Cassiterite exsolution with ilmenite lamellae in magnetite from the Huashan metaluminous tin granite in southern China

Sn⁴⁺ is generally the dominant form of tin in magnetite-series granites as shown by the presence of cassiterite or its incorporation into Ti-bearing minerals such as biotite and titanite. Little is known about the behavior of tin in magnetite. The Huashan granite is an oxidized tin granite in the Nanling Range, southern China, where it contains magnetite as the dominant Fe oxide mineral. It is included in biotite as an early phase and also as interstitial grains spatially associated with ilmenite, cassiterite, Sn-rich titanite (SnO₂ up to 5.9?wt.%), fluorite and apatite. This association indicates that tin enrichment occurred during the late stage of magma crystallization. Ilmenite lamellae display a trellis structure consistent with features of the “oxy-exsolution” process of Sn-bearing titanomagnetite precursor. Micro-inclusions of cassiterite (<1?μm in size) are found only within ilmenite lamellae. This suggests that magnetite with cassiterite inclusions is likely an indicator mineral of oxidized tin granites. Although rare in nature, Sn-bearing magnetite from weathered granites where concentrated in stream sediments, may serve as a strategic tracer for tin exploration in granite districts and in placer deposits, in general.     

南岭地区钨锡花岗岩的成矿矿物学：概念与实例

南岭地区的钨锡成矿作用与花岗岩岩浆活动有十分密切的关系。花岗岩的物源与成矿元素的初始富集、花岗岩的分异程度和花岗岩中流体性质与活动性集中体现了花岗岩对成矿的控制能力,即花岗岩的成矿能力。初步建立了南岭地区钨锡花岗岩的成矿矿物学研究体系。黑云母、榍石、锆石、锡石、金红石、黑钨矿、白钨矿和钨铁铌矿等是讨论的重点矿物,它们可用于判别花岗岩的成矿能力。首先以矿物晶体化学为基础,介绍了上述矿物在钨锡花岗岩中的岩相学特征、内部构造和矿物化学及其变化,并分别论证了花岗岩原始含矿性、花岗岩结晶演化和花岗岩中成矿元素活动性的矿物学标志;其次,系统对比了南岭地区三类钨锡花岗岩（准铝质含锡花岗岩、过铝质含锡花岗岩和过铝质含钨花岗岩）的成矿矿物学特征。以湖南骑田岭花岗岩复式岩体为实例,进行了芙蓉- 菜岭含锡花岗岩和新田岭含钨花岗岩的成矿矿物学对比研究。前者以黑云母、榍石为典型含锡矿物,它们在流体富集阶段,经热液蚀变作用,导致锡的淋滤和结晶富集作用;后者则以出现岩浆白钨矿和黑钨矿为特征。提出的钨锡花岗岩成矿矿物学研究体系有助于深化矿床学研究和矿床勘探工作,并将在今后工作中进一步完善。     

南岭中段花岗岩中榍石对锡成矿能力的指示意义

榍石是钙碱性花岗岩中常见的副矿物,因Ti4+与Sn4+具有相近的晶体化学性质,榍石可以有不同含量的Sn,因此,榍石是研究含锡花岗岩(特别是氧化型花岗岩)的有用矿物之一.本文选择南岭地区中段3个含锡花岗岩(骑田岭、花山、姑婆山)和3个尚未发现重要锡矿化的花岗岩(连阳、大东山、九峰)中的榍石进行了系统的矿物学研究.在这些花...     

华南与花岗岩有关的一种新类型的锡成矿作用：矿物化学、元素和同位素地球化学证据

华南是我国最重要的锡成矿省,产有大量的与花岗岩有关的大型-超大型锡多金属矿床。近年来,在湘南新探明一个超大型锡矿床—芙蓉锡矿床,其中,最重要的锡矿化产在骑田岭花岗岩体西南部的破碎蚀变带内,与绿泥石化密切相关。骑田岭花岗岩富含角闪石,具有较高的氧逸度,显示出准铝的地球化学特征,在花岗岩形成过程中发生过壳-慢岩浆混合作用。这些特点都表明骑田岭花岗宕并不同于一般的 S 型含锡花岗岩,而显示出 A 型花岗岩的地球化学特征。同位素定年分析表明,芙蓉锡矿床主成矿阶段的形成时代要晚于骑田岭花岗岩侵位年龄近20Ma。氢、氧同位素分析表明,发生过水-岩反应的大气降水在成矿流体中占有很重要的地位。硫同位素分析表明花岗岩和地层都提供了成矿所需的硫。因此,用花岗岩浆结晶分异过程中分离出富锡的岩浆流体来形成锡矿的传统模式并不适合于解释芙蓉锡矿的形成。我们认为芙蓉锡矿的形成主要与骑田岭花岗岩的绿泥石化蚀变有关,循环的大气降水与花岗岩发生水-岩反应,富锡的铁镁矿物在蚀变成绿泥石的同时释放出 Sn 和 Ti 等金属到流体中,当物理化学条件改变时,沉淀形成锡矿体。这是一种比较独特的锡矿化模式,丰富了华南与花岗岩有关的锡矿化类型。     

广西花山花岗岩云英岩化分带与锡成矿过程的矿物学研究

云英岩脉型锡矿是广西花山花岗岩的主要矿化类型之一。花山花岗岩是氧化型花岗岩,岩体中的锡主要以Sn4+ 的形式,赋存于黑云母、角闪石、榍石、金红石、钛铁矿和锡石等含锡矿物中。通过矿物学研究发现,云英岩化过程是：经充 分分异和演化形成的残余岩浆流体与中细粒黑云母花岗岩相互作用。首先,黑云母等原生含锡矿物中的锡在岩浆流体的作 用下被淋滤出,进入流体或次生矿物相,如金红石、白云母等,发生初步富集;其次,在蚀变后期,成矿流体使早先沉淀 的含锡矿物发生重溶,锡溶解进入成矿流体再次富集。锡在流体中与丰富的F- ,Cl - 等络阴离子结合成稳定的配合物运移, 随着云英岩化加深,流体的pH值升高、温度降低、络阴离子浓度降低,流体中配合物的稳定性降低发生沉淀形成锡矿化     

Petrological and geochemical characteristics of Zhaibei granites in Nanling region,Southeast China: Implications for REE mineralization

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K₂O + Na₂O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.     

Isotope geochronology,geochemistry, and mineral chemistry of the U-bearing and barren granites from the Zhuguangshan complex,South China: Implications for petrogenesis and uranium mineralization

The Zhuguangshan complex carries some of the most important granite-hosted uranium deposits in South China. Here we investigate the Changjiang and Jiufeng granites which represent typical U-bearing and barren granites in the complex, using zircon U-Pb ages, whole-rock geochemistry, Sr-Nd isotopic and zircon Hf isotopic data, and mineral chemistry, to constrain the petrogenesis and uranium mineralization. LA-ICP-MS zircon U-Pb dating shows that both the Changjiang and Jiufeng granites were emplaced ca. 160 Ma. These rocks show high silica, weakly to strongly peraluminous compositions, enrichment in Rb, Th, and U, and depletion in Ba, Nb, Sr, P, and Ti. These features coupled with the high initial ⁸⁷Sr/⁸⁶Sr ratios, negative εNd(t) values and εHf(t) values, and the Paleoproterozoic two stage model ages of these two granites suggest that the two granites belong to S-type granites, and the parental magmas of the two granites were derived from the Paleoproterozoic metasedimentary rocks. However, the granitoids show different mineralogical characteristics. The biotite in the Changjiang granite belongs to siderophyllite, marking higher degree of chloritization, whereas the biotite in the Jiufeng granite is ferribiotite, characterized by only slight chloritization. Compared with the Jiufeng granite, the biotite in the Changjiang granite has lower crystallization temperature and oxygen fugacity, but higher F content, and the uraninite has higher UO₂ content but lower ThO₂ content, and stronger corrosion. The chemical ages of uraninites from both granites are (within error) consistent with the zircon U-Pb ages and are considered to represent the emplacement ages of granites. Chemical ages of pitchblende in the Changjiang granite yield 118 ± 8 Ma, 87 ± 4 Ma, and 68 ± 6 Ma, representing multiple episodes of hydrothermal events that are responsible for the precipitation of U ores in the Changjiang uranium ore field. Our study suggests that the degree of magma differentiation and physicochemical conditions of the magmatic-hydrothermal system are the key factors that control the different U contents of these two granites. The mineralogical characteristics of uraninite and biotite can be used to distinguish between U-bearing and barren granites, and serve as a potential tool for prospecting granite-hosted uranium deposits.     

Petrogenesis of Lingshan highly fractionated granites in the Southeast China: Implication for Nb-Ta mineralization

Whole rock major and trace element and Sr-, Nd- and Hf-isotope data, together with zircon U-Pb, Hf- and O-isotope data, are reported for the Nb-Ta ore bearing granites from the Lingshan pluton in the Southeastern China, in order to trace their petrogenesis and related Nb-Ta mineralization. The Lingshan pluton contains hornblende-bearing biotite granite in the core and biotite granite, albite granite and pegmatite at the rim. In addition, numerous mafic microgranular enclaves occur in the Lingshan granites. Zircon SIMS U-Pb dating gives consistent crystallization ages of ca. 132 Ma for the Lingshan granitoids and enclaves, consistent with the Nb-Ta mineralization age of ∼132 Ma, indicating that mafic and felsic magmatism and Nb-Ta mineralization are coeval. The biotite granites contain hornblende, and are metaluminous to weakly peraluminous, with high initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7071–0.7219, negative ε_Nd(t) value of −5.9 to −0.3, ε_Hf(t) values of −3.63 to −0.32 for whole rocks, high δ¹⁸O values and negative ε_Hf(t) values for zircons, and ancient Hf and Nd model ages of 1.41–0.95 Ga and 1.23–1.04 Ga, indicating that they are I-type granites and were derived from partial melting of ancient lower crustal materials. They have variable mineral components and geochemical features, corresponding extensive fractionation of hornblende, biotite and feldspar, with minor fractionation of apatite. Existence of mafic microgranular enclaves in the biotite granites suggests a magma mixing/mingling process for the origin of the Lingshan granitoids, and mantle-derived mafic magmas provided the heat for felsic magma generation. In contrast, the Nb-Ta mineralized albite granites and pegmatites have distinct mineral components and geochemical features, which show that they are highly-fractionated granites with extensive melt and F-rich fluid interaction in the generation of these rocks. The fluoride-rich fluids induce the enrichment in Nb and Ta in the highly evolved melts. Therefore, we conclude that the Nb-Ta mineralization is the result of hydrothermal process rather than crystal fractionation in the Lingshan pluton, which provides a case to identify magmatic and hydrothermal processes and evaluate their relative importance as ore-forming processes.     

In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit,Western Junggar,NW China

Titanite (sphene, CaTiSiO₅) is sensitive to changes in temperature, oxygen and water fugacity, and fluid composition. In order to understand formation processes and the nature of hydrothermal fluids, various types of titanite from Cu ores at the Baogutu reduced porphyry Cu deposit were chosen for detailed study. Magmatic titanite is associated with biotite, plagioclase and K-feldspar, whereas hydrothermal titanite occurs with K-feldspar, chlorite, actinolite and calcite. The formation of hydrothermal titanite was related to hydration of igneous minerals under high fH₂O, whereas the widespread replacement of ilmenite by titanite (without magnetite) indicates a relatively low oxygen fugacity. Magmatic titanite has low Al, high Fe, Y, Sn, Zr, Nb and REE contents, relative to hydrothermal titanite. On the basis of the Zr-in-titanite and Al-in-chlorite geothermometers, formation temperatures for magmatic and hydrothermal titanite are estimated to be 687–739 °C and 250–670 °C, respectively. The gradual decrease in REE, Y and Sn contents from magmatic to late hydrothermal titanite was probably caused by precipitation of REE-bearing minerals. Magmatic and hydrothermal titanites have similar chondrite-normalized REE patterns with negative Eu anomalies and relatively flat HREE. Randomly selected titanites have Nd isotopic compositions similar to the host rocks. Thus, both magmatic and hydrothermal titanite are believed to have been predominantly derived from a mantle source.     

The muscovite granites: Parental rocks to the Nanling Range tungsten mineralization in South China

Muscovite granites (MGs) in the Nanling Range (South China) occur as satellite intrusions within or surrounding batholitic biotite monzogranites (BMs). The MGs are massive and fine-grained with a porphyritic texture, and contain quartz, K-feldspar and albite in nearly equal portions. The accessory minerals in the MGs include alumina-rich minerals (e.g., Mn- and Fe-rich garnet, andalusite, topaz, and tourmaline), anatase, rutile, wolframite, cassiterite, xenotime, chalcopyrite, molybdenite, and volatile-rich minerals (e.g., microlite, topaz, tourmaline, fluorite, and calcite). Compared with the BMs, the MGs are geochemically enriched in major elements of Si, K, and Na, and incompatible trace elements of Rb, Cs, Y, U, Nb, Ta, W, Sn, Pb, Bi, Li, and Be, and depleted in major elements of Fe, Mg, Ca, Ti, and P, and compatible trace elements of Ba, Sr, Co, Ni, Cr, Cd, V as well as Zr and Hf. The chondrite-normalized REE patterns of the MGs are flat with large negative Eu anomalies. The mineralogical and geochemical features of the MGs indicate that they crystallized from highly fractionated granitic magmas. Zircons separated from the MG samples, which were collected from six different tungsten deposits, show characters of hydrothermal origin according to their morphologies, chemical compositions and inclusions. In-situ U–Pb dating of the zircons yields a weighted mean ²⁰⁶Pb/²³⁸U age of 133.4 ± 1.0 Ma. This age is similar to the mean age of the zircons from wolframite-bearing quartz veins (WQVs) in the Nanling Range (133.7 ± 1.3 Ma) reported from our previous study. Zircon Hf isotopes also reveal that the MGs and the WQVs are homologous. These mineralogical, geochemical and zirconological features indicate that the MGs are the parental rocks of the tungsten deposits in the Nanling Range. This study provides a new guidance for the exploration of magmatic-hydrothermal tungsten deposits.     

Malayaite and tin‐bearing silicates from a skarn at Doradilla via Bourke,New South Wales

An extensive complex zoned skarn is developed at the contact of a leucoadamellite intrusive at Doradilla, NW New South Wales. The skarn is a disequilibrium assemblage resulting from a progressive sequence of replacement of a carbonate precursor. Early grossular‐clinopyroxene rocks are replaced by andradite with 0.5–3.5 wt.% SnO₂ clinopyroxene and quartz. Later alteration along fractures and bedding planes of the garnet‐clinopyroxene quartz assemblage has produced calcite‐malayaite (CaSn0.95Ti0.05SiO₅) veins. The final replacement stage was the overprinting of the silicate phases by assemblages containing sulphides, cassiterite, magnetite, titanite, fluorite, biotite and chlorite. The tin content of garent increases with increasing andradite component suggesting replacement of Fe³⁺ by Sn⁴⁺. Associated clinopyroxenes contain 0.1% SnO₂. The coexistence of titanite and its tin isomorph malayaite with extremely limited solid solution indicates late stage skarn temperatures of less than 400°C.     

Indium mineralisation in SW England: Host parageneses and mineralogical relations

The SW England ore region contains significant amounts of indium (In) in Early Permian granite-related skarn and lode parageneses and, to a lesser extent, Triassic epithermal “crosscourse” veins. Ore parageneses that predate granite emplacement (Devonian and Lower Carboniferous sedimentary exhalative and vein parageneses) are largely devoid of In. Cadmium (Cd) and gallium (Ga) occur widely in all sulphide-bearing parageneses across the region with sphalerite concentrations locally reaching 1.74 wt% Cd and 1750 ppm Ga.Indium displays a strong affinity to sulphide-bearing magmatic-hydrothermal parageneses. It occurs in silicate-sulphide skarns, polymetallic sulphide lodes and sulphide-bearing portions of greisen-bordered sheeted vein systems and quartz-tourmaline lodes across the region. Magnetite-silicate skarns and quartz-tourmaline lodes that are devoid of sulphide, in contrast, were comparatively unfavourable for In precipitation. The highest In concentrations are found in mineral lodes associated with the Carnmenellis and St Agnes granites, which are the districts that had the highest historical production of Sn. Total In concentrations in these areas locally exceed 430 ppm, while concentrations elsewhere are systematically below 200 ppm.The principal In hosts are chalcopyrite, sphalerite and stannite group minerals with local concentrations within cassiterite and tennantite. Surprisingly, chalcopyrite accounts for the majority of the In budget throughout the region, although concentrations are highest in sphalerite and stannite group minerals. Sphalerite locally contains up to 1.42 wt% In, chalcopyrite has up to 2200 ppm and stannite group minerals up to 6800 ppm. No In was detected in löllingite, arsenopyrite, rutile, haematite, magnetite, tourmaline, biotite, chlorite, galena, bornite, chalcocite or pyrrhotite. Scattered concentrations in pyrite relate to impurities rather than incorporation by solid solution. Roquesite and possibly dzhalindite or native In formed locally where In-bearing chalcopyrite or sphalerite has been replaced by bornite and quartz. The In partitioning between sphalerite and chalcopyrite varies broadly between 1:1 and 10:1.Sporadic In was included in Triassic crosscourse veins as a result of interactions between migrating CaCl₂-rich basinal brines and earlier formed granite-related parageneses. The interactions involved at least two distinct components: 1) Incorporation of clasts of magmatic-hydrothermal veins in crosscourse veins during faulting, and 2) Dissolution and re-precipitation of magmatic-hydrothermal vein minerals in crosscourse fluids. Local concentrations reach 140 ppm In.The magmatic-hydrothermal parageneses in SW England are comparable to the South China Tin Belt, Mount Pleasant, as well as Erzgebirge/Krušné Hory. Magmatic-hydrothermal fluids associated with peraluminous granites have developed a variety of skarn, greisen, lode and veins parageneses by interactions with their host rocks and contained fluids. Crosscourse epithermal mineralisation occurred as In was transported by CaCl₂-rich basinal brines in a similar manner as In-bearing veins in the West Shropshire ore field.     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Late Triassic U-bearing and barren granites in the Miao'ershan batholith,South China: Petrogenetic discrimination and exploration significance

The Miao'ershan uranium ore district is one of the most important granite-hosted uranium producers in South China. There are several Triassic granite plutons in the Miao'ershan batholith, but uranium ore deposits mainly occur within the Douzhashan granitic body. Precise zircon U–Pb dating indicated that these Triassic granite plutons were emplaced during 204 to 215 Ma. The Douzhashan U-bearing granite lies in the central part of the Miao'ershan batholith, and has higher U contents (8.0 to 26.1 ppm, average 17.0 ppm) than the nearby Xiangcaoping granite (5.0 to 9.3 ppm, average 7.0 ppm) and the Yangqiaoling granite (6.4 to 18.3 ppm, average 11.5 ppm) in the south part of the batholith. The Douzhashan granite is composed of medium-grained two-mica granite, whereas the Xiangcaoping and Yangqiaoling granites are composed of porphyritic biotite granite. Both the Xiangcaoping and Douzhashan granites have high A/CNK ratios (> 1.10), high (⁸⁷Sr/⁸⁶Sr)_i ratios (> 0.720) and low ε_Nd(t) values (− 11.3 to − 10.4), suggesting that they belong to strongly peraluminous S-type granites. The Douzhashan granite has low CaO/Na₂O ratios, high Rb/Sr and Rb/Ba ratios, indicating a partial melting origin of clay-rich pelitic rocks. In contrast, the Xiangcaoping granite formed from clay-poor psammite-derived melt. The Yangqiaoling granite shows different geochemical characteristics with the Douzhashan and Xiangcaoping granites, indicating a different magma source. The Yangqiaoling granite has higher ε_Nd(t) of − 9.4 to − 8.3 and variable A/CNK values from 0.98 to 1.19, suggesting a mixture source of meta-sedimentary rocks and meta-igneous rocks. Crystallization fractionation is not the main mechanism for U enrichment in the Douzhashan granite. We suggest that U-rich pelitic rock sources may be the key factor to generate peraluminous U-bearing granites in South China. Searching for those granites which are reduced, strongly peraluminous and were derived from U-rich pelitic rocks, is the most effective way for exploring granite-hosted U deposits.     

Variscan Sn–W–Mo metallogeny in the gravity picture of the Krušné hory/Erzgebirge granite batholith (Central Europe)

Late Variscan wolframite (± molybdenite) and cassiterite–wolframite greisen, skarn and vein deposits occur in a close spatial association with the granites of the Krušné hory/Erzgebirge batholith (KHEB) in Central Europe. We examined the distribution of the deposits in relation to the gravity field affected by Late Variscan granites using the data from previous gravity and metallogenic studies. Late Variscan granites are differentiated into earlier biotite monzogranites (low-F granites) and later biotite or lithium mica syenogranites (high-F granites) in accordance with the previous classifications. All the outcrops of granites in the KHEB region and their hidden continuation are confined to the Bouguer anomaly contour of − 20 mGal. The Sn–W–Mo (rare metal) deposits and occurrences are within the gravity contour of − 30 mGal with the exception of the Grossschirma stratiform tin deposit in the Freiberg polymetallic ore district. We constructed a geological model based on the gravity data along two profiles across the KHEB showing the position of some rare metal deposits and of outcropping and hidden granite bodies. The models show that the overlapping of earlier and later granites is in the areas of the most intense regional gravity minima. These coincide with the Eastern Volcano-Plutonic Complex (Altenberg minimum), which encloses large volumes of felsic extrusives, microgranite dikes and granites, and the Western Plutonic Complex (Eibenstock minimum), with small volumes of felsic dikes and predominance of earlier and later granites, with no extrusives preserved. There is no distinct relationship between the masses of Late Variscan granites and the distribution and the sizes of associated W ± Mo and Sn–W deposits. We prefer the idea that rare metal mineralization was formed by hydrothermal fluids derived from outside of presently outcropping granites. It originated in two cycles: one connected with the formation of earlier granites producing W ± Mo associations and the other one associated with later granites connected with Sn–W mineralization. Mineralizing fluids were probably generated by mantle–crustal interaction in the crust near the mantle–crust boundary as also indicated by lamprophyric intrusions coeval with the Late Variscan granitic magmatism.     

Mineralogical evidence for crystallization conditions and petrogenesis of ilmenite-series I-type granitoids at the Baogutu reduced porphyry Cu deposit (Western Junggar,NW China): Mössbauer spectroscopy,EPM and LA-(MC)-ICPMS analyses

Primary ore-forming minerals retain geochemical signatures of magmatic crystallization information and can reveal the petrochemical conditions prevalent at the time of their formation. The Baogutu deposit is a typical reduced porphyry Cu deposit. Amphibole and biotite Fe³⁺/ΣFe ratios, minerals (feldspar, biotite, amphibole, zircon and apatite), in situ elemental and apatite Nd isotopic compositions were determined by Mössbauer spectroscopy, electron probe microanalysis, and laser ablation multiple-collection inductively coupled plasma mass spectrometry, respectively, to investigate the magma oxidation state, petrogenesis, source features, and to constrain the carbon species at magmatic stages for the intrusive phases. The results show that the primary plagioclase and amphibole in the mineralized diorite to granodiorite porphyry and post ore hornblende diorite porphyry are distinct (An_26-55 versus An_60-69; Mg-hornblende versus tschermakite). In particular, the amphibole shows distinct major and trace element compositions with light rare earth element enrichments and negative Eu anomalies in Mg-hornblende and light rare earth element depletions and no Eu anomalies in tschermakite. All the analyzed biotites are primary igneous phases with a biotite phenocryst profile showing significant variations of Zn, Cr, Sc and Sr from core to rim. These results may indicate the occurrence of mixing between two distinct magmas during mineral formation. Titanium in zircon and Si¹ in amphibole thermometries indicate that magma crystallized at >900 °C and continued to ∼650 °C. In situ apatite Nd isotope (εNd(t) = 5.6–7.6, T_DM2 = 620–460 Ma), indicate absence of significant reduced sedimentary contamination and the source of juvenile lower crust. Slightly decreasing Fe³⁺/ΣFe ratios from biotite and amphibole to whole rock indicate decreasing oxygen fugacity during magma crystallization. Recalculated biotite compositions according to Fe³⁺/ΣFe ratios indicate fO₂ values of less than Ni-NiO buffer (NNO) which show slightly lower values than that estimated according to zircon/melt distribution coefficients Ce anomalies (∼ΔNNO + 0.6). These values are consistent with the features of reduced porphyry Cu deposits. Crystallization of other mineral phases significantly affects the reliability of oxybarometer of zircon/melt distribution coefficients Eu anomalies and Mn contents in apatite. This oxidation state suggests that only CO₂ was present at the magmatic stage, and implies that CH₄ formed during CO₂ reduction occurring later hydrothermal alteration. The alteration of primary amphibole to actinolite released Ti, Al, Fe, Mn, Na and K to the fluid with later precipitation of titanite, albite and minor ilmenite and magnetite during actinolite alteration.     

A crustal source for ca. 165 Ma post-collisional granites related to mineralization in the Jianglang dome of the Songpan-Ganzi Orogen,eastern Tiebtan Plateau

The Wenjiaping and Wulaxi granite plutons are located in the Jianglang dome, which is a key domain for providing deep insight into the tectonic evolution of the Songpan-Ganzi Orogen. Two granites are composed chiefly of K-feldspar, quartz, biotite with minor plagioclase and hornblende. This study presents zircon U-Pb chronology, geochemistry and Hf isotope data to explore their petrogenesis and metallogenic implications. Zircon U-Pb dating provides crystallization ages of 164.5 ± 0.9 Ma and 163.4 ± 0.9 Ma for the Wenjiaping granite, and 164.3 ± 1.7 Ma for the Wulaxi granite. This indicates that they were formed synchronously. They also contain inherited zircons related to the Rodinia and Gondwana supercontinents and the Emeishan large igneous province. Their mineral assemblages lack peraluminous (e.g., garnet and cordierite) and high-temperature (e.g., pyroxene and fayalite) minerals. They are characterized by low A/CNK (1.10–0.99), FeO^T/MgO (8.55–2.83) and K₂O/N₂O ratios (1.34–0.51) with low Zr + Nb + Ce + Y concentrations (average 258 ppm) and zircon saturation temperatures (781–651 °C). Their Al₂O₃, P₂O₅ and SiO₂ contents show negative correlations, and they thus fit the I-type granite definition. Some major and trace elements exhibit strong correlations, implying extensive fractional crystallization (e.g., hornblende and ilmenite) during the magma evolution. Two granites show enrichment in light rare earth elements and large ion lithophile elements, and depletion in high field strength elements. They have low Mg^# values (38.7–17.3) and Y/Nb ratios (0.45–0.16), and yield dominantly negative ε_Hf(t) values (1.4–−13.9), indicating a heterogeneous source and their derivation from remelting of ancient continental crust (e.g., Mesoproterozoic Liwu Group in this region) with minor juvenile crust. Combined with prior studies, we conclude that the Wenjiaping and Wulaxi granites were formed in a post-collisional extensional regime, and were responsible for the 163.7–151.1 Ma magmatic hydrothermal Cu-W mineralization in the Jianglang dome. In addition, two granite plutons intrude this dome and they are undeformed, implying that the doming was during the Early to Middle Jurassic.     

Mineralogical,geochemical and Sr-Nd isotopes characteristics of fluorite-bearing granites in the Northern Arabian-Nubian Shield,Egypt: Constraints on petrogenesis and evolution of their associated rare metal mineralization

The Central Eastern Desert (CED) of Egypt, a part of Neoproterozoic Arabian Nubian Shield (ANS), embraces a multiplicity of rare metal bearing granitoids. Gabal El-Ineigi represents one of these granitic plutons and is a good example of the fluorite-bearing rare metal granites in the ANS. It is a composite pluton consisting of a porphyritic syenogranite (SG; normal granite) and coarse- to medium-grained highly evolved alkali-feldspar granite (AFG; fluorite and rare metal bearing granite) intruded into older granodiorite and metagabbro-diorite rocks. The rock-forming minerals are quartz, K-feldspar (Or_94-99), plagioclase (An_0-6) and biotite (protolithonite-siderophyllite) in both granitic types, with subordinate muscovite (Li-phengite) and fluorite in the AFG. Columbite-(Fe), fergusonite-(Y), rutile, zircon and thorite are the main accessory phases in the AFG while allanite-(Ce) and epidote are exclusively encountered in the SG. Texture and chemistry of minerals, especially fluorite, columbite and fergusonite, support their magmatic origin. Both granitic types are metaluminous to weakly peraluminous (A/CNK = 0.95–1.01) and belong to the post-collisional A2-type granites, indicating melting of underplated mafic lower crust. The late phase AFG has distinctive geochemical features typical of rare metal bearing granites; it is highly fractionated calc-alkaline characterized by high Rb, Nb, Y, U and many other HFSE and HREE contents, and by extremely low Sr and Ba. Moreover, the REE patterns show pronounced negative Eu anomalies (Eu/Eu¹ = 0.03 and 0.06) and tetrad effect (TE_1,3 = 1.13 and 1.27), implying extensive open system fractionation via fluid–rock interactions that characterize the late magmatic stage differentiation. The SG is remarkably enriched in Sr, Ba and invariably shows a relative enrichment in light rare-earth elements (LREEs). The SG rocks (569 ± 15 Ma) are characterized by relatively low initial ⁸⁷Sr/⁸⁶Sr ratios (0.7034–0.7035) that suggest their derivation from the mantle, with little contamination from the older continental crust. By contrast, the AFG has very high ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr ratios that reflect the disturbance of the Rb-Sr isotopic system and may give an indication for the high temperature magma-fluid interaction. The positive εNd(t) values of AFG (+7.40) and SG (+5.17), corresponding to young Nd-T_DM2 ages ranging from 707 to 893 Ma, clearly reflect the juvenile crustal nature of Gabal El-Ineigi granitoids and preclude the occurrence of pre-Neoproterozoic continental crust in the ANS. The field relationships, chemical, petrological and isotopic characteristics of El-Ineigi SG and AFG prove that they are genetically not associated to each other and indicate a complex origin involving two compositionally distinct parental magmas that were both modified during magmatic fractionation processes. We argue that the SG was formed by partial melting of a mid-crustal source with subsequent fractional crystallization. In contrast, the AFG was generated by partial melting and fractionation of Nb- and Ta-rich amphibole (or biotite) of the lower crust. The appreciable amounts of fluorine in the magma appears to be responsible for the formation of rare metal element complexes (e.g., Nb, Ta, Sn and REEs), and could account for the rare metal mineralization in the El-Ineigi AFG.     

Tin-bearing minerals at the Furong tin deposit,South China: Implications for tin mineralization

It remains poorly constrained whether remobilization of Sn from granites and prograde skarns plays an essential role in forming economic (skarn-type) tin mineralization. Using both electron probe microanalysis and laser ablation–inductively coupled plasma–mass spectrometry methods, in-situ Sn contents, as well as major elements, were analyzed for numerous silicates and magnetite from fresh granite, altered granite, and skarn at the large Furong Sn deposit (530,000 t Sn @ 0.8% Sn) in the Nanling Range, South China. Hornblende and biotite in fresh granite are the main Sn-bearing phases (Sn = 44–321 ppm), while plagioclase and K-feldspar are poor in Sn (< 5 ppm). In altered granite, tin is hosted mainly by hydrothermal muscovite (299–583 ppm) replacing plagioclase, but rarely by chlorite (mostly <10 ppm) replacing hornblende and biotite. In contrast, most silicates (garnet, diopside, vesuvianite, pargasite and epidote) and magnetite from tin skarn are Sn-rich (47–44,241 ppm), except for Sn-poor phlogopite and scapolite (< 10 ppm). In particular, garnet, pargasite, and epidote reach tin concentrations in the percent range. Tin generally enters the stannous silicates and magnetite through substitutions for octahedral Al^vi and Fe³⁺. Comparisons of Sn contents between magmatic and hydrothermal minerals in granite, prograde and retrograde minerals related to tin skarn indicate that remobilization of Sn from granite and prograde skarn is not a pre-requisite to form tin mineralization.     

Geology and genesis of the Hehuaping magnesian skarn-type cassiterite-sulfide deposit,Hunan Province,Southern China

Magnesian skarn-type tin deposits are relatively rare in the world. The Hehuaping cassiterite-sulfide deposit in southern China, having a total reserve of approximately 130,000 t of tin, 50,000 t of lead and 10,000 t of zinc, is identified as such type. The deposit is related to the Late Jurassic (157 Ma) Hehuaping medium- to coarse-grained biotite granite that intruded the Middle Devonian Qiziqiao dolomite Formation and the Tiaomajian sandstone Formation. Four paragenetic stages of skarn and ore formation have been recognized: I. prograde stage, II. retrograde stage, III. cassiterite-sulfide stage and IV. carbonate stage. Alteration zoning between fresh granite and unaltered country rocks can be identified. The skarn are typified by Mg-mineral assemblages of forsterite, spinel, diopside, tremolite, serpentine, talc, and phlogopite. The geochemistry of various skarn minerals shows a gradually decrease of Mg end member and, correspondingly, an increase of Fe- and especially Mn end members along the process of skarn alteration.Tin mineralization developed during the late retrograde stage resulted in cassiterite–magnetite-diopside skarn. However, the deposition of cassiterite occurred predominantly as cassiterite-sulfide veins along fractures and interlayer fracture zones during stage III. The petrogeochemistry of Hehuaping granite, as well as S- and Pb isotopic analyses suggest that the ore-forming elements have a magmatic source originated from the upper crust. The HO isotopic and fluid-inclusion analyses indicate that high-temperature ore-forming fluids in early anhydrous skarn stage (stage I) are also magmatic origin. In comparison, the retrograde fluids are characterized by relatively low salinity (2 to 10 wt.% NaCl equiv) and low temperature (220 to 300 °C), suggesting a mixed origin of meteoric waters with magmatic fluids. The major ore-forming stage III fluids are characterized by lower temperature (170 to 240 °C) and salinity (1 to 6 wt.% NaCl equiv), indicating fluid mixing could be an efficient tin-mineralizing mechanism. Meteoric waters are dominant in stage IV, resulting in a further lowering of temperature (130 to 200 °C) and salinity (0.4 to 1 wt.% NaCl equiv).