Determination of the Tin Stable Isotopic Composition in Tin‐bearing Metals and Minerals by MC‐ICP‐MS

This study uses MC‐ICP‐MS for the precise analysis of the stable tin isotopic composition in ore minerals of tin (cassiterite, stannite), tin metal and tin bronze. The ultimate goal is to determine the provenance of tin in ancient metal objects. We document the isotope compositions of reference materials and compare the precision of different isotope ratios and the accuracy of different procedures of mass fractionation correction. These data represent a base with which isotopic data of future studies can be directly compared. The isotopic composition of cassiterite and stannite can be determined after reduction to tin metal and bronze, respectively. Both metals readily dissolve in HCl, but while the solutions of tin metal can be directly measured, the bronze solutions must be purified with an anion exchanger. The correction of the mass bias is best performed with an internal Sb standard and an empirical regression method. A series of Sn isotope determinations on commercially available mono‐element Sn solutions as well as reference bronze materials and tin minerals show fractionations ranging from about ?0.09‰ to 0.05‰/amu. The combined analytical uncertainty (2s) was determined by replicate dissolutions of reference materials of bronze (BAM 211, IARM‐91D) and averages at about 0.005‰/amu.     

Hydrothermal Alteration of Limestone and Mineral Exploration of Zn-Pb Skarn Deposits in the Sako-nishi Area of the Kamioka Mine, Central Japan

Abstract: Crystalline limestone of the Sako-nishi area in the Kamioka Zn-Pb mine, central Japan, is depleted in ¹⁸O and ¹³C toward the center of mineralization due to interaction with hydrothermal fluids with a dominant meteoric water component. The relationship between isotopic composition and mineral assemblage, texture, the chemical composition of the minerals, and the bulk chemical composition in the limestone was examined. A decrease in the δ¹⁸OSMOW value correlated with: (1) increase of fine-grained calcite which is enriched in Mn and exhibits a bright cathodoluminescence, (2) progressive hy-drothermal alteration of clinopyroxene in the original limestone into tremolite within the weakly-altered zone, and into chlorite and actinolite within the strongly-altered zone, (3) dominance of hydrothermal chlorite in altered limestone having δ¹⁸O values of less than 10%. This chlorite was enriched in Fe compared to mafic minerals in the unaltered limestone. The enrichment of Fe and Mn was more conspicuous in calcite and chlorite in skarn deposits. The occurrence and chemical composition of hydrothermal minerals in the limestone, skarn, and ore indicate that the ¹⁸O–depleted zones were formed in the later stage from fluids, which were responsible for mineralization and skarnization, and for Fe and Mn enrichment. The Al, Mn, and Fe contents, and the ratios of Mg/(Mg+Mn+Fe), Al/Mg, and Mn/Sr in the hydrochloric acid leachate of limestone varied with decreasing δ¹⁸O and δ¹³C values, reflecting increases in high-Mn calcite and high-Fe chlorite. These indexes were useful for the identification of hydrothermally altered limestone. Furthermore, the potential score weighted by each index was more effective and accurate means of detecting promising mineralization zones. An anomalous potential score due to the presence of hydrothermal minerals in the outcropping limestone occurred along the Atotsu–1GO fault. This structure indicates that the skarn deposits of the Sako-nishi area belong to Mozumi-type Zn–Pb skarn deposits, in which fissures and faults served as major passages for the hydrothermal fluid. High-Mn carbonate and high-Fe chlorite widely occur in base-metal vein deposits and Zn-Pb type skarn deposits. Leaching of altered rock with hydrochloric acid in addition to stable isotope composition and cathodoluminescence imaging is effective for geochemical exploration for hydrothermal deposits because it makes possible the detection of the elemental composition of hydrothermal minerals such as chlorite and carbonate and because of the rapidity and convenience of analysis.     

Mineralogy,Sulfur Isotope and Fluid Inclusion Studies of Hydrothermal Ore at the Hakurei Deposit,Bayonnaise Knoll,Izu‐Bonin Arc

Sulfide and sulfate ore samples collected from the Hakurei deposit of the Bayonnaise knoll were examined for the occurrence and chemical composition of minerals, including the sulfur isotopes and the microthermometry of fluid inclusions. Massive sulfide ore, mineralized volcanic rock, and anhydrite ore occur in descending order, from the seafloor to the bottom of the cored sample. The massive sulfide ore is dominated by sphalerite and accompanied by tennantite, chalcopyrite, and pyrite with lesser amounts of galena, enargite, and covellite. Amorphous silica is commonly precipitated on the surface of the sulfide minerals. As‐bearing minerals such as tennantite, enargite, and luzonite are common, while galena and Sb‐rich tetrahedrite are scarce. The mineral abundance and chemical composition of the minerals differs from that found in chimneys of the deposit. The sulfur isotope compositions in the minerals are +3.1–5.2‰ for sulfides and +19.6–21.8‰ for sulfate minerals. The homogeneous nature of the sulfur isotopes suggests that sulfur incorporated in the Hakurei deposit came from the reduction of aqueous sulfate in seawater.     

K-Ar Ages of Granitic Magmatism and Related Pegmatite Formation at the Umanotani-Shiroyama Mine, Shimane Prefecture, SW Japan and Their Bearings on Cooling History

Abstract. The Umanotani-Shiroyama pegmatite deposits, the largest producer of K-feldspar and quartz in Japan, are of typical granitic pegmatite. Ilmenite-series biotite granite and granite porphyry, hosting the ore deposits, and biotites separated from these rocks yielded K-Ar ages ranging from 89.0 to 81.4 Ma and 95.2 to 93.7 Ma, respectively. Muscovite and K-feldspar separated from the ore zone yielded K-Ar ages with the range of 96.2 to 93.1 Ma and 87.3 to 80.7 Ma, respectively. Muscovites from quartz-muscovite veins in the ore zone and in the granite porphyry yielded K-Ar ages of 90.4 and 76.3 Ma, respectively. K-feldspar is much younger in age than coexisting muscovite. It is noted that the K-Ar ages of biotite separates and the whole-rock ages are identical to those of muscovite and K-feldspar in the ore zone, respectively. These time relations, as well as field occurrence, indicate that the formation of the pegmatite deposits at the Umanotani-Shiroyama mine is closely related in space and time to a series of granitic magmatism of ilmenite-series nature. Using closure temperatures of the K-Ar system for biotite and K-feldspar (microcline), cooling rate of the pegmatite deposits is estimated to be about 82C/m.y. at the beginning, but slowed down to about 15C/m.y. in the later period.     

Mineralogy,Fluid Inclusion,and Hydrogen and Oxygen Isotope Studies of the Intrusion‐Related Yangla Cu Deposit in the Sanjiang Region,SW China: Implications for Metallogenesis and Deposit Type

The Yangla deposit is an intrusion‐related Cu deposit in the Jinshajiang tectonic belt (eastern Sanjiang region, SW China). Despite extensive studies that have been conducted on this deposit, the relationship between the granitic magma and Cu mineralization is still unclear, and hence, the genesis is debated. To answer this question, we conducted an integrated study of mineralogy, fluid inclusions (FIs), and hydrogen and oxygen (H‐O) isotopes. Three mineralization stages were identified based on the ore textures, alteration zonation, and crosscutting relationships: (i) pre‐ore prograde skarn (stage I), with the garnet and pyroxene dominated by andradite and diopside, respectively; (ii) syn‐ore retrograde alteration (stage II), which is subdivided into the early syn‐ore stage (stage IIa) marked by retrograde hydrated mineral assemblages and significant Fe‐Cu‐Mo‐Pb‐Zn sulfide mineralization, and the late syn‐ore stage (stage IIb) featured by quartz‐calcite veins; and (iii) late supergene mineralization (stage III), which is characterized by secondary azurite and malachite. These results of mineralogy, FIs, and H‐O isotopes indicate that: (i) Cu mineralization has a close temporal, spatial, and genetic relationship with skarn alteration; (ii) the ore fluids were magmatic dominated with late‐stage meteoric water incursion; and (iii) Type‐S (halite‐bearing) and Type‐V (vapor‐rich) FIs coexisted in garnet and clinopyroxene of stage I, indicating that fluid boiling might have occurred during this stage. From stage I to stage IIa, the FI type transformed from Type‐S + Type‐V + Type‐L (liquid‐rich) to Type‐V + Type‐L with the conduct of mineralization and was accompanied by the disappearance of Type‐S, and homogenization temperature and salinity also tended to decrease dramatically, which may be caused by the deposition of skarn minerals. At stage IIa, boiling of the ore fluids still continued due to the change from lithostatic to hydrostatic pressure, which triggered the precipitation of abundant quartz‐Cu‐Mo‐Fe sulfides. Furthermore, fluid mixing between a high‐temperature magmatic fluid and a low‐temperature meteoric water might cause a considerable drop in temperature and the deposition of Cu‐bearing quartz/calcite veins during stage IIb. Hence, we consider the Yangla deposit to be of a skarn type, genetically related to the Mesozoic magmatism in the Sanjiang region.     

Dual Control of Depositional Facies on Uranium Mineralization in Coal‐bearing Series: Examples from the Tuanyushan Area of the Northern Qaidam Basin,NW China

The uranium deposits in the Tuanyushan area of northern Qaidam Basin commonly occur in coal-bearing series. To decipher the U-enrichment mechanism and controlling factors in this area, a database of 72 drill cores, including 56 well-logs and 3 sampling wells, was examined for sedimentology and geochemistry in relation to uranium concentrations. The results show that coal-bearing series can influence uranium mineralization from two aspects, i.e., spatial distribution and dynamic control. Five types of uranium-bearing rocks are recognized, mainly occurring in the braided river and braided delta sedimentary facies, among which sandstones near the coals are the most important. The lithological associations of sandstone-type uranium deposits can be classified into three subtypes, termed as U-coal type, coal-U-coal type, and coal-U type, respectively. The coal and fine siliciclastic rocks in the coalbearing series confined the U-rich fluid flow and uranium accumulation in the sandstone near them. Thus, the coal-bearing series can provide good accommodations for uranium mineralization. Coals and organic matters in the coal-bearing series may have served as reducing agents and absorbing barriers. Methane is deemed to be the main acidolysis hydrocarbon in the U-bearing beds, which shows a positive correlation with U-content in the sandstones in the coal-bearing series. Additionally, the δ13 C in the carbonate cements of the U-bearing sandstones indicates that the organic matters, associated with the coal around the sandstones, were involved in the carbonation, one important component of alteration in the Tuanyushan area. Recognition of the dual control of coal-bearing series on the uranium mineralization is significant for the development of coal circular economy, environmental protection during coal utilization and the security of national rare metal resources.     

Phase Equilibria Constraints on Relations of Ore‐bearing Intrusions with Flood Basalts in the Panxi Region,Southwestern China

There are two types of temporally and spatially associated intrusions within the Emeishan large igneous province (LIP); namely, small ultramafic subvolcanic sills that host magmatic Cu-Ni-Platinum Group Element (PGE)-bearing sulfide deposits and large mafic layered intrusions that host giant Ti-V magnetite deposits in the Panxi region. However, except for their coeval ages, the genetic relations between the ore-bearing intrusions and extrusive rocks are poorly understood. Phase equilibria analysis (Q-Pl-Ol-Opx-Cpx system) has been carried out to elucidate whether ore-bearing Panzhihua, Xinjie and Limahe intrusions are co-magmatic with the picrites and flood basalts (including high-Ti, low-Ti and alkali basalts), respectively. In this system, the parental magma can be classified as silica-undersaturated olivine basalt and silica-saturated tholeiite. The equivalents of the parental magma of the Xinjie and Limahe peridotites and picrites and low-Ti basalts are silica-undersaturated, whereas the Limahe gabbro-diorites and high-Ti basalts are silica-saturated. In contrast, the Panzhihua intrusion appears to be alkali character. Phase equilibria relations clearly show that the magmas that formed the Panzhihua intrusion and high-Ti basalts cannot be co-magmatic as there is no way to derive one liquid from another by fractional crystallization. On the other hand, the Panzhihua intrusion appears to be related to Permian alkali intrusions in the region, but does not appear to be related to the alkali basalts recognized in the Longzhoushan lava stratigraphy. Comparably, the Limahe intrusion appears to be a genetic relation to the picrites, whereas the Xinjie intrusion may be genetically related to be low-Ti basalts. Additionally, the gabbro-diorites and peridotites of the Limahe intrusion are not co-magmatic, and the former appears to be derived liquid from high-Ti basalts.     

Sm–Nd and Ar–Ar Isotopic Dating of the Nuri Cu–W–Mo Deposit in the Southern Gangdese,Tibet: Implications for the Porphyry‐Skarn Metallogenic System and Metallogenetic Epochs of the Eastern Gangdese

The Nuri Cu–W–Mo deposit is a large newly explored deposit located at the southern margin of the Gangdese metallogenic belt. There are skarn and porphyry mineralizations in the deposit, but the formation age of the skarn and the relationship between the skarn and porphyry mineralizations are controversial. Constraints on the precise chronology are of fundamental importance for understanding the ore genesis of the Nuri deposit. To determine the formation age of the skarn, we chose garnets and whole rock skarn samples for Sm–Nd dating. We also selected biotite associated with potassic alteration for Ar–Ar dating to confirm the ore formation age of the porphyry mineralizations. The Sm–Nd ages of the skarn are 25.73 ± 0.92 – 25.2 ± 3.9 Ma, and the age of the potassic alteration is 24.37 ± 0.32 Ma. The results indicate that the skarn and porphyry mineralization are coeval and belong to a unified magmatic hydrothermal system. Combined with a previous molybdenite Re–Os age, we think that the hydrothermal activity of the Nuri deposit lasted for 1.2 – 2.1 Myr, which indicates that the mineralization formed rapidly. The chronologic results indicate that the Nuri deposit formed in the period of transformation from compression to extension in the late collisional stage of the collision between the Indian and Eurasian continents.     

Ore Geology,Fluid Inclusion,and S‐ and Pb‐Isotopic Constraints on the Genesis of the Chitudian Zn‐Pb Deposit,Southern Margin of the North China Craton

The Chitudian Zn‐Pb ore deposit, Luanchuan, Henan province, was recently discovered in the southern margin of the North China Craton. The Zn‐Pb orebodies are hosted in the Proterozoic Guandaokou and Luanchuan Groups, occurring as veins in interbedding fracture zones mainly in a WNW‐ and partially in a NS‐direction. The Zn‐Pb ores are characterized by banded, massive, and breccia structures, coarse crystal grains, and a simple mineral composition mainly of galena, sphalerite, pyrite, quartz, dolomite, and calcite. In addition to the vein type orebodies, there are Mo‐ and Zn‐bearing skarn orebodies in the northwest of the Chitudian ore field. Four types of primary fluid inclusions in quartz and calcite were recognized in the Chitudian Zn‐Pb ores, including aqueous, aqueous‐CO₂, daughter‐mineral‐bearing aqueous, and daughter‐mineral‐bearing aqueous‐CO₂ inclusions, with aqueous inclusion being most common. The homogenization temperatures of the fluid inclusions from the main mineralization stage are from 290°C to 340°C, and the salinities mainly from 3.7 to 14.8 wt% NaCl equivalent. In addition to CO₂, CH₄ and H₂S were detected in the vapor phase and HS^‐ in the liquid phase of the fluid inclusions by Laser Raman spectroscopy. The δ³⁴S_V‐CDT values of ore sulfides from the Chitudian deposit range from ?0.32‰ to 8.30‰, and show two modal peaks in the histogram, one from 1‰ to 4‰, and the other from 5‰ to 7‰. The former peak is similar to that of porphyry‐type Mo‐W deposits in the area, whereas the latter is relatively close to the sulfur in the strata. The ore sulfur may have been derived from both the magma and the strata. The Pb‐isotopic compositions of the ore minerals from Chitudian, with ²⁰⁶Pb/²⁰⁴Pb from 17.005 to l7.953, ²⁰⁷Pb/²⁰⁴Pb from 15.414 to 15.587, and ²⁰⁸Pb/²⁰⁴Pb from 37.948 to 39.036, are similar to those of Mesozoic porphyries in the Chitudian ore field, suggesting that the ore‐forming metals were mainly derived from the Mesozoic magmatic intrusions. The Chitudian Zn‐Pb deposit is interpreted to be a distal hydrothermal vein‐type deposit, which was genetically related to the proximal, skarn‐type Mo ore deposits in the region.