In-situ LA–ICP-MS trace elemental analyses of magnetite: The Mesozoic Tengtie skarn Fe deposit in the Nanling Range, South China
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Ore genesis
Mineral redox buffer
Sulfide Minerals
Abstract: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(‐Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits are of meteoric water origin whereas those for the Yoshiwara‐Sannotake Cu(‐Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively‐coupled plasma mass spectrometry (ICP‐MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase‐clinopyroxene rock, called Inishi rock) from the Kamioka Zn‐Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara‐Sannotake Cu(‐Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite‐normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn‐Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara‐Sannotake Cu(‐Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.
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인도네시아 까시한 지역 함 동-아연 스카른광체는 올리고신 후기 퇴적암류 중 석회암층을 따라 발달한다. 스카른광체의 괴상스카른대는 초기에서 후기로 단사휘석-석류석대, 석류석대, 석류석-녹염석대, 녹염석대 스카른으로 구분된다. 초기 괴상 스카른대에서 산출하는 단사휘석은 투휘석-헤덴버가이트 고용체로서, 초기 투휘석 단성분에 가까운 조성으로부터 후기 salitic 단사휘석으로의 조성변화가 확인된다. 이러한 단사휘석의 조성변화는 일반적인 스카른 광체에서의 수반 금속성분 (Cu 및 Zn광화작용)과 단사휘석 조성 상관관계와 잘 일치한다. 석류석의 경우 그로슐라-안드라다이트 고용체로서 매우 넓은 조성변화를 보여주며, 후기 석류석의 경우 Fe함량의 증가 경향성이 인지된다. 녹염석의 경우 클리노조이사이트-피스타사이트 고용체(65.8-76.2 mol. % 클리노조이사이트)로 확인된다. 상평형관계로 확인된 까시한 지역 함 동-아연 스카른광체는 약 0.5 kb의 환경에서 초기 약 $450^{\circ}C$ (단사휘석-석류석 및 석류석 스카른, ${\approx}450-370^{\circ}C$ ) 에서 시작되어 후기 $300^{\circ}C$ (석류석-녹염석 및 녹염석 스카른, ${\approx}370-300^{\circ}C$ ) 에 걸쳐 진행되었다. Copper-zinc-bearing skarns of the Kasihan area developed at limestone layers in the sedimentary facies of the Late Oligocene Arjosari Formation. The skarns consist mainly of fine-grained, massive clinopyroxene-garnet, garnet, garnet-epidote, and epidote skarns. Most copper and zinc(-lead) ore mineralization occur in the clinopyroxene-garnet and garnetepidote skarn, respectively. Clinopyroxene occurs as a continuous solid solution of diopside and hedenbergite (from nearly pure diopside up to ${\approx}34$ mole percent hedenbergite), with a maximum 28.2 mole percent johannsenite component. The early and late pyroxenes of Kasihan skarns are diopsidic and salitic, respectively. They fall in the fields typical Cu- and Zn-dominated skarns, respectively. Garnet displays a relatively wide range of solid solution between grossular and andradite with up to ${\approx}2.0$ weight percent MnO. Garnet in early pyroxene-garnet skarn ranges from 49.1 to 91.5 mole percent grossular (mainly ${\geq}78$ mole % grossular). Garnets in late garnet and garnet-epidote skarns range from 2.8 to 91.4 mole percent grossular (mainly ${\geq}70$ mole % for garnet skarn). Epidote compositions indicate solid solutions of clinozoisite and pistacite varying from 65.8 to 76.2 mole percent clinozoisite. Phase equilibria indicate that skarn evolution was the result of interaction of water-rich fluids ($X_{CO_2}{\leq}0.1$ ) with original lithologies at ${\approx}0.5$ kb with declining temperature (early clinopyroxene-garnet and garnet skarn, ${\approx}450$ to $370^{\circ}C$ ; late garnet-epidote and epidote skarn, ${\approx}370$ to $300^{\circ}C$ ).
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Andradite
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Abstract On the basis of geological studies of skarn deposits in China and by using thermodynamic models of the solid solution, the coexisting clinopyroxene‐ garnet pair in skarn deposits has been analysed and a coexisting clinopyroxene‐garnet acidometer developed. They can be used to estimate the medium condition under which the skarn was formed. The research on the acidity for the formation of various metallic skarn deposits in China suggests that skarns endowed with dissimilar types of mineralization and occurring in diverse environments differ in the acidity conditions for their formation and in the trend of acidity variation of ore‐bearing fluid. This, coupled with the study of oxygen fugacity of coexisting minerals, makes it possible to establish the oxygen fugacity‐ acidity facies of skarn deposits, which reflect the close genetic relationship between the metallization and the formation of skarn.
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The Nuocang Pb-Zn deposit is a newly discovered polymetallic skarn deposit in the southern Lhasa subterrane, western Gangdese, Tibet. The skarn occurs at the contact between the limestone of Angjie Formation and the Linzizong volcanic rocks of Dianzhong Formation (LDF), and the subvolcanic granite porphyry intruding those formations; the contact metasomatic skarn is well zoned mineralogically and texturally, as well as geochemically. The skarn minerals predominantly consist of an anhydrous to hydrous calc-silicate sequence pyroxene–garnet–epidote. The endoskarn mainly consists of an assemblage of pyroxene, garnet, ilvaite, epidote, and quartz, whereas the exoskarn is characterized proximal to distally, by decreasing garnet, and increasing pyroxene, ilvaite, epidote, chlorite, muscovite, quartz, calcite, galena, and sphalerite. Geochemical analyses suggest that the limestone provided the Ca for all the skarn minerals and the magmatic volatiles were the main source for Si (except the skarnified hornfels/sandstone, and muscovite-epidote-garnet-pyroxene skarn possibly from the host sandstones), with Fe and Mn and other mineralizing components. During the hydrothermal alteration, the garnet-pyroxene skarn and pyroxene-rich skarn gained Si, Fe, Mn, Pb, Zn, and Sn, but lost Ca, Mg, K, P, Rb, Sr, and Ba. However, the skarnified hornfels/sandstone, and muscovite-epidote-garnet-pyroxene skarn gained Fe, Ca, Mn, Sr, Zr, Hf, Th, and Cu, but lost Si, Mg, K, Na, P, Rb, Ba, and Li. The REEs in the skarn were sourced from magmatic fluids during the prograde stage. Skarn mineral assemblages and geochemistry indicate the skarn in the Nuocang deposit were formed in a disequilibrated geochemical system by infiltrative metasomatism of magmatic fluids. During the prograde stage, garnet I (And97.6Gro1.6) firstly formed, and then a part of them incrementally turned into garnet II (And64.4Gro33.8) and III (And70.22Gro29.1). The subsequent substitution of Fe for Al in the garnet II and III indicates the oxygen fugacity of the fluid became more reduced, then resulted in formation of significant pyroxene. However, the anisotropic garnet IV (And38.5Gro59.8) usually replaced the pyroxene. In the retrograde stage, the temperature decreased and oxygen fugacity increased, but hydrolysis increased with epidote, ilvaite, chlorite I, and muscovite forming with magnetite. The continuing decreasing temperature and mixing with meteoric water lead to Cu, Pb, and Zn saturation as sulfides. After the sulfides deposition, the continued mixing with large amounts of cold meteoric water would decrease its temperature, and increase its pH value (neutralizing), promoting the deposition of significant amounts of calcite and chlorite II. The geological, mineralogical, and geochemical characteristics of Nuocang skarn, suggest that the Nuocang deposit is of a Pb-Zn polymetallic type. Compared to the other typical skarn-epithermal deposits in the Linzizong volcanic area, it indicates that the Nuocang deposit may have the exploration potential for both skarn and epithermal styles of mineralization.
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Distal skarns form by the metasomatic reactions of a host rock induced by far-traveled hydrothermal fluids. Physical and structural characteristics and geochemical patterns of distal PbZn skarn bodies were studied at the Petrovitsa deposit in southern Bulgaria. Skarn bodies formed from the interaction of hydrothermal fluids with reactive host lithologies (marble and gneiss). These fluids were transported along sub-vertical feeder structures and lithological contacts. Epidote skarn developed in gneiss protolith, and pyroxene (johannsenite) skarn developed in marble. Detailed geological mapping, complimented by measurements of the internal structure of the skarn body using pyroxene growth versors, quantifies the propagation direction of the skarn body: 1) away from the major local fluid conduit (feeder structure), and 2) away from lithological contacts between aluminosilicate rock and marble. Such growth suggests that fluid flow was generally orthogonal to the skarn front propagation direction in the pyroxene skarn. Textural, mineralogical and geochemical data from skarn samples reveal multiple growth generations of major skarn calc-silicates epidote and pyroxene. The epidote skarn is characterized by limited spatial distribution and fine-grained epidote/clinozoisite growth associated with massive replacement and sulfide mineralization. The pyroxene skarn consists of acicular clinopyroxene crystals which form spheroidal aggregates with discrete growth banding. These bands are the physical representation of the cyclic fluid pulses which resulted in rhythmic skarn growth marked by geochemical banding. In situ geochemical analyses in the epidote skarn reveal early Al-rich epidote overprinted by Fe-rich epidote associated with higher Mn and Sr contents and irregular compositional banding. Clinopyroxene (Jo60–95) shows general increase in Na, Al, Mn, and REE + Y with distance from the feeder structure and lithologic contacts. These elements correlate with the distance traveled by the hydrothermal fluid from the feeder to the site of skarnification, which we define using a proxy based on the Al content of pyroxene crystals. This reflects an increasing degree of fluid "contamination" by interaction with the aluminosilicate host rocks and functions as a proxy for fluid transport distance. The spatial distribution of trace-elements in pyroxene on an outcrop scale is indicative of discrete pulses of hydrothermal fluid resulting in precipitation of skarn calc-silicates along the increasingly tortuous fluid pathway between the feeder structure and the skarn front, resulting in both the macro- and micro-scale chemical and textural variability of the skarn body.
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