Petrogenesis and Solidification Depth of the Jurassic Daebo and Cretaceous Bulguksa Granitic Rocks in South Korea

We investigated the Jurassic Daebo and Cretaceous Bulguksa granitic rocks in South Korea. The former are distributed mainly in the Gyeonggi and Yeongnam massifs and the latter are present in the Gyeongsan basin and Ogcheon belt. The Daebo granitic rocks generally are of ilmenite series and I to S type. These rocks are associated with Au–Ag hydrothermal deposits, whereas the Bulguksa granitic rocks are of magnetite series and I type, and are associated with Pb–Zn, Cu and Mo–W hydrothermal deposits, as well as Au–Ag hydrothermal deposits. The Daebo granitic rocks show adakitic signatures in their chemical compositions. They are considered to have been derived from partial melting of the thick lower continental crust. Conversely, the Bulguksa granitic rocks in the Gyeongsan basin are non‐adakitic and are considered to have been derived from partial melting of a mantle wedge. Magmas of the Daebo granitic rocks formed at relatively shallow levels, but solidified at deep levels compared with those of the Bulguksa granitic rocks. The Bulguksa granitic rocks in the central to western Ogcheon belt are considered to have been formed by fractionation of magmas derived from partial melting of continental crust. The total Al contents of biotite and hornblende in the granitic rocks increased, with the Bulguksa granitic rocks in the Gyeongsan basin < the Bulguksa granitic rocks in the Ogcheon belt and Gyeonggi and Yeongnam massifs and the Daebo granitic rocks in the Ogcheon belt < the Daebo granitic rocks in the Gyeonggi and Yeongnam massifs. This order corresponds to an increase in solidification depth.     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

内蒙古林西县哈什吐钼矿床辉钼矿铼-锇年龄及其地质意义

内蒙古哈什吐矿床是新发现的钼矿床。为进一步查明哈什吐钼矿床的形成时间,首次对主要钼矿体的10件辉钼矿样品进行铼-锇同位素分析,所获铼-锇同位素模式年龄变化范围为(147.0±2.1) Ma~(149.5±2.2) Ma,加权平均值为(148.22±0.67) Ma,获得等时线年龄为(148.8±1.6) Ma,MSWD值为0.95。铼-锇同位素年代数据及野外地质证据表明,哈什吐钼矿床为晚侏罗世构造-岩浆作用及相关流体活动的产物。哈什吐钼矿床辉钼矿的w(Re)介于(0.65~2.06)×10^-6,平均值为1.28×10^-6,通过与区域内同时期形成的若干相似类型钼矿床的Re含量对比分析,初步推测认为哈什吐钼矿床成矿物质源区具有更偏向于壳源的特征。哈什吐斑岩型钼矿床形成时代的厘定对于提高该矿床的理论研究水平和指导隐伏金属矿床的找矿勘查工作均具有重要意义。     

南岭地区成钨、成锡花岗岩组合的几个判别标志

南岭地区钨锡多金属成矿作用和区内中酸性-酸性花岗岩有着密切的成因联系。利用已发表的和野外收集的地质资料,本文尝试对区内成钨锡花岗岩组合(包括与钨锡矿相关的含钨锡花岗岩和成钨锡花岗岩)进行宏观地质判别。判别过程采用循序渐进的方式,首先将成钨锡花岗岩组合与不成矿花岗岩相区别,然后将含锡花岗岩和含钨花岗岩互相区别开来。相对于不成矿花岗岩,成钨锡花岗岩组合通常具有W、Sn、F、B化探组合异常、多期多阶段演化特点、适度的构造叠加(即存在明显的热液活动)等共同特点,且三者缺一不可。不成矿花岗岩一般具有W、Sn、F、B化探组合为背景值,岩性单一,少见晚期岩株、岩脉(演化不充分)及蚀变的特征。在野外地质工作中,含锡花岗岩一般为花岗闪长岩-二长花岗岩-二云母花岗岩岩性组合。基性端元以普遍发育暗色微粒包体、常见角闪石、含较多的黑云母为鉴别特征。酸性端元中可以含有少量白云母。而含钨花岗岩以黑云母二长花岗岩-二云母花岗岩-白云母花岗岩岩性组合为主,常见含B矿物电气石,基性端元少见或不见角闪石、含较少的黑云母,仅见变质岩、围岩捕掳体和黑云母团块,酸性端元白云母含量较高等组合特征可以与含锡花岗岩相区别。     

Crucial control on magmatic-hydrothermal Sn deposit in the Tengchong block,SW China: Evidence from magma differentiation and zircon geochemistry

Magmatic-hydrothermal Sn deposits are commonly associated with high silica magmas, but why most global high silica granites do not bear economic Sn ore grades remains unclear. Two crucial factors controlling magmatic-hydrothermal Sn mineralization, including advanced fractionation and depressurization-induced rapid cooling, were revealed in the case study of the Guyong granitic pluton linked with the Xiaolonghe Sn deposit, in the Tengchong block, SW China. The Guyong granitic pluton comprises three petrological facies: less evolved biotite syenogranite, evolved alkali granite and leucogranite, and highly evolved facies (the protolith of greisenized granite). Similar crystallization ages (～77 Ma) and gradual contact between different petrological facies indicate the Guyong granitic pluton records a continuous fractionation process. Monte Carlo-revised Rayleigh fractionation model suggests the fractionation degree of the Guyong pluton is markedly high (>87 wt.%) that can only be achieved by a high initial water (≥4 wt.%) content in the parent granitic magma revealed by rhyolite-MELTS calculation. Advanced degree fractionation causes the first Sn enrichment but it also significantly increases the viscosity of evolved magmas, suppressing the exsolution and transport of hydrothermal fluids. Hence, it must be compensated by the second critical factor: depressurization-induced rapid cooling, reflected by the occurrence of highly metamict zircons in the greisenized granite. The highly metamict feature, indicated by the large full width at half maximum (FWHM) values of zircon ν₃(SiO₄) peak (>19.5 cm^?1), suggests these zircons do not experience thermal annealing but rapidly ascend into a shallow cooling environment. Depressurization-induced rapid cooling facilitates exsolution and transport of hydrothermal fluids, interacting with wall rocks and resulting in Sn mineralization.     

Chemical composition of rock-forming minerals in granitoids associated with Au–Bi–Cu,Cu–Mo,and Au–Ag mineralization at the Freegold Mountain,Yukon, Canada: magmatic and hydrothermal fluid chemistry and petrogenetic implications

The chemical compositions of rock-forming minerals have been determined for both altered and least-altered igneous rocks spatially associated with numerous mineralized zones (Nucleus Au–Bi–Cu–As deposit, Revenue Au ± Cu and Stoddart Cu–Mo ± W mineral occurrences, and Laforma Au–Ag deposit) across the Freegold Mountain area, Yukon, Canada. Within the study area, K-feldspar has a narrow compositional range (89.4–91% Or), whereas plagioclase spans a wide range (4.4–70.07% An). In all of the investigated samples, T _Ab = T _An = T _Or, suggesting that magmatic equilibrium between the coexisting plagioclase and K-feldspar was maintained. Igneous amphibole phenocrysts from hypabyssal dikes are typically calcic, whereas the Stoddart Cu–Mo ± W, Laforma Au–Ag, and Goldy Au mineralization are associated with Mg-enriched primary amphibole of edenite composition, and Au–Bi–Cu–As mineralization from Nucleus is related to Al-enriched primary amphibole of ferropargasite composition. Primary biotite phenocrysts across the Freegold Mountain area re-equilibrated with oxidized magma (f(O₂) values between 10–13 and 10–11.5 bars, lying between the Ni/NiO and the magnetite/haematite buffers). However, biotite and amphibole phenocrysts from Stoddart, Goldy, Laforma, and the Highway zones crystallized from a more oxidized magma, as indicated by their elevated X _Mg up to 0.65, relative to biotite and hornblende from Nucleus and Revenue characterized by a lower X _Mg (typically < 0.50). This suggests that various sources and (or) rapid emplacement were involved in magma genesis, as further supported by the considerable variation of pressure (1.8–7.3 kb) of amphibole crystallization and of the total Al content in least-altered biotite (2.6–2.9 afu) within the Freegold Mountain area. Biotite and apatite equilibrated within the T range of 520–780°C, consistent with temperatures of equilibration between ilmenite and magnetite, and their compositions indicate that they formed from an oxidized I-type magma. Magma differentiated by fractional crystallization (indicated by the presence of normally zoned plagioclase with Ca-rich cores and Na-enriched outer rims) and multiple magma mixing (supported by the presence of reversed zoned plagioclase and coexistence of normally and reversely zoned plagioclase). Lower X _Mg biotite associated with the mineralized (Cu–Mo ± W) potassic alteration incorporated more F and Cl relative to least-altered biotite with higher X _Mg. In both Nucleus and Revenue Au–Cu mineralizations, secondary biotite composition varies with respect to the associated alteration mineral assemblages. Although secondary biotite in the skarn re-equilibrated with F-poor fluids, secondary biotite from the pervasive biotitization is related to F- and Cl-enriched fluids, and secondary biotite from the phyllitic zone is related to F-, Cl-, and Mg-depleted fluids, thus consistent with a change in mineralizing fluid composition during mineralization.     

Oxygen-isotope systematics of a strongly recrystallized granitic rock complex,Grenvillian Belt,SW Sweden

In the eastern, external part of the Grenvillian Belt in SW Sweden, five formations of granitic rocks were found in the basement of the Dalslandian Supracrustal Group. The granitic rocks have been strongly recrystallized but have preserved most of their granitic texture in the process. Most magmatic crystals have been pseudomorphed by metamorphic minerals: quartz, albite, chlorite, biotite, white mica, epidote, titanite, hematite, pyrite and carbonate. Two of the formations have subsequently been affected by a cataclastic deformation and at present consist of mylogneisses. ¹⁸O whole-rock values for the granitic rocks vary from +3.0 to +11.1. Quartz-apatite, quartz-zircon and quartz-titanite pairs show ¹⁸O/¹⁶O fractionations corresponding to equilibrium temperatures of 550–700° C, which are believed to reflect in the main continued closed-system isotopic exchange at high temperatures following solidification. In contrast highly positive ¹⁸O/¹⁶O fractionations for quartz-K-feldspar, quartz-biotite, quartz-chlorite and quartz-sericite pairs in some granitic samples indicate that these rocks have exchanged oxygen with heated, meteoric, H₂O dominated fluids. Other granitic samples, however, show virtually undisturbed magmatic ¹⁸O/¹⁶O fractionation values for the same mineral pairs, even though these rocks are equally altered.It is concluded that all granitic rock units recrystallized under greenschist facies conditions during the infiltration of fluids under the influence of hydrothermal convection systems set up by the intrusion of the granitic plutons. The fluids probably had a range of ¹⁸O values from ca. -14 to ca. +10, indicating the mixing of distinct fluid reservoirs, one of meteoric origin and the others of magmatic and/or metamorphic origin. The temperature of alteration is estimated at 450–500° C.Estimation of pre-alteration ¹⁸O whole rock values for the five granitic units suggests that three units should be assigned a dominantly S-type origin, where as the other two units may partly or wholly have an I-type origin.     

Characteristic Features of Tin–iron–copper Mineralization in the Anle-Huanggangliang Mining Area, Inner Mongolia, China

Abstract: The Anle Sn‐Cu and Huanggangliang Fe‐Sn deposits have been exploited in the Linxi district, which is located 165 km northwest of Chifeng City in northern China. In this study the formation mechanisms of the tin deposits in the Anle and Huanggangliang mining area were investigated to understand the mechanisms of tin mineralization in northern China. The veins of the Anle deposit are divided into cassiterite–quartz–chlorite veins, chalcopyrite‐bearing quartz veins, cassi–terite–chalcopyrite–bearing quartz veins and sphalerite‐quartz veins. The sequence of mineralization is tin mineralization (stage I), copper mineralization (stage II), and lead‐zinc mineralization (stage III). The Huanggangliang tin deposit consists of magnetite skarn orebodies and many cassiterite‐bearing feldspar–fluorite veins and veinlets cutting the magnetite orebodies. The fluid inclusions in quartz and fluorite in ores from the Anle and Huanggangliang tin deposits are divided into two‐phase fluid inclusions, vapor‐rich fluid inclusions and poly‐phase fluid inclusions. The final homogenization temperatures of fluid inclusions of quartz in the ores of the Anle deposit and fluorite of tin‐bearing feldspar veins in the Huanggangliang tin deposit range from 195 to 425C and from 215 to 450C, respectively. The fluids responsible for the Anle and Huanggangliang tin deposits were of very high temperature and NaCl‐rich ones containing K, Ca, Al, Si, Ti, Fe and Cl in addition to ore metals such as Sn and Cu. The temperature and chemical composition of fluid in fluid inclusions of igneous rocks in the mining area are very similar to those of fluid in fluid inclusions in the ores of these deposits. The fluid for these ore deposits had a close relation with the fluid coexisting with melt of Late Jurassic granitic rocks in this mining area. Salinities of fluid inclusions from these ore deposits and granitic rocks in the mining area were estimated to range from 35 to 50 wt % NaCl equivalent. Based on arsenopy‐rite geothermometry and fluid inclusion studies, a fluid containing 40 wt% NaCl (eq.) could be formed by phase separation of fluid having 6 wt% NaCl (eq.) at a temperature of 420 to 500C and a pressure of 0.3 to 0.4 kb. The temperatures and pressures presented above indicate an NaCl‐rich magmatic fluid derived from granitic melt that had intruded into a shallow level of crust caused the Sn–Fe–Cu mineralization of the mining area. The geological relationship between these ore deposits and granitic bodies around the ore deposits, and the similarity of fluids forming these ore deposits and coexisting with granitic melt, suggest that these ore deposits were formed by the activity of fluid derived from granitic melt in Late Jurassic age.     

闽西南十二排斑岩钼矿床地质特征、同位素年代学与岩石地球化学

十二排钼矿床位于上杭-云霄断裂带与闽西南拗陷的复合部位,是紫金山铜金矿田外围新近探明的一处具有中大型远景的斑岩型钼矿床。野外地质调查显示,其钼矿化呈细脉状、网脉状主要产出于黑云母二长花岗岩和黑云母花岗斑岩中。热液蚀变具有斑岩型矿床的分带特征,由黑云母花岗斑岩向外依次发育钾硅酸盐化带、绢英岩化带和青磐岩化带,钼矿体主要赋存于绢英岩化与钾硅酸盐化构成的叠加带中。锆石U-Pb定年结果表明,黑云母二长花岗岩和黑云母花岗斑岩分别形成于(143.1±0.9)Ma和(143.5±0.4)Ma。4件辉钼矿样品的Re-Os加权平均年龄为(143.9±2.1)Ma。辉钼矿的w(Re)为1.2×10~(-6)～7.8×10~(-6),说明成矿物质可能主要来自地壳。岩石地球化学分析结果显示,十二排含矿花岗岩具有相似的主量和微量元素组成,均属于弱过铝质高钾钙碱性I型花岗岩,其中,黑云母花岗斑岩表现出高分异花岗岩特征,两者可能是古老变质基底来源的熔体经历不同程度分异结晶的产物,并混入有少量幔源物质。综合已有的资料,文章认为十二排斑岩型钼矿化与早白垩世早期花岗质岩浆活动密切相关,上杭-云霄断裂带存在古太平洋板块俯冲后撤引发构造体制转换阶段的成岩成矿响应,进一步找矿勘查工作应加强评价早白垩世早期高分异花岗岩体的钼多金属成矿潜力。     

Composition of Volatile Components in Mineral-Hosted Fluid Inclusions at Hydrothermal Deposits. Water–Rock–Gas Systems in Ore-Forming Processes

The paper presents data on the average analyzed concentrations of volatile components (CO₂, CH₄ and other hydrocarbons, N₂, and H₂S) in natural fluids producing hydrothermal Au, Sn, W, Mo, Cu, Pb, and Zn mineral deposits. Characteristics of the gas regime at these deposits are determined. Thermodynamic simulations are carried out to model how compounds with volatile components are formed when water interacts with silicic and mafic rocks within wide P–T ranges. The speciation of volatile components determined by direct analysis is in good agreement with numerical simulations of water–rock systems (for silicic and mafic rocks). More reduced species with volatile components are formed in mafic rocks.     

Petrochemistry of Granitoids Along the Loei Fold Belt,Northeastern Thailand

Petrochemical characteristics of Permo‐Triassic granitoids from five regions (i) Mung Loei, (ii) Phu Thap Fah – Phu Thep, (iii) Phetchabun, (iv) Nakon Sawan – Lobburi, and (v) Rayong – Chantaburi along the Loei Fold Belt (LFB), northeastern Thailand were studied. The LFB is a north–south trending 800 km fold belt that hosts several gold and base‐metal deposits. The granitoids consist of monzogranite, granodiorite, monzodiorite, tonalite, quartz‐syenite, and quartz‐rich granitoids. These are composed of quartz, plagioclase, and K‐feldspar with mafic minerals such as hornblende and biotite. Accessory minerals, such as titanite, zircon, magnetite, ilmenite, apatite, garnet, rutile, and allanite are also present. Magnetic susceptibilities in the SI unit of granitoids vary from 6.5 × 10⁻³ to 15.2 × 10⁻³ in Muang Loei, from 0.1 × 10⁻³ to 29.4 × 10⁻³ in Phu Thap Fah – Phu Thep, from 2.7 × 10⁻³ to 34.6 × 10⁻³ in Petchabun, from 2.4 × 10⁻³ to 14.1 × 10⁻³ in Nakon Sawan – Lobburi, and from 0.03 × 10⁻³ to 2.8 × 10⁻³ in Rayong – Chantaburi. Concentration of major elements suggests that these intermediate to felsic plutonic rocks have calc‐alkaline affinities. Concentration of REE of the granitoids normalized to chondrite displays moderately elevated light REE (LREE) and relatively flat heavy (HREE) patterns, with distinct depletion of Eu. Rb versus Y/Nb and Nb/Y tectonic discrimination diagrams illustrate that the granitoids from Muang Loei, Phu Thap Fah – Phu Thep, Phetchabun, Nakon Sawan – Lobburi, and Rayong – Chantaburi formed in continental volcanic‐arc setting. New age data from radiometric K‐Ar dating on K‐feldspar from granodiorite in Loei and Nakhon Sawan areas yielded 171 ± 3 and 221 ± 5 Ma, respectively. K‐Ar dating on hornblende separated from diorite in Lobburi yielded 219 ± 8 Ma. These ages suggest that magmatism of Muang Loei occurred in the Middle Jurassic, and Nakon Sawan – Lobburi occurred in Late Triassic. Both Nb versus Y and Rb versus (Y + Nb) diagrams and age data indicate that Nakon Sawan – Lobburi granitoids intruded in Late Triassic at Nong Bua, Nakon Sawan province and Khao Wong Phra Jun, Lobburi province in volcanic arc setting. Muang Loei granitoids at the Loei province formed later in Middle Jurassic also in volcanic arc setting. The negative δ³⁴S_CDT values of ore minerals from the skarn deposit suggest that the I‐type magma has been influenced by light biogenic sulfur from local country rocks. The Au‐Cu‐Fe‐Sb deposits correlate with the magnetite‐series granitoids in Phetchabun, Nakon Sawan – Lobburi and Rayong – Chantaburi areas. Metallogeny of the Au and Cu‐Au skarn deposits and the epithermal Au deposit is related to adakitic rocks of magnetite‐series granitoids from Phetchabun and Nakon Sawan areas. All mineralizations along the LFB are generated in the volcanic arc related to the subduction of Paleo‐Tethys. The total Al (^TAl) content of biotite of granitoids increases in the following order: granitoids associated with Fe and Au deposit < with Cu deposit < barren granitoids. X_Mg of biotite in granitoids in Muang Loei indicates the crystallization of biotite in magnetite‐series granitoids under high oxygen fugacity conditions. On the other hand, low X_Mg (<0.4) of biotite in magnetite‐series granitoids in Phu Thap Fah – Phu Thep and Rayong – Chantaburi indicates a reduced environment and low oxygen fugacity, associated with Au skarn deposit (Phu Thap Fah) and Sb‐Au deposit (Bo Thong), respectively. The magnetite‐series granitoids at Phu Thap Fah having low magnetic susceptibilities and low X_Mg of biotite were formed by reduction of initially oxidizing magnetite‐series granitic magma by interaction with reducing sedimentary country rocks as suggested by negative δ³⁴S_CDT values.     

Magmatic‐Hydrothermal Mineralization Sequence in Xinlu Ore Field,Guangxi, South China: Constraints from Zircon U‐Pb,Molybdenite Re‐Os,and Muscovite Ar‐Ar Dating

The Xinlu Sn‐polymetallic ore field is located in the western Nanling Polymetallic Belt in northeastern Guangxi, South China, where a number of typical skarn‐, hydrothermal vein‐type tin deposits have developed. There are two types of Sn deposits: skarn‐type and sulfide‐quartz vein‐type. The tin mineralizations mainly occur on the south side of the Guposhan granitic complex pluton and within its outer contact zone. To constrain the Sn mineralization age and further understand its genetic links to the Guposhan granitic complex, a series of geochronological works has been conducted at the Liuheao deposit of the ore field using high‐precision zircon SHRIMP U‐Pb, molybdenite Re‐Os, and muscovite Ar‐Ar dating methods. The results show that the biotite‐monzogranite, which is part of the Xinlu intrusive unit of the Guposhan complex pluton, has a SHRIMP U‐Pb zircon age of 161.0 ± 1.5 Ma. The skarn‐type ore has a ⁴⁰Ar‐³⁹Ar muscovite plateau age of 160 ± 2 Ma (same as its isochron age), and the sulfide‐quartz vein‐type ore yields an Re‐Os molybdenite isochron age of 154.4 ± 3.5 Ma. The magmatic‐hydrothermal geochronological sequence demonstrated that the hydrothermal mineralization took place immediately following the emplacement of the monzogranite, with the skarn metasomatic mineralization stage predating the sulfide mineralization stage. Geochronologically, we have compared this ore field with 26 typical Sn deposits distributed along the Nanling Polymetallic Belt, leading to the suggestion of the magmatic‐metallogenic processes in the Xinlu ore field (ca. 161–154 Ma) as a component of the Early Yanshanian large‐scale Sn‐polymetallic mineralization event (peaked at 160–150 Ma) in the Nanling Range of South China. Petrogenesis of Sn‐producing granite and Sn‐polymetallic mineralization were probably caused by crust–mantle interaction as a result of significant lithospheric extension and thinning in South China in the Late Jurassic.     

Zr/Hf ratio as an indicator of fractionation of rare-metal granites by the example of the Kukulbei complex,eastern Transbaikalia

The concept of granitic melt fractionation as the main process in the concentration of rare elements in granites calls for the development of a reliable method to determine the evolutionary sequences of granite series. We propose to use for this purpose a zirconium-hafnium indicator, the Zr/Hf weight ratio in granitic rocks (Zaraisky et al., 1999, 2000). By the example of three classic regions of rare-metal deposits, eastern Transbaikalia, central Kazakhstan, and Erzgebirge (Czech Republic and Germany), it was empirically shown that the Zr/Hf ratio of granites decreases during the fractional crystallization of granite magmas in the sequence granodiorite → biotite granite → leucogranite → lithium-fluorine granite. The reason is the higher affinity of Hf compared with Zr to a granite melt. This implies that the crystallization and settling of accessory zircon will cause the progressive enrichment of Hf relative to Zr in the residual melt. As a result, the Zr/Hf ratio decreases regularly in the series of sequential phases of granite intrusion related to a single magma chamber from granodiorite to biotite granite, leucogranite, and Li-F granite (from 45-30 to 10-2). Our experimental investigations supported the preferential enrichment of haplogranite melt in Hf and zircon crystals in equilibrium with melt in Zr (T= 800°C and P = 1 kbar). The Zr/Hf indicator was tested by the example of the wellknown Kukulbei rare-metal granite complex of eastern Transbaikalia (J3), which is unique in the degree of fractionation of initial granite melt with the formation of three phases of granite emplacement and vein derivatives. An important feature of the complex is its “short” differentiation trend. It was supposed that the granite magma of the first phase is parental, and the later phases forming small intrusive bodies in large massifs of biotite granites of the first phase are sequential products of its crystallization differentiation in a magma chamber. The biotite granites of the first phase are barren. The leucocratic granites of the second phase are accompanied by tin-tungsten greisen deposits (e.g., Spokoininskoe), and the upper part of cupola-like stocks of Li-F amazonite granites of the third phase host apogranite-type tantalum deposits (Orlovka, Etyka, and Achikan). In addition to three granite phases, the Kukulbei complex includes dikes of ongonites, elvans, amazonite granites, and chamber miarolitic pegmatites. All of the granitic rocks of the complex have similar isotopic ages of 142± 0.6 Ma. The Zr/Hf ratio decreases systematically from phase 1 (40–25), to phase 2 (20–10), and phase 3 (10–2). The ongonites, elvans, and pegmatites have similar Zr/Hf ratios (15-5), falling between the ranges of leucocratic muscovite granites and Li-F granites. Compared with other granite series, the granitic rocks of the Kukulbei complex show specific petrographic and geochemical features: they are strongly enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From the early to late intrusion phases, the degree of enrichment and depletion in these element groups increases regularly. This is accompanied by a significant decrease (from 40 to 2) in Zr/Hf, which can be used as a reliable indicator of genetic relations, degree of fractionation, and rare-metal potential of granites. Granites with Zr/Hf values lower than 25 are promising for prospecting for Sn, W, Mo, and Be greisen deposits, whereas the formation of Ta deposits requires Zr/Hf values lower than 10.     

U-Pb Zircon Dating of the Yeniutan Granitic Intrusion in the Western Sector of the North Qilian Mountains

Zircons from granodiorite and biotite granite in the Yeniutan granitic intrusion in the western North Qilian Mountains yielded a weighted mean 206Pb/238U apparent age of 460±3 Ma, suggesting that the intrusion originated during the late stage of plate subduction. Its related Ta'ergou and Xiaoliugou deposits are two of the few large tungsten deposits formed in the plate subduction environment in the world. The U-Pb dating of the zircons from the biotite granite gave a discordant lower intercept age of 183±4 Ma, which implies that the Yanshanian event was probably superimposed on the North Qilian region.     

Coexistence of a Fluid Phase with Granitic Magma: Geochemical Characteristics of REE and Cu in Miyako Granite and in Scheelite-bearing Aplitic Veins at the Yamaguchi Cu-W Skarn Deposit, Iwate, Japan

Abstract: The North granitic body of the Miyako pluton is located in the Northern Kitakami belt, Northeast Japan. The formation of the scheelite–chalcopyrite–magnetite–bearing aplitic veins and scheelite–chalcopyrite–magnetite–bearing Yamaguchi skarn deposit was closely associated with the formation of the Miyako plutons. Petrographic facies of the North granitic body vary from quartz diorite in marginal zone (zone A), to tonalite and granodiorite (zone B), and to granite (zone C) in the central. The large numbers of aplitic veins distributed around the Yamaguchi mining area are divided into two groups: barren and scheelite–mag–netite–chalcopyrite–bearing aplitic veins. The latter cut massive clinopyroxene skarns of the Yamaguchi deposit, and are composed of plagioclase, K‐feldspar and titanite. Some plagioclase crystals have dusty cores with irregularly shaped K‐feldspar flakes, and clear rims of albite. Textures of plagioclase in the mineralized aplitic veins are different from the idiomorphic textures with sharp plagioclase crystal boundaries that occur in the North granitic body and barren aplitic veins. These textural data suggest that the mineralized aplitic veins were formed from hydrothermal fluid. Changes in the contents of major and minor (Rb, Sr, Sc, Co, Th, U) elements in the North Miyako granitic body are similar to those of zoned plutons formed by typical magmatic differentiation processes. On the other hand, concentrations of REE, especially middle to heavy REE, of granitic rocks in zone C and barren aplitic veins are significantly lower than those of granitic rocks in zones A and B. The hypothetical chondrite‐normalized REE patterns, calculated assuming fractional crystallization from zone B granitic melt, suggest that REE concentrations of the residual melt increased with the degree of fractional crystallization, and changed into a pattern with enriched LREE and strongly negative Eu anomaly. However, the REE patterns of granitic rocks in zone C are different from the hypothetical patterns. Moreover, the REE patterns of magnetite–scheelite–chalcopyrite aplitic veins are quite different from those of granitic rocks. The Cu contents of granitic rocks in the North Miyako body increase from zone A (5–26 ppm) to zone B (10–26 ppm), and then clearly decrease to zone C (5–7 ppm) and drastically increase to the barren aplitic veins (39–235 ppm). Concentrations of Cu in the mineralized aplitic veins are also higher than those of the granitic rocks in zone C. The decrease in REE and Cu contents of granitic rocks from zone B to zone C is not a result of simple magmatic fractional differentiation. Fluid inclusions in quartz from mineralized aplitic veins contain 3.3 wt% NaCl equivalent and 5.8 wt% CO₂. It was also demonstrated experimentally that the removal of MREE and HREE by fluid from melt enabled the formation of complexes of REE and ligands of OH^‐ and CO₃^2‐. Based on the possibility that the melt of the granitic rocks of zone C and the mineralized aplitic veins coexisted with CO₂‐bearing fluid, it is thought that REE were extracted from the melt to the CO₂‐bearing fluid, and that the REE in the mineralized aplitic veins were transported by the CO₂‐bearing fluid. It is likely that the low HREE and Cu contents of the granitic rocks in zone C could have been caused by the removal of those elements from the granitic melt by the fluid coexisting with the melt. The expelled materials could have been the sources of scheelite–magnetite–chalcopyrite–bearing aplitic veins and copper mineralization of the Yamaguchi Cu‐W skarn deposit.     

The mineralogy and chemical composition of the Woodlawn massive sulphide orebody

The main Woodlawn ore lens is a polymetallic, massive sulphide deposit’ with pyrite the major constituent, variable sphalerite, galena and chalcopyrite, and minor arsenopyrite, tetrahedrite‐tennantite, pyrrhotite and electrum. The silicate gangue minerals are chlorite, quartz, talc and sericitic mica. Other mineralization in the vicinity consists of footwall copper ore in chlorite schist and several smaller massive sulphide lenses. The predominant country rocks are felsic volcanics and shales, with abundant quartz, chlorite and mica, and talc in mineralized zones.

An important textural feature of the massive ore is the fine compositional banding. Bands, which vary in thickness from a few tens of micrometres to several millimetres, are produced by variations in the sulphide content. Post‐depositional metomorphism and minor fracturing have only slightly modified this banding.

Apart from the major element constituents—Pb, Zn, Fe, Cu and S—the ore is characterized by significant (100–1000 ppm) values for Ag, As, Cd, Mn, Sb and Sn, and lower (1–100 ppm) values of Au, Bi, Co, Ga, Hg, Mo, Ni, Tl. In and Ge. Variations in the base‐metal sulphide content, the gangue mineralogy, and trace elements, are used to separate the orebody into hanging‐wall and footwall zones. The hanging‐wall zone shows a more variable trace element content, with higher Tl, Sn, Ni, Mn, Ge and Sb, but lower Ag, Cd, and Mo, than the footwall zone.

In general style of mineralization, mineralogy, and chemistry, the Woodlawn deposit resembles other volcanogenic massive sulphide deposits in eastern Australia, in New Brunswick in Canada, and the Kuroko deposits of Japan.     

Comparative Studies of the Petrochemistry of Sn–W‐Mineralized Granitoids: Continent vs. Island Arc

Granitic rocks obtained during field excursions of the famed mineralized regions of the Erzgebirge, Germany (mainly tin‐bearing), and South China (mainly tungsten‐bearing) have been geochemically analyzed and their results are compared with similar (mainly tungsten‐bearing) granites in the island‐arc setting of Southwest Japan. The studied granitoids all belong to the ilmenite‐series. The collision‐related Erzgebirge granitoids are rich in K₂O and P₂O_5, have high A/CNK ratios (1.11–1.24, i.e. S type), but are also high in Ga/Al ratio (i.e., having some A‐type characteristics). In South China, the Xihuashan granites, in contrast, are very low in P₂O₅, and have A/CNK slightly above 1.0 (1.01–1.05), indicative of I type granites. The (Sn‐) W‐related granites of southwest Japan have similarly low P₂O₅ and A/CNK ratios, indicative also of I‐type. Both in the Xihuashan and southwest Japan, the tungsten‐related granites have high whole‐rock δ¹⁸O values implying involvement of W‐rich crustal rocks. Sn and W contents of the unaltered granites are lowest in the island‐arc setting where the related Sn–W deposits are smallest in size relative to the collision and continental margin settings of the Erzgebirge and South China.     

Oxygen isotopic study of the Cretaceous granitic rocks in Japan

The ( ¹⁸O values of nine Cretaceous granitic rocks from the low P/T type regional metamorphic zone of Japan are +10.0 to +13.2 relative to SMOW, while ten Cretaceous granitic rocks from the non-metamorphic zone are +7.9 to +9.8. The ¹⁸O-enrichment in the former rocks is mainly attributed to oxygen isotopic exchange between the granitic magma and the surrounding metamorphic rocks during regional metamorphism. The assimilation of ¹⁸O-rich country rocks is also possible in the cases such as gneissose granite and migmatite.The oxygen isotopic ratios of quartz-biotite pairs in the granitic rocks indicate that they are isotopically in near-equilibrium with each other. The quartz-biotite isotopic equilibrium temperatures estimated for these rocks range from 550° to 670° C. Feldspar is occasionally isotopically in disequilibrium with other minerals. This may be caused by exchange of oxygen isotopes between feldspar and hydrothermal or meteoric water after crystallization.     

滇西来利山与小龙河云英岩型锡矿成矿流体氧逸度特征对比

来利山锡矿床与小龙河锡矿床是滇西地区典型的云英岩型锡矿床。为揭示它们在成因上深层次的差异性,对来利山锡矿和小龙河锡矿的锡石进行了电子探针成分分析、镜下观察以及成矿环境对比分析。结果表明,锡石中的铁多以Fe~(3+)的形式与Sn~(4+)发生类质同象,氧逸度越高,锡石中Fe~(3+)越多,宏观上表现为锡石的颜色越深。来利山矿区锡石中Fe含量明显低于小龙河矿区,且锡石颜色明显比小龙河矿区颜色浅,反映了来利山锡矿成矿环境相对开放,成矿流体氧逸度偏低,流体中Sn络合物迁移能力较强,在花岗岩体外接触带的围岩裂隙中形成外云英岩型锡矿床;而小龙河锡矿成矿环境相对封闭,成矿流体氧逸度偏高,流体中Sn络合物迁移能力较弱,多在花岗岩体顶部的构造裂隙中形成内云英岩型锡矿床。     

40Ar‐39Ar and K‐Ar age constraints on the Early Proterozoic Tennant Creek Block,northern Australia,and the age of its gold deposits∗

⁴⁰Ar‐³⁹Ar age spectra on minerals from granitic, metamorphic and hydrothermal rocks confirm that the Early Proterozoic Tennant Creek Block was affected by two thermal events during its evolution. Although extensive alteration of biotite and feldspar within the granites precludes the direct determination of their cooling history, ⁴⁰Ar‐³⁹Ar analyses for hydrothermal muscovite from several nearby gold‐copper deposits indicate that regional cooling to below ～ 300°C was not prolonged. Flat, uniform muscovite age spectra were obtained from gold deposits east of the Tennant Creek town site and indicate a minimum age of 1825–1830 Ma for their formation. These ages are within error of those for the felsic volcanism of the Flynn Subgroup, and a genetic relationship between the two may exist. Samples from gold deposits elsewhere in the area indicate disturbance of the K‐Ar isotope system. The second thermal event to affect the region occurred at around 1700 Ma, and is confirmed by the ⁴⁰Ar‐³⁹Ar muscovite ages for the ‘Warrego’ granite (1677 ± 4 Ma) and for the metamorphism of the Wundirgi Formation (1696 ± 4 Ma).