Inferred Indium Resources of the Bolivian Tin‐Polymetallic Deposits

Tin‐polymetallic base metal deposits of Miocene age in the Eastern Cordillera in Bolivia were studied by ICP/MS and EPMA for major and minor elements, paying an attention to indium concentration of the ore deposits. The highest indium content and 1000 In/Zn ratio of individual ore deposits are 5,740 ppm and 22.2 for the Potosi deposits, 2,730 ppm and 7.4 for Bolivar deposit, 2,510 ppm and 17.5 for Siete Suyos–Animas deposits, and 1,290 ppm and 3.3 for San Vicente deposit. The same content and ratio of composite samples of the studied deposits are up to 292 ppm and 4.0 for Potosi deposits, 3,080 ppm and 11.3 for Huari Huari deposit, 100 ppm and 0.3 for Tuntoco deposit, 152 ppm and 1.8 for Porco deposit, 103 ppm and 59.2 for Animas deposit, and 1,160 ppm and 3.7 for Pirquitas deposit. Those of zinc concentrates are as follows: 1,080 ppm and 2.1 at San Lorenzo; 584 ppm and 1.7 at Bolivar; 499 ppm and 1.23 at Porco; 449 ppm and 1.21 at Reserva, and 213 ppm and 0.61 at Colquiri deposit. Indium occurs mostly in dark colored sphalerite and that of the Potosi deposit was found to have one of the highest concentrations, containing up to 1.27 wt% In. Petrukite was discovered in the Potosi deposit, and indium minerals are expected to occur in the Huari Huari deposit and others with the high 1000 In/Zn ratios. The indium contents of the zinc concentrates and composite samples were applied to the produced and remaining ores, then the total amounts of indium in the Bolivian tin‐polymetallic base metal deposits are speculated to be more than 12,000 tons In, which is bigger than that of South China (11,000 tons) and the Japanese Islands (9,000 tons). Sphalerites of the Potosi deposit have one of the highest ranges of indium, similarly to those of the San Vicente deposit. Both the San Vicente and Potosi deposits are rich in silver, implying significance of both silver‐polymetallic and tin‐polymetallic environments for the concentration of trace amounts of indium.     

Mineralogical evolution of indium in high grade tin-polymetallic hydrothermal veins — A comparative study from Tosham, Haryana state, India and Goka, Naegi district, Japan

Two tin-polymetallic vein-type deposits widely separated in time and space but with strong similarities in terms of mineralization style, ore mineralogy and chemistry have been studied comparatively with the aim of understanding the mineralogical evolution of In-rich hydrothermal systems. The Tosham deposit, Bhiwani district, Haryana, India, is of Neoproterozoic age and constitutes a Sn–Cu prospect with unusually high In content. The disseminated, crude stockwork and vein mineralization is hosted by greisenised metasedimentary rocks intruded by a porphyritic granite stock and by later rhyolitic effusives. The Goka deposit, Naegi district, Japan is probably of uppermost Cretaceous age and occurs close to a well fractionated ilmenite series granitoid body. The tin-polymetallic vein in the Goka deposit is hosted by a welded tuff unit close to a subvolcanic granodiorite porphyry.The main host minerals of indium in the Tosham and Goka ores are sphalerite, stannite, unidentified Zn–Cu–Fe–In–Sn–S phases and chalcopyrite. Up to 0.48 wt.% In has been noted in the Goka chalcopyrite, whereas at Tosham, the mineral has a maximum In concentration of 1220 ppm. At Goka the sphalerite contains up to 1.89 wt.% In, whereas In-bearing stannite carries up to ca. 9 wt.% of the metal. Roquesite is the other indium mineral present in the Tosham ores, but is absent in Goka. The mineral chemistry of the Tosham and Goka ores suggest that the In-bearing minerals belong to a multi-component Zn–Cu–Fe–(Ag)–Sn–In–S system. Based on various triangular plots of the atomic proportions of the main metals, it is inferred that there are end-member phases, roquesite and stannite, in the Tosham ores co-existing with chalcopyrite. The sphalerite is both pure end-member and Cu–In-bearing in both the Tosham and Goka ores. Some of the analysed stannite grains in Tosham ores could possibly be petrukite. The Zn–Cu–Fe–Sn–In–S system in the two ores has a Sn-poor, high-In solid solution phase and also a Sn-rich, low-In solid solution phase. It seems possible that these two solid solutions were the first to form during hydrothermal ore deposition at high temperatures from a disordered solid solution located at the (Cu + Ag):(Zn + Fe):(In + Sn) = 3:5:2 intersection in the (Cu + Ag)–(Zn + Fe)–(In + Sn) field. With decreasing temperatures, the Sn-poor, In-rich solid solution exsolved the Zn–In-mineral of Ohta [Ohta, E., 1980. Mineralization of Izumo and Sorachi veins of the Toyoha mine, Hokkaido, Japan. Bulletin, Geological Survey of Japan 31, 585–597. (in Japanese with English abstract).] and sphalerite, while the Sn-rich, In-poor solid solution was broken down to stannite and relatively-Cu-rich sphalerite.     

Indium in cassiterite and ores of tin deposits

The results obtained with LA-ICP-MS by less abundant lighter ¹¹³In isotope and EPMA show that in cassiterite of cassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins is characterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides of cassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to 433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore districts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impetus for further exploration of deposits with Sn–sulfide mineralization as the most promising indium resources in Russia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfide mineralization show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistage ore-forming processes doubled indium resources of deposits being the main factors in the formation of high grade indium mineralization.     

In, Sn, Pb and Zn Contents and Their Relationships in Ore-forming Fluids from Some In-rich and In-poor Deposits in China

All the indium-rich deposits with indium contents in ores more than 100×10- 6 seems to be of cassiterite-sulfide deposits or Sn-bearing Pb-Zn deposits, e.g., in the Dachang Sn deposit in Guangxi, the Dulong Sn-Zn deposit in Yunnan, and the Meng'entaolegai Ag-Pb-Zn deposit in Inner Mongolia, the indium contents in ores range from 98×10-6 to 236×10-6 and show a good positive correlation with contents of zinc and tin, and their correlation coefficients are 0.8781 and 0.7430, respectively. The indium contents from such Sn-poor deposits as the Fozichong Pb-Zn deposit in Guangxi and the Huanren Pb-Zn deposit in Liaoning are generally lower than 10×10-6, i.e., whether tin is present or not in a deposit implies the enrichment extent of indium in ores. Whether the In enrichment itself in the ore -forming fluids or the ore-forming conditions has actually caused the enrichment/depletion of indium in the deposits? After studying the fluid inclusions in quartz crystallized at the main stage of mineralization of several In-rich and In-poor deposits in China, this paper analyzed the contents and studied the variation trend of In, Sn, Pb and Zn in the ore-forming fluids. The results show that the contents of lead and zinc in the ore-forming fluids of In-rich and -poor deposits are at the same level, and the lead contents range from 22×10-6 to 81×10-6 and zinc from 164×10-6 to 309×10-6, while the contents of indium and tin in the ore-forming fluids of In-rich deposits are far higher than those of In-poor deposits, with a difference of 1-2 orders of magnitude. Indium and tin contents in ore-forming fluid of In-rich deposits are 1.9×10-6-4.1×10-6 and 7×100-6-55×10-6, and there is a very good positive correlation between the two elements, with a correlation coefficient of 0.9552. Indium and tin contents in ore-forming fluid of In-poor deposits are 0.03×10-6-0.09×10-6 and 0.4×10-6--2.0×10-6, respectively, and there is no apparent correlation between them. This indicates, on one hand, that In-rich ore-forming fluids are the material basis for the formation of In-rich deposits, and, on the other hand, tin probably played a very important role in the transport and enrichment of indium.     

Re–Os and U–Pb Geochronology of the Dawan Mo–Zn–Fe Deposit in Northern Taihang Mountains,China

The Dawan Mo–Zn–Fe deposit located in the Northern Taihang Mountains in the middle of the North China Craton (NCC) contains large Mo‐dominant deposits. The mineralization of the Dawan Mo–Zn–Fe deposit is associated with the Mesozoic Wanganzhen granitoid complex and is mainly hosted within Archean metamorphic rocks and Proterozoic–Paleozoic dolomites. Rhyolite porphyry and quartz monzonite both occur in the ore field and potassic alteration, strong silicic–phyllic alteration, and propylitic alteration occur from the center of the rhyolite porphyry outward. The Mo mineralization is spacially related to silicic and potassic alteration. The Fe orebody is mainly found in serpentinized skarn in the external contact zone between the quartz monzonite and dolomite. Six samples of molybdenite were collected for Re–Os dating. Results show that the Re–Os model ages range from 136.2 Ma to 138.1 Ma with an isochron age of 138 ± 2 Ma (MSWD = 1.2). U–Pb zircon ages determined by laser ablation inductively coupled plasma mass spectrometry yield crystallization ages of 141.2 ± 0.7 (MSWD = 0.38) and 130.7 ± 0.6 Ma (MSWD = 0.73) for the rhyolite porphyry and quartz monzonite, respectively. The ore‐bearing rhyolite porphyry shows higher K₂O/Na₂O ratios, ranging from 58.0 to 68.7 (wt%), than those of quartz monzonite. All of the rock samples are classified in the shoshonitic series and characterized by enrichment in large ion lithophile elements; depletion in Mg, Fe, Ta, Ni, P, and Y; enrichment in light rare earth elements with high (La/Yb)_n ratios. Geochronology results indicate that skarn‐type Fe mineralization associated with quartz monzonite (130.7 ± 0.6 Ma) formed eight million years later than Mo and Zn mineralization (138 ± 2 Ma) in the Dawan deposit. From Re concentrations in molybdenite and previously presented Pb and S isotope data, we conclude that the ore‐forming material of the deposit was derived from a crust‐mantle mixed source. The porphyry‐skarn type Cu–Mo–Zn mineralization around the Wanganzhen complex is related to the primary magmatic activity, and the skarn‐type Fe mineralization is formed at the late period magmatism. The Dawan Mo–Zn–Fe porphyry‐skarn ores are related to the magmatism that was associated with lithospheric thinning in the NCC.     

Indium Mineralization in the Yejiwei Sn‐Polymetallic Deposit of the Shizhuyuan Orefield,Southern Hunan,China

The Y ejiwei deposit, which is located in the southern H unan W –Sn –Pb –Z n M etallogenic B elt in south C hina, is a large‐scale porphyry–skarn–veinlet‐type deposit containing 806 t I n. M ineralization occurs as porphyry‐type S n (stockworks), skarn‐type S n–C u, marble‐hosted‐type S n–C u (veinlet), and vein‐type P b–Z n ores. Thirty‐five ore samples were collected from the Y ejiwei deposit for bulk and mineral chemical composition, microscopic observation and electron microprobe analyses. The porphyry‐type S n ores contain variable amounts of I n (2.3–76 ppm; mean of 17.4 ppm) with local I n enrichment (226 ppm) and 1000 × I n/Z n values are 3.8–52.4. The skarn‐type C u–S n ore is richest in I n (12.3–214 ppm; mean of 114 ppm), and 1000 × I n/Z n values are 2.4–117. In contrast, the In content of the marble‐hosted‐type C u–S n ores is relatively low (7.4–34.9 ppm; mean of 20.3 ppm), and 1000 × I n/Z n is in the range of 0.61–5.5, and the vein‐type P b–Z n ores in the external zone contain the lowest I n contents (7.2–17.0 ppm; mean of 12.1 ppm) with 1000 × I n/Z n values of 0.07–0.09. The ore minerals in the deposit include pyrite, pyrrhotite, cassiterite, and I n‐bearing minerals of sphalerite, chalcopyrite, and stannite. Although only trace amounts of sphalerite are hosted in the porphyry ores, the sphalerite contains the highest I n content (0.27–10.1 wt.% I n) in the deposit. We observed the highest I n contents of all I n‐bearing sphalerite reported in C hina. The I n contents of sphalerite in the skarn‐type ore range from 0.15 to 0.56 wt.%, whereas the marble‐hosted‐, and vein‐type ores have lower I n contents (0.00–0.04, and 0.03–0.06 wt.%, respectively). The In resources of the Y ejiwei deposit are mainly hosted in skarn ores of the No. 31 and No. 32 orebodies. The genesis of I n in the Y ejiwei deposit was closely related to the shallow intrusive environment of related igneous rocks. As W –S n–M o–B i–C u–P b–Z n–A g mineralization is widespread in south H unan, this study would suggest a focus on skarn‐type S n–Z n deposits for the future prospecting of I n resources.     

Noble Gas and Stable Isotopic Constraints on the Origin of the Ag–Cu Polymetallic Ore Deposits in the Baiyangping Area,Yunnan Province,SW China

The Lanping basin, Yunnan province, SW China, is located at the juncture of the Eurasian and Indian Plates in the eastern part of the Tibetan Plateau. The Lanping basin, in the Sanjiang Tethyan metallogenic province, is a significant Cu–Ag–Zn–Pb mineralized belt in China that includes the largest sandstone‐hosted Zn–Pb deposit in the world, the Jinding deposit, as well as several Ag–Cu deposits (the Baiyangping and Jinman deposits). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7,000 t Ag, are mainly hosted in Meso‐Cenozoic clastic rocks and are dominantly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the basin. The Baiyangping, Babaoshan, and Hetaoqing ore deposits are representative of the epithermal base metal deposits in the Lanping basin. The microthermometric data show that the ore‐forming fluids for these deposits were low temperature (110–180 °C) and had bimodal distribution of salinity at moderate and mid to high salinities (approximately 2–8 wt.% and 18–26 wt.% NaCl equivalent). The C and O isotope data indicate that the ore‐forming fluids were related to hot basin brines. We present new He and Ar isotope data on volatiles released from fluid inclusions contained in sulfides and in barite in these three deposits. ³He/⁴He ratios of the ore‐forming fluids are 0.01 to 0.14 R/Ra with a mean of 0.07 Ra (where R is the ³He/⁴He ratio and Ra is the ratio for atmospheric helium). This mean value is intermediate to typical ³He/⁴He ratios for the crust (R/Ra = 0.01 to 0.05) and the ratio for air‐saturated water (R/Ra = 1). The mean ratio is also significantly lower than the ratios found for mantle‐derived fluids (R/Ra = 6 to 9). The ⁴⁰Ar/³⁶Ar ratios of the ore‐forming fluids range from 298 to 382 with a mean of 323. This value is slightly higher than that for the air‐saturated water (295.5). The ³He/⁴He ratios of fluids from the fluid inclusions imply that the ore‐forming fluid for the Baiyangping, Babaoshan, and Hetaoqing deposits was derived from the crust and that any mantle‐derived He was negligible. The content of the radiogenic Ar ranges between 0.2 to 20.4%, and the proportion of air‐derived ⁴⁰Ar averages 94.1%. This indicates that atmospheric Ar was important in the formation of these deposits but that some radiogenic ⁴⁰Ar was derived from crustal rocks. Based on these observations coupled with other geochemical evidence, we suggest that the ore‐forming fluids responsible for the formation of the Ag–Cu–Pb–Zn polymetallic ore deposits in the Baiyangping area of the Lanping basin were mainly derived from crustal fluids. The fluids may have mixed with some amount of air‐saturated water, but there was no significant involvement of mantle‐derived fluids.     

铟矿床时空分布、成矿背景及其成矿过程

铟是一种稀散金属元素,特殊的地球化学性质导致其难以形成独立的矿床,均以伴生矿产的形式产出于富锡岩浆热液与陆相火山-次火山热液系统,以及相对贫锡的海底(火山)热液系统。研究表明,铟矿床广泛分布于活动的大洋或大陆板块边缘,成因上主要与板块俯冲以及碰撞作用密切相关,少量与火山岩以及喷流沉积岩相关的块状硫化物矿床形成的有利构造背景则是弧后环境和裂谷环境。在不同地质历史时期,铟的巨量堆积作用主要有新第三纪、白垩纪、泥盆纪三个时期,对应的矿化类型分别以浅成低温热液-锡多金属脉型、矽卡岩型以及块状硫化物(VMS)型矿床为主,其中与铟成矿作用相关的岩浆岩多为A型或S型花岗岩。铟独立矿物目前报道约15种,主要包括自然铟、硫铟铜矿、铟石、樱井矿、羟铟石等,其中以硫铟铜矿最为广泛。绝大多数铟主要以类质同象的形式赋存于闪锌矿中,其次为黝锡矿、锌黄锡矿、黄铜矿、锡石、黝铜矿、砷黝铜矿等。富铟闪锌矿通常形成于高温热液体系,常显示阶段性富集特征,最普遍的置换机制为(Ag,Cu)~++In~(3+)2Zn~(2+)。文章指出为完善铟金属成矿理论,需进一步加强铟的成矿物质来源、铟沉淀的物理化学条件及其与主矿种成生关系的研究。     

Rare earth element geochemistry of the Woxi W–Sb–Au deposit, Hunan Province, South China

The Woxi W–Sb–Au deposit in Hunan, South China, is hosted by Proterozoic metasedimentary rocks, a turbiditic sequence of slightly metamorphosed (greenschist facies), gray-green and purplish red graywacke, siltstone, sandy slate, and slate. The mineralization occurs predominantly (> 70%) as stratabound/stratiform ore layers and subordinately as stringer stockworks. The former consists of rhythmically interbedded, banded to finely laminated stibnite, scheelite, quartz, pyrite and silty clays, whereas the latter occurs immediately beneath the stratabound ore layers and is characterized by numerous quartz + pyrite + gold + scheelite stringer veins or veinlets that are typically either subparallel or subvertical to the overlying stratabound ore layers. The deposit has been the subject of continued debate in regard to its genesis. Rare earth element geochemistry is used here to support a sedimentary exhalative (sedex) origin for the Woxi deposit. The REE signatures of the metasedimentary rocks and associated ores from the Woxi W–Sb–Au deposit remained unchanged during post-depositional processes and were mainly controlled by their provenance. The original ore-forming hydrothermal fluids, as demonstrated by fluid inclusions in quartz from the banded ores, are characterized by variable total REE concentrations (3.5 to 136 ppm), marked LREE enrichment (La_N/Yb_N = 28–248, ∑LREE/∑HREE = 16 to 34) and no significant Eu-anomalies (Eu/Eu = 0.83 to 1.18). They were most probably derived from evolved seawater that circulated in the clastic sediment pile and subsequently erupted on the seafloor. The bulk banded ores are enriched in HREE (La_N/Yb_N = 4.6–11.4, ∑LREE/∑HREE = 3 to 14) and slightly depleted in Eu (Eu/Eu = 0.63 to 1.14) relative to their parent fluids. This is interpreted as indicating the influence of seawater rather than a crystallographic control on REE content of the ores. Within a single ore layer, the degree of HREE enrichment tends to increase upward while the total REE concentrations decrease, reflecting greater influence and dilution of seawater. There is a broad similarity in chondrite-normalized REE patterns and the amount of REE fractionation of the banded ores in this study and exhalites from other sedex-type polymetallic ore deposits, suggesting a similar genesis for these deposits. This conclusion is in agreement with geologic evidence supporting a syngenetic (sedex) model for the Woxi deposit.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

Geological features and origin of the Huize carbonate-hosted Zn–Pb–(Ag) District, Yunnan, South China

The Huize Zn–Pb–(Ag) district, in the Sichuan–Yunnan–Guizhou Zn–Pb–(Ag) metallogenic region, contains significant high-grade, Zn–Pb–(Ag) deposits. The total metal reserve of Zn and Pb exceeds 5 Mt. The district has the following geological characteristics: (1) high ore grade (Zn + Pb ≥ 25 wt.%); (2) enrichment in Ag and a range of other trace elements (Ge, In, Ga, Cd, and Tl), with galena, sphalerite, and pyrite being the major carriers of Ag, Ge, Cd and Tl; (3) ore distribution controlled by both structural and lithological features; (4) simple and limited wall-rock alteration; (5) mineral zonation within the orebodies; and (6) the presence of evaporite layers in the ore-hosting wall rocks of the Early Carboniferous Baizuo Formation and the underlying basement.Fluid-inclusion and isotope geochemical data indicate that the ore fluid has homogenisation temperatures of 165–220 °C, and salinities of 6.6–12 wt.% NaCl equiv., and that the ore-forming fluids and metals were predominantly derived from the Kunyang Group basement rocks and the evaporite-bearing rocks of the cover strata. Ores were deposited along favourable, specific ore-controlling structures. The new laboratory and field studies indicate that the Huize Zn–Pb–(Ag) district is not a carbonate-replacement deposit containing massive sulphides, but rather the deposits can be designated as deformed, carbonate-hosted, MVT-type deposits. Detailed study of the deposits has provided new clues to the localisation of concealed orebodies in the Huize Zn–Pb–(Ag) district and of the potential for similar carbonate-hosted sulphide deposits elsewhere in NE Yunnan Province, as well as the Sichuan–Yunnan–Guizhou Zn–Pb–(Ag) metallogenic region.     

Geologic, fluid inclusion and isotopic characteristics of the Jinding Zn–Pb deposit, western Yunnan, South China: A review

With a reserve of  200 Mt ore grading 6.08% Zn and 1.29% Pb (i.e., a metal reserve of  15 Mt) hosted in Cretaceous and Tertiary terrestrial rocks, the Jinding deposit is the largest Zn–Pb deposit in China, and also the youngest sediment-hosted super giant Zn–Pb deposit in the world. The deposit mainly occurs in the Jinding dome structure as tabular orebodies within breccia-bearing sandstones of the Palaeocene Yunlong Formation (autochthonous) and in the overlying sandstones of the Early Cretaceous Jingxing Formation (allochthonous). The deposit is not stratiform and no exhalative sedimentary rocks have been observed. The occurrence of the orebodies, presence of hangingwall alteration, and replacement and open-space filling textures all indicate an epigenetic origin. Formation of the Jinding Zn–Pb deposit is related to a period of major continental crust movement during the collision of the Indian and Eurasian Plates. The westward thrusts and dome structure were successively developed in the Palaeocene sedimentary rocks in the ore district, and Zn–Pb mineralisation appears to have taken place in the early stage of the doming processes.The study of fluid inclusions in sphalerite and associated gangue minerals (quartz, celestine, calcite and gypsum) shows that homogenisation temperatures ranged from 54 to 309 °C and cluster around 110 to 150 °C, with salinities of 1.6 to 18.0 wt.% NaCl equiv. Inert gas isotope studies from inclusions in ore- and gangue-minerals reveal 2.0 to 15.6% mantle He, 53% mantle Ne and a considerable amount of mantle Xe in the ore-forming fluids. The Pb-isotope composition of ores shows that the metal is mainly of mantle origin, mixed with a lesser amount of crustal lead. The widely variable and negative δ³⁴S values of Jinding sulphides suggest that thermo-chemical or bacterial sulphate reduction produced reduced sulphur for deposition of the Zn–Pb sulphides. The mixing of a mantle-sourced fluid enriched in metals and CO₂ with reduced sulphide-bearing saline formation water in a structural–lithologic trap may have been the key mechanism for the formation of the Jinding deposit.The Jinding deposit differs from known major types of sediment-hosted Zn–Pb deposits in the world, including sandstone-type (SST), Mississippi Valley type (MVT) and sedimentary-exhalative (SEDEX). Although the fine-grained ore texture and high Zn/Pb ratios are similar to those in SEDEX deposits, the Jinding deposit lacks any exhalative sedimentary rocks. Like MVT deposits, Jinding is characterised by simple mineralogy, epigenetic features and involvement of basinal brines in mineralisation, but its host rocks are mainly sandstones and breccia-bearing sandstones. The Jinding deposit is also different from SST deposits with its high Zn/Pb ratios, among other characteristics. Most importantly, the Jinding deposit was formed in an intracontinental terrestrial basin with an active tectonic history in relation to plate collision, and mantle-sourced fluids and metals played a major role in ore formation, which is not the case for SEDEX, MVT, and SST. We propose that Jinding represents a new type of sediment-hosted Zn–Pb deposit, named the ‘Jinding type’.     

Indium Enrichment in the Meng'entaolegai Ag-Pb-Zn Deposit, Inner Mongolia, China

Abstract. The Meng'entaolegai In-rich Ag-Pb-Zn deposit is located in the eastern part of Inner Mongolia. It is one of the In-richest deposits in China. Large amounts of quartz and sulfide minerals constitute a hydrothermal quartz-sulfide vein deposit within a Hercynian acidic granite massif, which occupies an area of about 400 km². Thirty-six orebodies, controlled strictly by the E-W trend faults, are found in the orefield of 6 km in length from east to west and 200 to 1,000 m in width from south to north. The ore minerals are mainly galena, sphalerite and pyrite, and subordinate chalcopyrite, arsenopyrite, cassiterite and stannite with many Ag-minerals. The gangue minerals are mainly quartz, calcite, sericite and chlorite. Economic components of the deposit are dominated by Pb andZn (reserves of Pb and Zn are 0.17 Mt and 0.37 Mt, and their grades are 1 % and 2.3 %, respectively), with Ag, Sn, In and Cd (1,800 t Ag, >2,000 t Sn, >500 t In and 1,800 t Cd) as by-products. Indium is highly enriched in ores and its contents are 9 to 295 ppm in ores and 85 to 2,660 ppm in sphalerite. Analytical results show that the ore-forming fluid of this deposit contains 0.8–3.5 ppm In and 4–36 ppm Sn, and the two elements show a very good positive correlation with a correlation coefficient of 0.8672, while the correlation between In and Zn in the ore-forming fluids, with a correlation coefficient of 0.5723, is not as good as that between In and Sn. This indicates that indium has an affinity with tin in the ore-forming fluids. The authors think that this is probably the main reason why those In-rich deposits spread over the world are simultaneously enriched in tin.     

Mineralogy and geochemistry of indium-bearing polymetallic veins in the Sarvlaxviken area,Lovisa, Finland

A number of polymetallic vein mineralizations of different styles and metal associations, including base, alloy, noble and critical metals, have been discovered around the Sarvlaxviken bay in the westernmost parts of the Mesoproterozoic Wiborg Batholith, south-eastern Finland. The veins occur in two rapakivi granite varieties: coarse-grained wiborgite; and medium-grained Marviken granite. The veins are divided into five groups based on the dominant metal associations.The Li–As–W–Zn–Mn, Pb–Zn and Cu–As–In associations are hosted by wiborgite, and are strongly controlled by a NNW-trending tectonic pattern that evolved in two main stages. The Li–As–W–Zn–Mn association (generation 1) formed in a typical greisen environment with Li-bearing mica in significant alteration halos around a narrow quartz vein. This greisenization was accompanied by silicification, followed by sericitization and chloritization. The Pb–Zn association occurs in a similar vein type but without typical high-temperature minerals and is considered to have formed at a higher crustal level. Generations 2a and 2b formed under more brittle conditions leading to fracturing, quartz veining and metal precipitation of ore minerals. This metal association is characterized by very high contents of Cu, As and up to 1490 ppm In but with ≤ 0.4% Zn, which leads to very high In/Zn ratios (up to 8400) enabling formation of abundant roquesite.The As–Sn–Cu and Mo–Bi–Be associations are hosted by alteration zones without hydrothermal quartz in the Marviken granite. Mineralization with moderately high contents of As, Sn and Cu is associated with greisenization while mineralization with spectacular contents of Be as well as high contents of Mo and Bi is associated with sericitization, chloritization and berylification.The internal age relations between the wiborgite-hosted, NNW-trending veins show a clear evolution from a typical greisen type environment (the Li–As–W–Zn–Mn and Pb–Zn associations of generation 1) to cooler and more brittle conditions governing quartz veining and precipitation of ore minerals belonging to the Cu–As–In association (generations 2a and 2b). The age relations between these wiborgite-hosted veins and the veins in the Marviken granite are more uncertain but the presence of a NS-trending granitic dyke on the eastern side of the Sarvlaxviken bay, with similar ore-fertile geochemical composition as the Marviken granite, indicates that the tectonically controlled veins formed simultaneously with the emplacement of the Marviken granite and associated hydrothermal activity.The polymetallic veins in the Sarvlaxviken bay are unique for the Fennoscandian Shield, not the least for the locally high indium grades and spectacular roquesite grains. There is an obvious exploration potential for similar veins (and hence a number of base, alloy, noble and critical metals) also elsewhere in the entire Wiborg Batholith.     

U–Pb and Re–Os Geochronology of the Tongcun Molybdenum Deposit and Zhilingtou Gold‐Silver Deposit in Zhejiang Province,Southeast China,and Its Geological Implications

Mesozoic ore deposits in Zhejiang Province, Southeast China, are divided into the northwestern and southeastern Zhejiang metallogenic belts along the Jiangshan–Shaoxing Fault. The metal ore deposits found in these belts are epithermal Au–Ag deposits, hydrothermal‐vein Ag–Pb–Zn deposits, porphyry–skarn Mo (Fe) deposits, and vein‐type Mo deposits. There is a close spatial–temporal relationship between the Mesozoic ore deposits and Mesozoic volcanic–intrusive complexes. Zircon U–Pb dating of the ore‐related intrusive rocks and molybdenite Re–Os dating from two typical deposits (Tongcun Mo deposit and Zhilingtou Au–Ag deposit) in the two metallogenic belts show the early and late Yanshanian ages for mineralization. SIMS U–Pb data of zircons from the Tongcun Mo deposit and Zhilingtou Au–Ag deposit indicate that the host granitoids crystallized at 169.7 ± 9.7 Ma (2σ) and 113.6 ± 1 Ma (2σ), respectively. Re–Os analysis of six molybdenite samples from the Tongcun Mo deposit yields an isochron age of 163.9 ± 1.9 Ma (2σ). Re–Os analyses of five molybdenite samples from the porphyry Mo orebodies of the Zhilingtou Au‐Ag deposit yield an isochron age of 110.1 ± 1.8 Ma (2σ). Our results suggest that the metal mineralization in the Zhejiang Province, southeast China formed during at least two stages, i.e., Middle Jurassic and Early Cretaceous, coeval with the granitic magmatism.     

Isotope geochemistry and Re–Os geochronology of the Yanjiagou Mo deposit in the central North China Craton

The Yanjiagou deposit, located in the central North China Craton (NCC), is a newly found porphyry‐type Mo deposit. The Mo mineralization here is spatially associated with the Mapeng batholith. In this study, we identify four stages of ore formation in this deposit: pyrite phyllic stage (I), quartz–pyrite stage (II), quartz–pyrite–molybdenite stage (III), which is the main mineralization stage, and quartz–carbonate stage (IV). We present sulphur and lead isotope data on pyrite, and rhenium and osmium isotopes of molybdenite from the porphyry deposit and evaluate the timing and origin of ore formation. The δ³⁴S values of the pyrite range from ‐1.1‰ to −0.6‰, with an average of −0.875‰, suggesting origin from a mixture of magmatic/mantle sources and the basement rocks. The Pb isotope compositions of the pyrite show a range of 16.369 to 17.079 for ²⁰⁶Pb/²⁰⁴Pb, 15.201 to 15.355 for ²⁰⁷Pb/²⁰⁴Pb, and 36.696 to 37.380 for ²⁰⁸Pb/²⁰⁴Pb, indicating that the ore‐forming materials were derived from a mixture of lower crust (or basement rocks) and mantle. Rhenium contents in molybdenite samples from the main ore stage are between 74.73 to 254.43 ppm, with an average of 147.9 ppm, indicating a mixed crustal‐mantle source for the metal. Eight molybdenite separates yield model ages ranging from 124.17 to 130.80 Ma and a mean model age of 128.46 Ma. An isochron age of 126.7 ± 1.1 Ma (MSWD = 2.1, initial ¹⁸⁷Os = 0.0032 ± 0.0012 ppb) is computed, which reveals a close link between the Mo mineralization and the magmatism that generated the Mapeng batholith. The age is close to the zircon U–Pb age of ca. 130 Ma from the batholith reported in a recent study. The age is also consistent with the timing of mineralization in the Fuping ore cluster in the central NCC, as well as the peak time of lithosphere thinning and destruction of the NCC. We evaluate the spatio‐temporal distribution of the Mo deposits in the NCC and identify three important molybdenum provinces along the northern and southern margins of the craton formed during three distinct episodes: Middle to Late Triassic (240–220 Ma), Early Jurassic (190–175 Ma), and Late Jurassic to Early Cretaceous (150–125 Ma). The third period is considered to mark the most important metallogenic event, coinciding with the peak of lithosphere thinning and craton destruction in the NCC. Copyright © 2014 John Wiley & Sons, Ltd.     

广西大厂锡矿铟的地球化学特征及成因机制初探

广西大厂锡矿位于江南古陆西南缘,桂西北海西-印支期被动陆缘裂谷盆地北部的断裂凹陷盆地中,是中国重要的、以锡为主的有色金属矿床。它主要由长坡-铜坑和高峰矿床、拉么矿床、大福楼矿床和亢马矿床等组成,其铟资源量约6 000 t。文章在对长坡-铜坑矿床、高峰矿床以及拉么矿床不同类型围岩（包括花岗岩质岩石）、矿石以及不同矿床类型中矿石矿物（硫化物和氧化物）中的In、Cu、Cd、Sn、Fe、Zn等微量元素分析的基础上,结合不同类型矿床、不同矿物组合中硫化物的微量元素电子探针测试以及硫同位素分析结果,初步认为大厂锡矿岩浆源区是富铟的,在正常的沉积岩中不存在铟的初始富集;In主要赋存于闪锌矿中,与层状和块状的矿体关系密切。在成矿作用过程中,In的分布和富集对矿物组合和矿石类型具有明显的选择性。大厂铟矿的形成是富铟的岩浆源区重融产生含铟岩浆,在岩浆侵位冷却过程中,由岩浆结晶所产生的流体携带In、Cu、Fe、Zn、Sn等成矿元素从岩浆中出溶,形成含In的成矿流体。水-岩反应以及在大气降水来源流体的参与下,导致In、Cu、Fe、Zn、Sn等从成矿流体中沉淀、富集成矿。     

Ore Genesis of the Lunwei Granite‐Related Scheelite Deposit in the Wuyi Metallogenic Belt,Southeast China: Constraints from Geochronology,Fluid Inclusions,and H–O–S Isotopes

A granite‐related scheelite deposit has been recently discovered in the Wuyi metallogenic belt of southeast China. The veinlet–disseminated scheelite occurs mainly in the inner and outer contact zones of the porphyritic biotite granite, spatially associated with potassic feldspathization and silicification. Re–Os dating of molybdenite intergrowths with scheelite yield a well‐constrained isochron age of 170.4 ± 1.2 Ma, coeval with the LA–MC–ICP–MS concordant zircon age of porphyritic biotite granite (167.6 ± 2.2 Ma), indicating that the Lunwei W deposit was formed in the Middle Jurassic (~170 Ma). We identify three stages of ore formation (from early to late): (I) the quartz–K‐feldspar–scheelite stage; (II) the quartz–polymetallic sulfide stage; and (III) the quartz–carbonate stage. Based on petrographic observations and microthermometric criteria, the fluid inclusions in the scheelite and quartz are determined to be mainly aqueous two‐phase (liquid‐rich and gas‐rich) fluid inclusions, with minor gas‐pure and CO₂‐bearing fluid inclusions. Ore‐forming fluids in the Lunwei W deposit show a successive decrease in temperature and salinity from Stage I to Stage III. The homogenization temperature decreases from an average of 299 °C in Stage I, through 251 °C in Stage II, to 212 °C in Stage III, with a corresponding change in salinity from an average of 5.8 wt.%, through 5.2 wt.%, to 3.4 wt.%. The ore‐forming fluids have intermediate to low temperatures and low salinities, belonging to the H₂O–NaCl ± CO₂ system. The δ¹⁸O_H2O values vary from 1.8‰ to 3.3‰, and the δD_V‐SMOW values vary from –66‰ to –76‰, suggesting that the ore‐forming fluid was primarily of magmatic water mixed with various amounts of meteoric water. Sulfur isotope compositions of sulfides (δ³⁴S ranging from –1.1‰ to +2.4‰) and Re contents in molybdenite (1.45–19.25 µg/g, mean of 8.97 µg/g) indicate that the ore‐forming materials originated mainly in the crust. The primary mechanism for mineral deposition in the Lunwei W deposit was a decrease in temperature and the mixing of magmatic and meteoric water. The Lunwei deposit can be classified as a porphyry‐type scheelite deposit and is a product of widespread tungsten mineralization in South China. We summarize the geological characteristics of typical W deposits (the Xingluokeng, Shangfang, and Lunwei deposits) in the Wuyi metallogenic belt and suggest that porphyry and skarn scheelite deposits should be considered the principal exploration targets in this area.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

New data on mineralogy and metallogeny of scarns in the Pitkyaranta ore region

A wide application of modern precision research techniques to the studies of Pitkyaranta ores allowed us to find increased contents of indium (to 0.33%), silver (447 g/t), gold (0.2–0.4 g/t), and palladium (0.2 g/t). A series of rare minerals previously not found here was also discovered. Among ore minerals, these are roquesite, zavartskite, electrum, stutzite, altaite, bismite, glaucodot, cervelleite, hedleyite, pavonite, cannonite, plantnerite, lindkvistite, ashoverite, etc. The discovery of roquesite and electrum is the most important in terms of metallogeny. Roquesite (indium sulfide) is found in Karelia for the first time. The highest indium contents in direct correlation to those of zinc are characteristic for polymetallic ores of the Pitkyaranta ore fields with sphalerite as the concentrating mineral (to 0.5% of In). The predicted zinc resources are evaluated to ∼2.5 million t for the Pitkyaranta group of ore deposits, and to 400 000 t for the Hopunvaara region. Respectively, the resources of indium amount to ∼2400 t (total) and 600 t for the Hopunvaara region.