Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(–Fe) Deposits in Japan

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.     

Genesis of the Kamioka Skarn Deposits: An Important Role of Clinopyroxene Skarn and Graphite-bearing Limestone in Precipitating Sulfide Ore

Abstract: A genetical relationship between skarn formation and mineralization is investigated for the Kamioka skarn deposits which are the largest Zn-Pb producer in Japan. In the Mozumi deposit, one of main deposits in the Kamioka mining area as well as Tochibora and Maruyama, clinopyroxene skarn was generally subjected to later replacement by garnet or magnetite–calcite–quartz during the Zn-Pb mineralization. The replacement of hedenbergitic clinopyroxene by andraditic garnet resulted in the formation of diopsidic clinopyroxene relicts. With the progress of replacement, the S/So value (So: an estimated area occupied by an original clinopyroxene grain in a thin section, S: a total area of relict clinopyroxene fragments) which is an index of the degree of replacement decreases from 0. 7 to 0. 1, and the hedenbergite mole percent of relict clinopyroxene decreases drastically from about 65 to less than 40. A close association of andraditic garnet and sphalerite suggests that heden-bergitic clinopyroxene skarn played an important role to reduce the relatively oxic ore-forming fluid enriched in Zn²⁺ and SO4^2– and to precipitate sphalerite from the fluid. Ferrous iron in the hedenbergitic clinopyroxene skarn was oxidized to form andraditic garnet. Besides this garnet formation, the mineral assemblage of magnetite–calcite–quartz replaced the clinopyroxene skarn at the time of mineralization. In both cases, the reduction of relatively oxic ore-forming fluid by hedenbergitic clinopy-roxene skarn at the later stage brought about the precipitation of sulfide minerals. In contrast, these types of later replacement are not found in the Tochibora deposit. Instead, graphite-bearing crystalline limestone and relatively fresh clinopyroxene skarn are common. Mineralized clinopyroxene skarn has high graphite carbon contents relative to barren one, suggesting that the amount of graphite in the skarn was an important controlling factor for mineralization. It is very likely that the graphite played a role of reducing agent during the mineralization in the Tochibora deposit.     

Constraints on the mineralization processes of the Makeng iron deposit,eastern China: Fluid inclusion,H–O isotope and magnetite trace element analysis

The Makeng iron deposit is located in the Yong’an-Meizhou depression belt in Fujian Province, eastern China. Both skarn alteration and iron mineralization are mainly hosted within middle Carboniferous-lower Permian limestone. Five paragenetic stages of skarn formation and ore deposition have been recognized: Stage 1, early skarn (andradite–grossular assemblage); Stage 2, magnetite mineralization (diopside–magnetite assemblage); Stage 3, late skarn (amphibole–chlorite–epidote–johannsenite–hedenbergite–magnetite assemblage); Stage 4, sulfide mineralization (quartz–calcite–fluorite–chlorite–pyrite–galena–sphalerite assemblage); and Stage 5, carbonate (quartz–calcite assemblage). Fluid inclusion studies were carried out on inclusions in diopside from Stage 2 and in quartz, calcite, and fluorite from Stage 4.Halite-bearing (Type 1) and coexisting two-phase vapor-rich aqueous (Type 3) inclusions in the magnetite stage display homogenization temperatures of 448–564 °C and 501–594 °C, respectively. Salinities range from 26.5 to 48.4 and 2.4 to 6.9 wt% NaCl equivalent, respectively. Two-phase liquid-rich aqueous (Type 2b) inclusions in the sulfide stage yield homogenization temperatures and salinities of 182–343 °C and 1.9–20.1 wt% NaCl equivalent. These fluid inclusion data indicate that fluid boiling occurred during the magnetite stage and that fluid mixing took place during the sulfide stage. The former triggered the precipitation of magnetite, and the latter resulted in the deposition of Pb, Zn, and Fe sulfides. The fluids related to magnetite mineralization have δ¹⁸O_fluid-VSMOW of 6.7–9.6‰ and δD of −96 to −128‰, which are interpreted to indicate residual magmatic water from magma degassing. In contrast, the fluids related to the sulfide mineralization show δ¹⁸O_fluid-VSMOW of −0.85 to −1.04‰ and δD of −110 to −124‰, indicating that they were generated by the mixing of magmatic water with meteoric water. Magnetite grains from Stage 2 exhibit oscillatory zoning with compositional variations in major elements (e.g., SiO₂, Al₂O₃, CaO, MgO, and MnO) from core to rim, which is interpreted as a self-organizing process rather than a dissolution-reprecipitation process. Magnetite from Stage 3 replaces or crosscuts early magnetite, suggesting that later hydrothermal fluid overprinted and caused dissolution and reprecipitation of Stage 2 magnetite. Trace element data (e.g., Ti, V, Ca, Al, and Mn) of magnetite from Stages 2 and 3 indicate a typical skarn origin.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

矿物——成矿与找矿

单颗粒矿物微量元素激光原位定量分析测试数据的大量积累和研究,使矿物成为矿床地球化学研究和矿床勘查的重要示踪剂。本文重点选择磁铁矿、磷灰石、石榴子石、榍石、锆石、绿泥石和绿帘石等的原位分析研究所获得的认识,介绍单颗粒矿物成分组合及变化在矿床类型划分、成矿年龄测定、氧逸度、成矿过程与物质来源、找矿与勘探等方面的应用。不同矿床类型中普遍存在的矿物,如磁铁矿、磷灰石等的微量元素含量及组合差异,提供了矿床类型识别的标志。单颗粒矿物,特别是矿石矿物和密切共生矿物如锡石、铌钽铁矿、赤铁矿、石榴子石、方解石等的原位定年,使成矿年龄的直接准确测定成为现实。矿物中变价元素,如Fe、V、Mn、Ce、Eu含量和/或比值的变化,指示了成矿过程氧逸度及其变化特点。从矿物核部向震荡环带与边部的微量元素含量或同位素组成的变化,示踪了成矿过程中流体来源或性质的变化。斑岩和矽卡岩矿床中与成矿作用关系密切的蚀变矿物,如绿泥石、绿帘石的形成温度、特征微量元素比值,如Ti/Sr、Ti/Co、V/Ni、Mg/Sr等,与距矿床中心距离呈线性函数关系,可定量预测距矿床中心的距离,使以绿泥石、绿帘石为代表的找矿指示矿物研究迅速发展。     

In-situ LA–ICP-MS trace elemental analyses of magnetite: The Mesozoic Tengtie skarn Fe deposit in the Nanling Range,South China

The Nanling Range in South China hosts numerous world-class W–Sn deposits and some Fe deposits. The Mesozoic Tengtie Fe skarn deposit in the southern Nanling Range is contemporaneous with the regional Sn mineralization. The deposit is composed of numerous ore bodies along the contacts between the late Paleozoic or Mesozoic carbonate rocks and the Yanshanian Lianyang granitic complex. Interaction of the magma with hosting dolomitic limestone and limestone formed calcic (Ca-rich) and magnesian (Mg-rich) skarns, respectively. The Tengtie deposit has a paragenetic sequence of the prograde stage of anhydrous skarn minerals, followed by the retrograde stage of hydrous skarn minerals, and the final sulfide stage. Magnetite in the prograde and retrograde skarn stages is associated with diopside, garnet, chlorite, epidote, and phlogopite, whereas magnetite of the final stage is associated with chalcopyrite and pyrite. Massive magnetite ores crosscut by quartz and calcite veins are present mainly in the retrograde skarn stage. Laser ablation ICP-MS was used to determine trace elements of magnetite from different stages. Some magnetite grains have unusually high Ca, Na, K, and Si, possibly due to the presence of silicate mineral inclusions. Magnetite of the prograde stage has the highest Co contents, but that of the sulfide stage is extremely poor in Co which partitions in sulfides. Magnetite of magnesian skarns contains more Mg, Mn, and Al than that of calcic skarns, attributed to the interaction of the magma with compositionally different host rocks. Magnetite from calcic and magnesian skarns contains 6–185 ppm Sn and 61–1246 ppm Sn, respectively. The high Sn contents are not due to the presence of cassiterite inclusions which are not identified in magnetite. Instead, we believe that Sn resides in the magnetite structure. Regionally, intensive Mesozoic Sn mineralization in South China indicates that concurrent magmatic–hydrothermal fluids may be rich in Sn and contribute to the formation of high-Sn magnetite. Our study demonstrates that trace elements of magnetite can be a sensitive indicator for the skarn stages and wall-rock compositions, and as such, trace elemental chemistry of magnetite can be a potentially powerful fingerprint for sediment provenance and regional mineralization.     

Geochemistry,fluid inclusion and stable isotope constraints (C and O) of the Sivrikaya Fe-skarn mineralization (Rize,NE Turkey)

The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr_{79.45−99.03}Grs_0−17.9Prs_0.97−2.65 and Di_69.1−77.1Hd_22.2−29.8Jhn_0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (T_h) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl₂ in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl₂, FeCl₂, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH₄ was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ¹⁸O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ¹⁸O values of marine limestones. Decreases in δ¹⁸O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ¹³C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH₄ and CH₂ in fluid inclusions can be explained by the thermal degradation of these organic materials.     

Origin and evolution of hydrothermal fluids in the Taochong iron deposit,Middle–Lower Yangtze Valley,Eastern China: Evidence from microthermometric and stable isotope analyses of fluid inclusions

The Middle–Lower Yangtze River Valley is one of the most important metallogenic belts in China, hosting numerous Cu–Fe–Au–Mo deposits. The Taochong deposit is located in the northern part of the Fanchang iron ore district of the Middle–Lower Yangtze River metallogenic belt. The Fe-orebody is hosted by Middle Carboniferous to Lower Permian limestones. Skarns and Fe-orebodies occur as tabular bodies along interlayer-gliding faults, at some distance from the inferred granitic intrusions. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity—the skarn, iron oxide (main mineralization stage), and carbonate stages—all contributed to the formation of the Taochong iron deposit. The skarn stage is characterized by the formation of garnet and pyroxene, with high-temperature, hypersaline hydrothermal fluids with isotopic compositions similar to those of typical magmatic fluids. These fluids were probably generated by the separation of brine from a silicate melt instead of the product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by actinolite, chlorite, quartz, calcite and hematite. The hydrothermal fluids at this stage are represented by saline fluid inclusions that coexist with vapor-rich inclusions with anomalously low δD values (− 66‰ to − 94‰). The decrease in ore fluid δ¹⁸O_water with time and decreasing depth is consistent with the decreases in fluid salinity and temperature. The fluid δD values also show a decreasing trend with decreasing depth. Both fluid inclusion and stable isotopic data suggest that the ore fluid during the main period of mineralization was evolved by the boiling of various mixtures of magmatic brine and meteoric water. This process was probably induced by a drop in pressure from lithostatic to hydrostatic. The carbonate stage is represented by calcite veins that cut across the skarn and orebody, locally producing a dense stockwork. This observation indicates the veins formed during the waning stages of hydrothermal activity. The fluids from this stage are mainly represented by a variety of low-salinity fluid inclusions, as well as fewer high-salinity inclusions. These particular fluids have the lowest δ¹⁸O_water values (− 2.2‰ to 0.4‰) and a wide of range of δD values (− 40‰ to − 81‰), which indicate that they were originated from a mixture of residual fluids from the oxide stage, various amounts of meteoric water, and possibly condensed vapor. Low-temperature boiling probably occurred during this stage.We also discuss the reasons behind the anomalously low δD values in fluid inclusion water extracted by thermal decrepitation from quartz at high temperatures, and suggest that calcite data provide a possible benchmark for adjusting low δD values found in quartz intergrown with calcite.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal’negorsk Ore Region (Primorye)

The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag–Pb–Zn deposits of the region. It was pointed out that the δ³⁴S modal values range from–1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ³⁴S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.     

Zinc-lead skarn deposits at Leadville, New South Wales, Australia, and their distinction from volcanic-hosted massive sulphides

Exploration of Zn-rich sulphide deposits at Leadville, northern Lachlan Fold Belt, New South Wales, for over two decades has been largely on the premise that the mineralisation represents felsic volcanic-hosted massive sulphides (VHMS). Deposits are hosted by ?Silurian felsic metavolcanic, psammopelitic and calcareous metasedimentary rocks which have been intruded by the late Carboniferous I-type Gulgong Granite. Evidence for an epigenetic replacement (skarn) origin of the deposits, rather than representing metamorphosed volcanogenic massive sulphides, includes the proximity of evolved granitic intrusives and reactive carbonate rocks, a skarn mineral assemblage (with characteristic prograde and retrograde stages), lack of textural or lithological indications of an exhalative origin, and gossan and sulphide compositions consistent with Zn-Pb skarns and atypical of Lachlan Fold Belt VHMS deposits. Furthermore, sulphide lead isotope ratios are significantly more radiogenic than signatures for VHMS deposits in the Lachlan Fold Belt. Carbonate δ¹³C and δ¹⁸O and sulphide δ³⁴S values are consistent with the interaction of magmatic hydrothermal fluids with Palaeozoic carbonate rocks and a largely magmatic source of sulphur. It is concluded that the Leadville deposits are of skarn type, genetically related to the Gulgong Granite.     

Association of Electrum and Calcite and Its Significance to the Genesis of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract. Mineral assemblage, precipitation sequence and textures of the gold‐bearing veins from the Hishikari epithermal vein‐type deposits, southern Kyushu, Japan, were examined. In addition, fluid inclusion microthermometry and carbon and oxygen isotopic compositions of calcite were determined. Calcite, and that replaced by quartz, were commonly observed throughout the precipitation sequence of the veins. Thus, calcite must be a more common gangue constituent initially than observed presently. Association of calcite and electrum is observed immediately subsequent to columnar adularia in some vein samples. In addition, close association of electrum with pseudo‐acicular quartz, and electrum with truscottite were observed. The initial coprecipitation of electrum and calcite might be a common phenomenon in the gold‐bearing veins at the Hishikari deposits. The Th (homogenization temperature) data from the Honko‐Sanjin deposits are generally higher than those from the Yamada deposit. Samples that show association of calcite and electrum yielded higher Th (206–217°C, average) than the Th data from calcite associated with low‐grade Au ore or barren (180–204°C, average). The measured Tm (temperature of last melting point of ice) range from ‐0.4 to 0.0°C. The result suggests that the salinity of the hydrothermal solution was low during the precipitation both of calcite associated with Au mineralization and of barren calcite. Fluid inclusion evidence suggestive of boiling of hydrothermal solution for the precipitation of calcite was not recognized in the present work. The δ¹³C and δ¹⁸O values of calcite range from ‐10.8 to —4.7 % and from +3.2 to +15.2 %, respectively. The δ¹³C value of H₂CO₃ and the δ¹⁸O value of H₂O in the hydrothermal fluids calculated assuming isotopic equilibrium with calcite using the temperature obtained by fluid inclusion microthermometry, range from ‐14.4 to ‐9.1 %, and from ‐6.2 to +5.5 %, respectively. Thus, the calculated δ¹⁸O values of H₂O for calcite further confirm the presence of the ¹⁸O‐enriched ore fluids during the mineralization at the Hishikari deposits. The hydrothermal solution isotopically equilibrated with the sedimentary basement rocks was responsible for the gold mineralization associated with calcite.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

The geology and genesis of the iron skarns of the Turgai belt,northwestern Kazakhstan

The magnetite deposits of the Turgai belt (Kachar, Sarbai and Sokolov), in the Valerianovskoe zone of the southern Urals, Kazakhstan, contain a combined resource of over 3 Gt of iron oxide ore. The deposits are hosted by carbonate sediments and volcaniclastic rocks of the Carboniferous Valerianovka Supergroup, and are spatially related to the gabbroic to granitoid composition intrusive rocks of the Sarbai–Sokolov intrusive series. The magnetite deposits are developed dominantly as metasomatic replacement of limestone, but also, to a lesser extent, of volcanic rocks. Pre-mineralisation metamorphism and alteration resulted in the formation of wollastonite and the silicification of limestone. Magnetite mineralisation is associated with the development of a high temperature skarn assemblage of diopside, grossular–andradite garnet, actinolite, epidote and apatite. Sub-economic copper-bearing sulphide mineralisation overprints the magnetite mineralisation and is associated with deposition of hydrothermal calcite and the formation of an extensive sodium alteration halo dominated by albite and scapolite. Chlorite formation accompanies this stage and further later stage hydrothermal overprints. The replacement has in places resulted in preservation of primary features of the limestone, including fossils and sedimentary structures in magnetite, skarn calc-silicates and sulphides.Analysis of Re–Os isotopes in molybdenite indicates formation of the sulphide mineral assemblage at 336.2 ± 1.3 Ma, whilst U–Pb analyses of titanite from the skarn alteration assemblage suggests skarn alteration at 326.6 ± 4.5 Ma with re-equilibration of isotope systematics down to ~ 270 Ma. Analyses of mineral assemblages, fluid inclusion microthermometry, O and S isotopes suggest initial mineralisation temperatures in excess of 600 °C from hypersaline brines (45–50 wt.% NaCl eq.), with subsequent cooling and dilution of fluids to around 150 °C and 20 wt.% NaCl eq. by the time of calcite deposition in late stage sulphide-bearing veins. δ¹⁸O in magnetite (− 1.5 to + 3.5‰) and skarn forming silicates (+ 5 to + 9‰), δ¹⁸O and δ¹³C in limestone and skarn calcite (δ¹⁸O + 5.4 to + 26.2‰; δ¹³C − 12.1 to + 0.9‰) and δ³⁴S in sulphides (− 3.3 to + 6.6‰) and sulphates (+ 4.9 to + 12.9‰) are all consistent with the interaction of a magmatic-equilibrated fluid with limestone, and a dominantly magmatic source for S. All these data imply skarn formation and mineralisation in a magmatic–hydrothermal system that maintained high salinity to relatively late stages resulting in the formation of the large Na-alteration halo. Despite the reported presence of evaporites in the area there is no evidence for evaporitic sulphur in the mineralising system.These skarns show similarities to some members of the iron oxide–apatite and iron oxide–copper gold deposit classes and the model presented here may have implications for their genesis. The similarity in age between the Turgai deposits and the deposits of the Magnitogorsk zone in the western Urals suggests that they may be linked to similar magmatism, developed during post-orogenic collapse and extension following the continent–continent collision, which has resulted in the assembly of Laurussian terranes with the Uralide orogen and the Kazakh collage of the Altaids or Central Asian Orogenic Belt. This model is preferred to the model of simultaneous formation of very similar deposits in arc settings at either side of an open tract of oceanic crust forming part of the Uralian ocean.     

Genesis of the Nanyangtian scheelite deposit in southeastern Yunnan Province,China: evidence from mineral chemistry,fluid inclusions,and C–O isotopes

The Nanyangtian skarn-type scheelite deposit is an important part of the Laojunshan W–Sn polymetallic metallogenic region in southeastern Yunnan Province, China. The deposit comprises multiple scheelite ore bodies; multilayer skarn-type scheelite ore bodies are dominant, with a small amount of quartz vein-type ore bodies. Skarn minerals include diopside, hedenbergite, grossular, and epidote. Three mineralization stages exist: skarn, quartz–scheelite, and calcite. The homogenization temperatures of fluid inclusions in hydrothermal minerals that formed in different paragenetic phases were measured as follows: 221–423 °C (early skarn stage), 177–260 °C (quartz–scheelite stage), and 173–227 °C (late calcite stage). The measured salinity of fluid inclusions ranged from 0.18% to 16.34% NaCleqv (skarn stage), 0.35%–7.17% NaCleqv (quartz–scheelite stage), and 0.35%–2.24% NaCleqv (late calcite vein stage). Laser Raman spectroscopic studies on fluid inclusions in the three stages showed H₂O as the main component, with N₂ present in minor amounts. Minor amounts of CH₄ were found in the quartz–scheelite stage. It was observed that the homogenization temperature gradually reduced from the early to the late mineralization stages; moreover, δ¹³C_PDB values for ore-bearing skarn in the mineralization period ranged from ? 5.7‰ to ? 6.9‰ and the corresponding δ¹⁸O_SMOW values ranged from 5.8‰ to 9.1‰, implying that the ore-forming fluid was mainly sourced from magmatic water with a minor amount of meteoric water. Collectively, the evidence indicates that the formation of the Nanyangtian deposit is related to Laojunshan granitic magmatism.     

Geochemical Indication of Sinian Bedded Siliceous Rocks in the Hunan-Guizhou-Guangxi Area and Their Environmental Significance

In the Hunan-Guizhou-Guangxi area there have developed very thick bedded siliceous rocks of the late Sinian. The rocks have a fairly pure composition, with an average content of siliceous minerals exceeding 95%. They are relatively rich in Fe and Mn, and poor in Al, Ti and Mg. The Fe/Ti, (Fe+Mn)/Ti, Al/(Al+Fe+Mn) and U/Th ratios and the Al-Fe-Mn and Fe-Mn-(Ni+Co+Cu)×10 triangle diagrams all show that they are hydrothermal sedimentary siliceous rocks. In the rocks the total amount of REEs is low, the δCe shows an obvious negative anomaly and the 8Eu a weak anomaly, and LREE>HREE, all indicating that they are products of hydrothermal processes. The δ30Si and δ18O values, as well as the formation temperature of the rocks all clearly show that the silica forming the rocks comes from hot water. Besides, analyses of the depositional environment of the rocks using the MnO/TiO2 ratio and the δCe and δ30Si values yield the same conclusion that they are formed in environments from continental marginal slope     

Geology, Ar-Ar Age and Mineral Assemblage of Eocene Skarn Cu-Au±Mo Deposits in the Southeastern Gangdese Arc, Southern Tibet: Implications for Deep Exploration

Abstract. Medium‐ and large‐scaled skarn Cu‐Au±Mo deposits, e.g. Kelu, Liebu, Chongmuda and Chenba among others, are distributed in Shannan area of the Gangdese Cu‐Au metallogenic belt. Intrusions‐related skarn copper mineralization belongs to high K and calc‐alkaline rock series, located in late collision volcano‐magmatic arc and formed between 20 to 30 Ma. Copper mineralization occurs at exocontact zone of the lower Cretaceous Bima Group carbonate and other calcareous‐bearing sedimentary rocks with intrusions. At present, three main mineralization types are identified, including skarn type, hydrothermal vein type and porphyry type. Mineralizing associations are Cu‐Mo, Cu‐Au and Cu. In ore districts, those mineralization types form an entire porphyry‐skarn Cu‐Au±Mo ore‐forming system. Alterations of the exocontact are mainly skarnization and hornfelsization, while the alterations of the endocontact are mainly sericitization, silicification, and chloritization of intrusion. In the study area, the endoskarn is not well developed. Copper mineralization occurs mainly in the exocontact in the form of stratoid, lenticular and pockety ore body. Veined mineralization can be seen in marblized and hornfelsed siltstone, being away from the contact zone. In the endocontact, the mineralization is mainly veinlet‐like and disseminated. In Shannan area, skarnization can be divided into early skarnization stage and late hydrous silicate stage. The early skarnization stage is featured by mainly andradite and grossular skarn, containing minor diopside, hedenbergite, magnetite and some copper minerals; and the late hydrous silicate stage is of replacement of garnet skarn by chlorite, epidote, quartz and calcite together with sulfides precipitation. The latter is the main stage of copper mineralization. Bornite is the dominant ore mineral associated with minor chalcopyrite and pyrite; and gold as well as silver are distributed in bornite and wittichenite. Results of microthermometry study of fluid inclusions in quartz of late hydrous silicate stage from different deposits show intermediate temperature and low to intermediate‐salinity features for all samples. The dominant inclusion type is composed of two phases, being about 4 to 15 % vapor and 85 to 96 % liquid at room temperature. Homogenization temperatures range from 232 to 335d?C. Salinities have been recorded between 4.2 and 15.5 wt% NaCl equivalent. Boiling fluid inclusions are not identified and it indicates that metal deposition mainly resulted from water‐rock reactions. The results of sulfur isotope analysis indicate that the sulfur isotope values (δ³⁴S 1.29–1.68 %o) of the samples collected from skarns are similar with that from the endocontact (δ³⁴S 1–1.75 %o). Both of them have very close sulfur isotope values (near δ³⁴S 0 %o), which indicate the sulfur of both the skarn type and the porphyry type mineralization was from deep sources. Ages determined on biotite from ore‐bearing intermediate porphyries by Ar‐Ar methods range from 23.77±0.29 to 29.88±0.56 Ma, showing that skarn copper mineralization in the study area evidently is older than the porphyry Cu(‐Mo) mineralization in Gangdese, and likely representing another metallogenic event. The Cu‐Au skarn deposits in the Kelu‐Liebu‐Chongmuda belt are interpreted as the shallow level, skarn‐related deposits in a porphyry‐skarn mineralization. Appearance of porphyry copper mineralization in some skarn deposits implies that skarn copper mineralization of the study area resemble to those in northern sub‐metallogenic belt, having uniform porphyry‐skarn ore‐forming system. Therefore, it is presumed there should be potential to find deep level porphyry‐type Cu‐Au mineralization targets.     

Re–Os isotopic ages of pyrite and chemical composition of magnetite from the Cihai magmatic–hydrothermal Fe deposit, NW China

The Eastern Tianshan Orogenic Belt of the Central Asian Orogenic Belt and the Beishan terrane of the Tarim Block, NW China, host numerous Fe deposits. The Cihai Fe deposit (>90 Mt at 45.6 % Fe) in the Beishan terrane is diabase-hosted and consists of the Cihai, Cinan, and Cixi ore clusters. Ore minerals are dominantly magnetite, pyrite, and pyrrhotite, with minor chalcopyrite, galena, and sphalerite. Gangue minerals include pyroxene, garnet, hornblende and minor plagioclase, biotite, chlorite, epidotite, quartz, and calcite. Pyrite from the Cihai and Cixi ore clusters has similar Re–Os isotope compositions, with ～14 to 62 ppb Re and ≤10?ppt common Os. Pyrrhotite has ～5 to 39 ppb Re and ～0.6 ppb common Os. Pyrite has a mean Re–Os model age of 262.3?±?5.6 Ma (n?=?13), in agreement with the isochron regression of ¹⁸⁷Os vs. ¹⁸⁷Re. The Re–Os age (～262 Ma) for the Cihai Fe deposit is within uncertainty in agreement with a previously reported Rb–Sr age (268?±?25 Ma) of the hosting diabase, indicating a genetic relationship between magmatism and mineralization. Magnetite from the Cihai deposit has Mg, Al, Ti, V, Cr, Co, Ni, Mn, Zn, Ga, and Sn more elevated than that of typical skarn deposits, but both V and Ti contents lower than that of magmatic Fe–Ti–V deposits. Magnetite from these two ore clusters at Cihai has slightly different trace element concentrations. Magnetite from the Cihai ore cluster has relatively constant trace element compositions. Some magnetite grains from the Cixi ore cluster have higher V, Ti, and Cr than those from the Cihai ore cluster. The compositional variations of magnetite between the ore clusters are possibly due to different formation temperatures. Combined with regional tectonic evolution of the Beishan terrane, the Re–Os age of pyrite and the composition of magnetite indicate that the Cihai Fe deposit may have derived from magmatic–hydrothermal fluids related to mafic magmatism, probably in an extensional rift environment.