Rhenium–Osmium Isotope Measurements in Marine Shale Reference Material SBC‐1: Implications for Method Validation and Quality Control

In this study, the USGS black shale reference material SBC‐1 was investigated as a matrix‐matched reference material for both intra‐laboratory calibration and inter‐laboratory comparison of high‐precision Re‐Os dating for organic‐rich sedimentary rocks. This reference material was analysed for Re‐Os isotopic composition by three digestion protocols – inverse aqua regia, CrO₃‐H₂SO₄ and H₂O₂‐HNO₃. The results for SBC‐1 obtained by inverse aqua regia digestion yielded similar Re mass fractions but slightly (~ 5%) higher Os mass fractions and lower ¹⁸⁷Os/¹⁸⁸Os values than the CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions. The data set of inverse aqua regia digestion exhibited strong correlations in plots of ¹⁸⁷Os/¹⁸⁸Os vs. 1/¹⁹²Os and ¹⁸⁷Os/¹⁸⁸Os vs. ¹⁸⁷Re/¹⁸⁸Os, which may signify the incorporation of detrital Re and Os into organic matter in the Re‐Os system. Similar correlations were also observed for the CrO₃‐H₂SO₄ digestion data set, but not for that of H₂O₂‐HNO₃. The data indicate that there is an amount of non‐hydrogenous Os in SBC‐1 and that CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions would minimise liberation of the non‐hydrogenous Os component. We propose that SBC‐1 may be a more suitable reference material to monitor the influence of detrital Re and Os on Re‐Os isochron age data, especially for samples with less organic matter and more siliceous detritus.     

Metallogenesis and hydrothermal evolution of Middle Jurassic porphyry Mo deposits in the southern Zhangguangcai Range,NE China: evidence from fluid inclusions,H–O–S isotopes,and Re–Os geochronology

A major metallogenic belt with substantial resources of gold, lead, zinc, copper, and molybdenum is present in the southern Zhangguangcai Range, NE China. Several large porphyry Mo deposits are located in this belt, as for example at Jidetun, Fu’anpu, and Daheishan. Five molybdenite samples from the Jidetun deposit yielded an Re–Os isochron age of 168.6 ± 2.1 Ma (mean standard weighted deviation = 0.20), and this is consistent with the Re–Os isochron ages of the other Mo deposits in the southern Zhangguangcai Range, giving a Middle Jurassic age for metallogenesis. The Jidetun, Fu’anpu, and Daheishan deposits all tend to have weakly enriched ³⁴S values of 0.80‰–3.20‰ and relatively low Re contents ranging from 3.073 to 43.567 ppm, which indicates the ore-forming materials were derived mainly from granitic magmas that had an origin in the mixture of crust and mantle. Three stages of mineralization can be identified in the deposits at Jidetun, Fu’anpu, and Daheishan. The original ore-forming fluids in stage I were characterized by high-temperature magmatic hydrothermal fluids that were most likely derived by exsolution from the Middle Jurassic ore-bearing magmas. However, two different fluid systems, NaCl–H₂O–CO₂ fluids and NaCl–H₂O fluids, were widespread in stage I of porphyry Mo deposits in the southern Zhangguangcai Range. Taking into account the regional geological characteristics and tectonic setting, we suggest that two different emplacement modes of the ore-bearing magmas explain the different fluid systems in stage I: the first magmas were emplaced along the contact zones between the strata and earlier granitoids, whereas the second magmas were emplaced entirely within the earlier granitoid intrusions. The stage II and III fluids were characterized by relatively lower temperatures and low H–O isotopic values, indicating a gradual evolution from magmatic to meteoric sources.     

Multiple Mesozoic porphyry-skarn Cu (Mo–W) systems in Yidun Terrane,east Tethys: Constraints from zircon U–Pb and molybdenite Re–Os geochronology

Porphyry Cu ± Mo ± Au deposits typically formed in volcanoplutonic arcs above subduction zones. However, there is increasing evidence for the occurrence of porphyry deposits related to magmas generated after the underplating arc has ceased. Post-subduction lithospheric thickening, lithospheric extension, or mantle lithosphere delamination could trigger the remelting of subduction-modified arc lithosphere and lead to the formation of post-subduction porphyry deposits. The NNW-trending Yidun Terrane, located in the eastern Tethys, experienced subduction of Garze–Litang oceanic plate (a branch of the Paleotethys) in the Late Triassic and witnessed two mineralization events respectively associated with the ca. 215 Ma arc-related intermediate–felsic porphyries and the 88–79 Ma mildly-alkaline granitic porphyries. It is, therefore, an ideal place to investigate the genetic linkage between the subduction-related porphyry deposits and post-subduction porphyry deposits. Our new in situ zircon U–Pb dating of the two granitic intrusions (biotite granite, 213.4 ± 0.9 Ma; monzogranite porphyry, 86.0 ± 0.4 Ma) in the Xiuwacu district, the molybdenite Re–Os age (84.7 ± 0.6 Ma) of the mineralization, and previously published geochronological data, together show the spatially overlapping distribution of the multiple Mesozoic porphyry systems in the Late Triassic Yidun arc system. Furthermore, the arc-like elemental signatures and the mixed Sr–Nd–Hf isotopic signatures of the Late Cretaceous ore-related porphyries (i.e., originating from a mixed components between the ∼215 Ma juvenile arc crust and the Mesoproterozoic mafic lower crust) indicate a genetic linkage between the Late Triassic and Late Cretaceous porphyry systems. This suggests that the remelting of underplated arc-related mafic rocks formed during the subduction of the Garze–Litang Ocean could be responsible for the mixing between the mantle-derived components and the Mesoproterozoic lower crustal materials, when post-subduction transtension occurred in the Late Cretaceous. The formation of the Late Cretaceous porphyry–skarn Cu–Mo–W deposits could most likely be related to the remelting of Late Triassic residual sulfide-bearing Cu-rich cumulates in the subduction-modified lower crust that triggered by the Late Cretaceous transtension.     

Age and origin of uranium mineralization in the Camie River deposit (Otish Basin,Québec,Canada)

The Camie River uranium deposit is located in the southeastern part of the Paleoproterozoic Otish Basin (Québec). The uranium mineralization consists of disseminated and vein uraninite and brannerite precipitated close to the unconformity between Paleoproterozoic fluviatile, pervasively altered, sandstones and conglomerates of the Matoush Formation and the underlying sulfide-bearing graphitic schists of the Archean Hippocampe greenstone belt. Diagenetic orange/pink feldspathic alteration of the Matoush Formation consists of authigenic albite cement partly replaced by later orthoclase cement, with the Na₂O content of clastic rocks increasing with depth. Basin-wide green muscovite alteration affected both the Matoush Formation and the top of the basement Tichegami Group. Uraninite with minor brannerite is mainly hosted by subvertical reverse faults in basement graphitic metapelites ± sulfides and overlying sandstones and conglomerates. Uranium mineralization is associated with chlorite veins and alteration with temperatures near 320 °C, that are paragenetically late relative to the diagenetic feldspathic and muscovite alterations. Re-Os geochronology of molybdenite intergrown with uraninite yields an age of 1724.0 ± 4.9 Ma, whereas uraninite yields an identical, although slightly discordant, 1724 ± 29 Ma SIMS U-Pb age. Uraninite has high concentrations in REE with flat REE spectra resembling those of uraninite formed from metamorphic fluids, rather than the bell-shaped patterns typical of unconformity-related uraninite. Paragenesis and geochronology therefore show that the uranium mineralization formed approximately 440 million years after intrusion of the Otish Gabbro dykes and sills at ∼2176 Ma, which constrains the minimum age for the sedimentary host rocks. The post-diagenetic stage of uraninite after feldspathic and muscovite alterations, the paragenetic sequence and the brannerite-uraninite assemblage, the relatively high temperature for the mineralizing event (∼320 °C) following the diagenetic Na- and K-dominated alteration, lack of evidence for brines typical of unconformity-related U deposits, the older age of the Otish Basin compared to worldwide basins hosting unconformity-related uranium deposits, the large age difference between basin fill and mineralization, the older age of the uranium oxide compared to ages for worldwide unconformity-related U deposits, and the flat REE spectra of uraninite do not support the previous interpretation that the Camie River deposit is an unconformity-associated uranium deposit. Rather, the evidence is more consistent with a PaleoProterozoic, higher-temperature hydrothermal event at 1724 Ma, whose origin remains speculative.     

古老大陆岩石圈地幔再循环与蛇绿岩中铬铁矿床成因

不同地区、不同时代蛇绿岩中不同类型铬铁矿岩的Re-Os同位素研究表明,在铬铁矿石或围岩中均存在极度亏损的具有大陆岩石圈地幔属性的物质。新疆达拉布特古生代蛇绿岩带中萨尔托海富Al铬铁矿岩的Os同位素组成为0.1109～0.1256,对应的模式年龄为3.5～0.6Ga;西藏班公湖—怒江中生代蛇绿岩带中东巧富Cr铬铁矿石及围岩Os同位素组成介于0.1175～0.1261,对应的模式年龄为1.5～0.1Ga;雅鲁藏布江中生代蛇绿岩带中罗布莎富Cr铬铁矿岩的Os同位素变化范围为0.1038～0.1266,对应的模式年龄为3.37～0.28Ga,而该带中不含矿的泽当二辉橄榄岩的Os同位素组成为0.1256～0.1261,没有古老大陆岩石圈地幔属性的物质存在,与新特提斯洋地幔Os组成较为接近。推测在蛇绿岩形成过程中,古老大陆岩石圈地幔参与循环有利于形成铬铁矿床,明确提出"熔体与古老大陆岩石圈地幔反应成矿"的假说,指出蛇绿岩带中存在的古老微陆块可能是找矿的指示标志。     

Low-rhenium molybdenite by metamorphism in northern Sweden: Recognition, genesis, and global implications

Re–Os dating of molybdenite is an accurate means to date intrusions and intrusion-related ore deposits using the model age or isochron approach. But, molybdenite has a new niche in the greenschist- to granulite-facies metamorphic environment. Re–Os ages for metamorphic molybdenite may be used to construct regional metamorphic histories. Age significance and accuracy are established by analyzing multiple molybdenite separates extracted from single, petrographically-characterized molybdenite occurrences. In this study, twelve geologically distinct molybdenite-bearing samples from two small Mo districts in northern Sweden trace a 150 m.y. Paleoproterozoic Svecofennian metamorphic history from 1900 to 1750 Ma. These data reveal a little-known, widespread and protracted, Late Svecofennian anatexis in northern Sweden.The Kåtaberget Mo–(Cu, F) deposit is located in the Moskosel granite batholith north of the economically-renown Skellefte district. Four different molybdenite samples from outcrop at Kåtaberget indicate an intrusion age of 1895 ± 6 Ma with the formation of later pegmatite–aplite at 1875 ± 6 Ma. The Allebuoda (Björntjärn) and Munka Mo–(W) deposits in the Rappen district are represented by three outcrop and five drill core samples of molybdenite-bearing aplite–pegmatite–granite. These two deposits were previously described as intrusion-related Climax-type Mo mineralization. Re–Os ages for molybdenites from these deposits range from 1865 to 1750 Ma and, significantly, Re concentrations are markedly low, extending to the sub-ppm level. Age agreement within the deposits is conspicuously lacking, whereas, with one exception, age agreement within any single sample (geologic occurrence), as established by analysis of additional molybdenite separates, is very good. These data, together with fundamental geologic observations discussed in this paper, suggest that Mo–(W) mineralization in northern Sweden is not intrusion-related, but the local product of episodic melting of Archean–Paleoproterozoic supracrustal gneisses related to the Svecofennian orogeny. Petrographic traverses across the boundary between widespread, foliation-parallel units of aplitic to pegmatitic pink granite and hosting biotite gneiss directly capture the process of ore formation. Dehydration breakdown of zircon-rich biotite aligned with the foliation in the gneiss is accompanied by formation of new pristine, post-deformational biotite plus sulfides, oxides, hydrothermal zircon and fluorite, all associated with microcline-dominant leucosomes.This process has profound implication for the traditional leucogranite, intrusion-related genesis attributed to the broad classification of Mo–W–Sn–base and precious metal mineralization (e.g., South Mountain Batholith, Nova Scotia; Okiep, Namaqualand, South Africa; Mactung, Yukon; Pogo–Liese, Tintina, Alaska; Carajás and Goiás–Rio Tocantins, Brazil; New England Batholith, NSW, Australia; Bergslagen, Sweden; Nevoria, Western Australia; Alpeinerscharte, Austria; Erzgebirge, Germany; Sardinia–Corsica Batholith). In addition to biotite, metallogenic contributions (e.g., Mo, W, Sn, U, Bi, Cu, Pb, Zn, Fe, Ni, Co, Au, Ag, Te, As, Sb, REE) in various combinations may also be controlled by breakdown of amphibole. In effect, the trace element composition of dehydrating or recrystallizing components in a gneissic rock essentially defines the local and district metallogenic suite. In the absence of focusing structures (e.g., shear zones, sheeted vein development), this process will generally form small and disconnected subeconomic deposits with erratic and unpredictable grades. Low Re content in associated molybdenite is a key indicator for a subeconomic origin by local melting of biotite gneiss (Mo–W) or muscovite schist (Sn–W).     

从铼的地球化学性质看我国铼找矿前景

铼是生产涡轮发动机耐高温超级合金的核心元素,被誉为改变航空业的金属。斑岩铜矿伴生的辉钼矿和还原性沉积岩中的硫化物是铼的主要赋存矿物。从目前铼的产量来看,全球近一半的铼产出于智利的斑岩铜钼矿床。据美国地质调查局估计,智利的铼探明储量在1300吨。其他国家依次是美国、俄罗斯、秘鲁等国,均在300吨左右。从现有的数据估算我国目前的铼储量约为250吨,以辉钼矿伴生为主。从地球化学的角度来看,铼是地球上最稀有的金属之一;作为中度不相容的亲铜、亲铁元素,铼倾向于在岩浆中富集;铼对硫逸度、氧逸度敏感,在表生过程中可以通过氧化还原过程富集于黑色页岩等还原性沉积物中。封闭、半封闭的海湾是其常见的富集位置。在埃迪卡拉纪和寒武纪,大气中的氧气含量大幅度上升,是表生过程中铼迁移、富集的最佳时期。我国华南广泛分布形成于近海环境的埃迪卡拉纪-寒武纪黑色页岩,仅鄂西分布范围就有数千平方千米,厚度可以达到200m,其中铼的含量达到0. 1×10~(-6)～0. 6×10~(-6),远景资源量在万吨以上,是寻找铼矿的最佳选区之一。     

东昆仑热水钼多金属矿床辉钼矿Re Os同位素年龄及地质意义

热水钼多金属矿床位于青海省东昆仑造山带东段,是近年来新发现的一处斑岩型钼矿床。该矿床钼矿体主要分为四个矿带,矿体呈条带状,脉状等产出,矿石矿物以辉钼矿为主,围岩蚀变较为发育,具有一定分带性,呈面型蚀变,线性排布特征。本文通过Re-Os同位素定年方法对钼矿区6件辉钼矿样品进行了精确年龄测定,其模式年龄介于229.4±3.1~230.6±3.1Ma之间,年龄分布范围较为集中,平均为230.17Ma,等时线年龄为228.6±7.9Ma,MSWD=0.25,模式年龄加权平均值为230.2±2.5Ma,MSWD=0.025,表明成矿作用形成于印支期。6件辉钼矿样品Re含量介于13.02×10~(-6)~17.7×10~(-6),指示成矿物质可能主要来源为壳幔混合。结合已有成矿年龄研究,认为东昆仑造山带印支期成矿作用强烈,主要可分为两期,印支早期与印支晚期,形成一系列矿床,在印支晚期后碰撞阶段与岩浆热液相关的矿床具有较大成矿潜力。     

Triassic magmatism and Mo mineralization in Northeast China: geochronological and isotopic constraints from the Laojiagou porphyry Mo deposit

The Laojiagou Mo deposit is a newly discovered porphyry Mo deposit located in the Xilamulun Mo metallogenic belt, Northeast China. Mo mineralization mainly occurred within the monzogranite and monzogranite porphyry. Re–Os isochron dating of molybdenites indicate a mineralization age of 234.9 ± 3.1 Ma. Zircon LA–ICP–MS U–Pb analysis for monzogranite porphyry and monzogranite yield ²⁰⁶Pb/²³⁸U ages of 238.6 ± 1.8 and 241.3 ± 1.5 Ma, respectively, indicating that Laojiagou Mo mineralization is related to Middle Triassic magmatism. Hf isotopic compositions of zircons from both monzogranite porphyry and monzogranite are characterized by positive ε_Hf(t) values [ε_Hf(t) = 2.9–7.3 and 1.5–7.9, respectively] and young T_DM2 model ages, which implies that the magma was derived from juvenile crust created during accretion of the Central Asian Orogenic Belt (CAOB). Identification of the Laojiagou Mo deposit adds another important example of Triassic Mo mineralization in the Xilamulun Mo metallogenic belt where most Triassic Mo deposits in northeast China cluster around the northern margin of North China Craton. Based on the regional geological setting and geochronological and Hf isotope characteristics, we propose that Triassic Mo deposits and related magmatic rocks in northeast China formed during the last stages of evolution of the CAOB. These deposits formed during post-collisional extension after the closure of the Palaeo-Asian Ocean and amalgamation of the North China–Mongolian Block with the Siberian Craton.     

鄂东南地区龙角山—付家山斑岩体成因及其对成矿作用的指示

龙角山铜钨矿床是鄂东南地区典型的层控式矽卡岩型矿床。本文利用LA-ICP-MS锆石U-Pb法及辉钼矿Re-Os法对该矿床进行了详细的年代学研究。结果表明,矿区内的花岗闪长斑岩形成于144±1Ma,成矿作用发生于144.7±2.9Ma,成岩成矿作用近于同时发生,均为早白垩世。这意味着成矿作用与花岗闪长斑岩的演化存在密切联系。龙角山—付家山花岗闪长斑岩为高钾钙碱性系列,具有高Al2O3(14.99%~16.16%)、Sr(751×10-6~1382×10-6)含量和Sr/Y(65~99)、La/Yb(40~48)比值,以及低Y(12×10-6~15×10-6)、Yb(0.93×10-6~1.23×10-6)含量,与典型埃达克质岩的地球化学特征基本一致。全岩(87Sr/86Sr)i值为0.70603,εNd(t)值为-5.1,锆石εHf(t)值介于-0.5~-4.8之间。元素地球化学、全岩Sr-Nd同位素及锆石Hf同位素特征一致表明龙角山—付家山花岗闪长斑岩主要来源于富集岩石圈地幔的部分熔融作用,在成岩过程中可能伴随着镁铁质矿物的分离结晶作用。此外,与铜山口成矿斑岩体相比,龙角山—付家山花岗闪长斑岩具有较低的氧逸度,这很可能是导致两斑岩体在矿化类型上(前者以铜钼矿化为主,后者以铜钨矿化为主)存在差异的主要原因。