 또는 As 광석중에서 산출되며, 비독사석 휘창연석 비스무스 황동석 섬아연석과 밀접한 공생관계를 보여준다. 유비철석(硫砒鐵石) II의 화학조성은 Ni, Co의 함량이 극히 미량이며, As/S>1으로 과잉(過剩)의 비소를 함유한다. 유비철석(硫砒鐵石) III은 최후기 열수광맥 형성시기에 정출되었으며, 황철석 방연석 섬아연석 자류철석과 밀접한 공생관계(共生關係)를 보여준다. 유비철석(硫砒鐵石) III의 화학조성(化學組成)은 $$As/S1{\leq_-}1$$로 과잉(過剩)의 S를 함유한다. 유비철석(硫砒鐵石) I 은 Ni, Co의 함유량이 1%이상이므로 지질온도계(地質溫度計)로 사용할 수 없지만, 유비철석(硫砒鐵石) II 는 비스무스-휘창연석의 공생관계(共生關係)를 보여 주고 있으므로, 이를 Kretschmar and Scott (1976)에 의한 $1/T-f(S_2)$도에 적용시켜보면 유비철석(硫砒鐵石) II의 정출환경은 $T=460{\sim}470^{\circ}C$, log $f(S_2)=-7.4{\sim}7.0$이고, 유비철석(硫砒鐵石) III의 정출환경은 $T=320{\sim}440^{\circ}C$, log $f(S_2)=-9.0{\sim}7.0$으로 추정된다. Arsenopyrite in arsenic and polymetallic ores from calcic Fe-W skarn deposit of the Ulsan mine, Republic of Korea, has been investigated by means of electron microprobe analysis and X-ray diffractometry. As a result, it is revealed that the Ulsan arsenopyrite may be classified into the following three species with different generation on the basis of its mode of occurrence, chronological order during polymetallic mineralization and chemical composition; arsenopyrites I, II and III. 1) Arsenopyrite I-(Ni, Co)-bearing species belonging to the oldest generation, which has crystallized together with (Ni, Co)-arsenides and -sulpharsenides in the early stage of polymetallic mineralization. In rare cases, it contains a negligible amount of antimony. It occurs usually as discrete grains with irregular outline, showing rarely subhedral form, and is diffused in skarn zone. The maximum contents of nickel and cobalt are 10.04 Ni and 2.45 Co (in weight percent). Occasionally, it shows compositional zoning with narrow rim of lower (Ni+Co) content. 2) Arsenopyrite II-arsenian species, in which (Ni+Co) content is almost negligible, may occur widely in arsenic ores, and its crystallization has followed that of arsenopyrite I. It usually shows subhedral to euhedral form and is closely associated with $l{\ddot{o}}llingite$, bismuth, bismuthinite, chalcopyrite, sphalerite, bismuthian tennantite, etc. It is worthy of note that arsenopyrite II occasionally contains particles consisting of both bismuth and bismuthinite. 3) Arsenopyrite III-(Ni, Co)-free, S-excess and As-deficient species is close to the stoichiometric composition, FeAsS. It occurs in late hydrothermal veins, which cut clearly the Fe-W ore pipe and the surrounding skarn zone. It shows euhedral to subhedral form, being extremely coarse-grained, and is closely associated with pyrite, "primary" monoclinic pyrrhotite, galena, sphalerite, etc. Among three species of the Ulsan arsenopyrite, arsenopyrite I does not serve as a geothermometer, because (Ni+Co) content always exceeds 1 weight percent. In spite of the absence of Fe-S minerals as sulphur-buffer assemblage, the presence of $Bi(l)-Bi_2S_3$ sulphur-buffer enables arsenopyrite II to apply successfully to the estimation of either temperature and sulphur fugacity, the results are, $T=460{\sim}470^{\circ}C$, and log $f(S_2)=-7.4{\sim}7.0$. With reference to arsenopyrite III, only arsenopyrite coexisting with pyrite and "primary" monoclinic pyrrhotite may serve to restrict the range of both temperature and sulphur fugacity, $T=320{\sim}440^{\circ}C$, log $f(S_2)=-9.0{\sim}7.0$. These temperature data are consistent with those obtained by fluid inclusion geothermometry on late grandite garnet somewhat earlier than arsenopyrite II. At the beginning of this paper, the geological environments of the ore formation at Ulsan are considered from regional and local geologic settings, and physicochemical conditions are suspected, in particular the formation pressure (lithostatic pressure) is assumed to be 0.5kb (50MPa). The present study on arsenopyrite geothermometry, however, does not bring about any contradictions against the above premises. Thus, the following genetical view on the Ulsan ore deposit previously advocated by two of the present authors (Choi and Imai) becomes more evident; the ore deposit was formed at shallow depth and relatively high-temperature with steep geothermal gradient-xenothermal conditions.