Fluid inclusions and C-H-O-S isotope systematics of early Permian porphyry Mo mineralization of the West Junggar region,NW China: the Suyunhe example

ABSTRACT

The Suyunhe porphyry Mo deposit, located in the West Junggar terrane, is the largest molybdenum deposit found in Xinjiang to date, with a proven reserve of 0.57 Mt. The Suyunhe deposit is associated with Early Permian granitic rocks, which emplaced into the volcano-sedimentary sequences of the Middle Devonian Barluk Formation. Four metallogenic stages are identified in this study. Stage I is marked by the quartz-magnetite-K-feldspar±biotite±pyrite±molybdenite veins, which mainly occurred in the intensively potassic alternation zone and were formed at high temperature (>481°C), high salinity (58.6?65.18 wt.%), and relatively high oxygen fugacity conditions with a fluid system of NaCl-H₂O-CO₂. Stage II is the main metallogenic stage and develops numerous quartz-molybdenite±pyrite veins associated with muscovite–chlorite alteration, which were formed by immiscible fluids at medium-high temperature (210?427°C), medium-high salinity (43.36?49.90 wt.%), and relatively low oxygen fugacity conditions with the fluid system of NaCl-H₂O-CO₂-CH₄-C₂H₆. After the main Mo-mineralization, quartz-polymetallic sulphides veins associated with quartz–sericite alteration were formed by fluids at medium-low temperature, low-salinity conditions with the fluid system of NaCl-H₂O-CO₂ in stage III. The following quartz-polymetallic sulphide veins are quartz-calcite±pyrite veins associated with calcite alteration, which were formed by fluids at low temperature and low-salinity conditions with a fluid system of NaCl-H₂O in stage IV.

The δ¹⁸O‰ values indicate that the ore fluids of stages I and II are dominated by magmatic water, whereas stages III and IV are dominated by meteoric water. A wide range of δ³⁴S‰ values (?7.1 to 3.4‰) of sulphides between stages I and II indicates that increasing the reducibility plays an important role in molybdenum mineralization. The δ¹³C_CH4 values suggest that CH₄ of the ore fluids mainly results from the assimilation–contamination of carbonaceous country rocks, and partly derives from magma. However, the δ¹³C_CO2 values suggest that CO₂ of the ore fluids mainly originates from magma, and minor derives from wall-rocks as well as meteoric water.     

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.     

Control of magmatic oxidation state in intracontinental porphyry mineralization: A case from Cu (Mo–Au) deposits in the Jinshajiang–Red River metallogenic belt,SW China

The Jinshajiang–Red River porphyry Cu (Mo–Au) metallogenic belt (JRMB) is the most important intracontinental porphyry Cu (Mo–Au) mineralizing zone in the Sanjiang region, southwest China. The belt contains a number of giant deposits, including Yulong (6.50 Mt Cu) and Beiya (315 t Au) in the northern and center parts, and several small deposits in the southern part (e.g., Tongchang, 0.03 Mt Cu + Mo; Chang'anchong, 0.04 Mt Cu + Mo; Habo, 0.57 Mt Cu + Mo; and Chang'an 31 t Au). In order to investigate the mechanisms controlling the variation in size of these deposits, the LA-ICP-MS zircon U–Pb dating, bulk-rock geochemistry, and zircon trace-element analyses have been performed on the mineralization-related porphyries from the Tongchang district. Zircon U–Pb dating yielded concordant ages of 34.2 ± 0.6 Ma (Tongchang), 33.7 ± 0.8 Ma (Chang’anchong), 35.7 ± 0.5 Ma (Habo) and 34.6 ± 1.2 Ma (Chang’an). These porphyries are peraluminous with relatively high potassium contents (K₂O: 4.2–5.7 wt%), and show shoshonitic affinities. Bulk rock Fe₂O₃/FeO ratios vary from 0.51 to 0.97, typical of moderately oxidized to strongly oxidized magmas. Zircon Ce⁴⁺/Ce³⁺ values vary between 25.9 and 371.8 with a mean of 129.3. The log(ƒo₂) values vary from −20.7 to −9.6, and plot within the range of FMQ (fayalite-magnetite-quartz oxygen buffer) to MH (magnetite- hematite oxygen buffer), indicating an oxidizing parental magma. The mineralized porphyries from the Yulong and Beiya deposits, which were previous considered to have formed under the same tectonic conditions as those in the Tongchang district, have higher mean zircon Ce⁴⁺/Ce³⁺ values of 249.4 and 399.5, suggesting that the oxygen fugacities of the porphyries in the Tongchang district is relatively lower. This might imply that oxygen fugacity is an important factor that led to the differentiation of deposit size in the JRMB, and that larger porphyry deposits are associated with more oxidized magmas.     

Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit,southwest China

Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ⁶⁵Cu values (δ⁶⁵Cu = [(⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ⁶⁵Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ⁶⁵Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.     

西藏尕尔勤铜矿床花岗闪长斑岩地球化学特征及成矿作用研究

对尕尔勤铜矿床花岗闪长斑岩及其锆石的稀土元素进行了分析,并对其成矿作用进行了研究。结果表明,花岗闪长斑岩稀土元素总含量变化范围不大（ΣREE=48.64×10-6~78.12×10-6）,LREE/HREE=8.67~11.68,所有样品都呈轻稀土元素相对富集、重稀土元素亏损的右倾型分配模式;δEu由弱负异常→弱正异常演化,这是因为地幔底辟作用引发地壳部分重熔形成长英质岩浆的过程中,逐步消弱了结晶分异导致的负Eu异常进而出现弱的正Eu异常。锆石具有典型的振荡环带,稀土总量较高（ΣREE=735.78×10-6~6792.10×10-6）,相对亏损轻稀土,富集重稀土,正Ce异常明显,并呈现弱的负Eu异常,这是因为在地幔流体作用下,重稀土元素及Ce较其它轻稀土元素更容易进入锆石晶格所致,Eu呈弱的负异常则是成岩后期岩体受氧化淋滤所致。综合分析,揭示出地幔流体作用导致花岗闪长斑岩具有壳幔混染甚至成矿特征,同时还能透过岩浆与围岩发生物质和能量的交换,导致变质砂岩成矿的成因机制。      

扬子陆块东南缘升天坪锌矿床地质特征、闪锌矿Rb-Sr定年及其地质意义

升天坪锌矿床位于扬子陆块东南缘雪峰山地区,是湘西地区产于陡山沱组的中型锌矿床。采用同位素稀释法对主成 矿期闪锌矿进行Rb-Sr同位素组成分析,获得等时线年龄为490 Ma,初始锶同位素组成87Sr/86Sr为0.71235。该等时线年龄代 表了该矿床的主成矿阶段年龄,说明矿床形成的地质时代为晚寒武世,成矿作用发生于加里东中期。成矿作用时代与闪锌 矿初始锶同位素比值特征反映成矿物质或成矿流体由基底岩石（板溪群） 和震旦系碳酸盐岩地层共同提供。结合矿床地质 特征与区内铅锌矿成矿地质背景,认为周边板块碰撞的远程效应为热液成矿提供了构造驱动力,加里东期的构造运动对升 天坪锌矿床的形成起着重要作用。升天坪锌矿床严格受地层控制,矿床类型为沉积-改造型层控矿床。     

四川雪宝顶W-Sn-Be矿床矿物学特征和形成机制

四川雪宝顶W-Sn-Be矿床位于龙门山西北缘,主要赋存在盘口和浦口岭花岗岩之间的大理岩张性裂隙中。雪宝顶矿床中出现的矿物晶体颗粒巨大,且矿脉中矿物分带明显。矿脉在花岗岩中主要由绿柱石、锡石、白云母和钾长石(fd1、fd2和fd3)组成,在大理岩围岩中则由绿柱石、白钨矿、锡石、萤石、方解石、石英、钠长石晶体(Ab4和Ab5)以及针状电气石和细粒磷灰石组成。3种不同形态的钾长石和2种不同形态的钠长石贯穿了整个矿脉的演化。随着围岩从花岗岩到大理岩的转换,晶体颗粒从小于1 cm的绿柱石、锡石演化至可达20 cm的绿柱石、锡石、萤石和白钨矿。采用EPMA、XRF、ICP-MS对单矿物颗粒进行全岩测试分析,结果显示:雪宝顶板状绿柱石介于Na-Li绿柱石和Li-Cs绿柱石之间,白钨矿中富集∑REE+Y(350×10~(-6)),白云母属于含Li白云母,磷灰石属于氟磷灰石,钾长石和钠长石比较纯净[fd1(Or 95.34~93.96)、fd2(Or 96.28~97.88)、fd3(Or 95.74~98.39)、Ab4(Ab 99.19~100)、Ab5(Ab 99.58~100)]。结合前人研究资料推测矿床形成机制为:在花岗岩演化的晚期,富F流体的脱熔作用大量富集了Li、Rb、Cs、W、Sn、Be、P等元素。这些来自于熔体的元素以不同的化合物形式(如SnF)在分离结晶过程中富集,通过成矿流体运移然后在花岗岩裂隙中小规模沉淀。花岗岩体的冷却引发的体积缩小导致了大理岩围岩中出现了放射状的张性裂隙。张性裂隙是控制成矿流体输运的主要通道,并引发了流体不混溶(相分离)。这个过程还伴随着包裹体均一温度不断下降和含矿络合物与围岩之间不断发生反应导致络合物不断分解。此时,成矿围岩从花岗岩变成大理岩,含F络合物大量被破坏造成成矿物质W-Sn-Be等元素大量沉淀,形成颗粒巨大的矿物晶体。选取与大颗粒绿柱石晶体共生的云母样品进行Ar-Ar定年并获得反等时线年龄195.7±2.5 Ma,代表了雪宝顶矿床形成的主成矿期年龄。     

小兴安岭西北部与永新金矿有关岩浆岩的年代学和地球化学及成矿构造环境

永新金矿是近年发现的大型蚀变岩型脉状金矿床,闪长玢岩脉等与金矿脉相互穿切并侵入于上盘龙江组火山岩中。锆石LA ICP MS U-Pb测年显示,龙江组安山岩结晶年龄为(1137 ± 18)Ma,闪长玢岩结晶年龄为(1148 ± 19)Ma,均形成于早白垩世晚期。二者钠钾含量变化相对较大,相对富铝富铁、钙镁含量中等,从火山岩到脉岩表现为钙碱性向碱性系列过渡特征。火山岩、脉岩与矿石的稀土元素配分曲线有很好的一致性,矿石稀土含量低于岩石。岩石微量元素总体显示Zr、Hf、Nd、U等明显富集,而Nb、Ta、Th、P、Ti等明显亏损。在Sr/Y-Y和(La/Yb)N-(Yb)N图解中,所有样品均落入经典岛弧岩石范围;在Nb-Y、Ta-Yb的构造环境判别图中均处于火山弧岩浆岩区,在(La/Yb)N-δEu变异图上落在壳-幔型岩浆范围。结合矿床稳定同位素及区域金矿时空分布规律等综合特征,认为永新金矿的形成与早白垩世古太平洋板块俯冲所引发的(火山)岩浆活动有关。     

大兴安岭中北段古中公路钼矿床形成时代与矿床成因

古中公路钼矿床含矿岩体为碎裂硅化片麻状二长花岗岩体,蚀变呈带状分布,成矿过程可划分为钾长石+石英、石英+辉钼矿及石英+黄铁矿3个阶段。2件辉钼矿样品的Re-Os同位素模式年龄分别为(142.4±2.9)Ma和(142.3±2.0)Ma,表明矿床为早白垩世构造-岩浆活动的产物;辉钼矿中w(Re)含量分别为11.894×10~(-6)和11.584×10~(-6),暗示成矿物质主要为地壳来源,可能有地幔物质的参与。流体包裹体研究表明:主成矿阶段的石英中主要以气液两相包裹体为主,其次为含子晶三相包裹体,CO_2三相包裹体最少;不同类型包裹体的均一温度范围为196.3℃~450℃,盐度可分为0.18%~12.62%和45.33%~53.26%两个不同区间。因此,成矿流体为中高温、高盐度的Na Cl-H2O-CO2体系,在热液成矿阶段可能发生过流体沸腾作用,且是钼矿的主要形成机制。综合成矿地质条件、矿床地质特征及成矿流体特征认为,该矿床成因上属斑岩型,形成于区域伸展的构造环境。     

兴蒙造山带及华北板块北缘钼矿化——进展、规律、问题与成因初探

兴蒙造山带及其南侧受古亚洲洋南向俯冲所影响的华北板块北缘内各有1条显著的中生代斑岩钼成矿带,并在东西两侧首尾相连。文章综述了伸展环境下的斑岩钼矿床的研究进展,对兴蒙造山带及华北板块北缘内这2条钼成矿带的成矿背景、分布规律、矿床共生组合特点、成矿岩浆的属性、巨量金属和水的来源以及斑岩铜、钼矿化的异同等进行了总结,并从成矿岩浆源区塑造过程的角度初步探讨了巨型钼成矿带的形成特点。这2条钼成矿带在地质特征和区域矿床组合上非常相似,具有相似的启动时间和峰值时间,与区域内的斑岩铜矿化在时代上具有不共生的特点,矿化特征也与美国科罗拉多地区产出的高F型斑岩钼化类似,二者构成了统一的整体。元素地球化学对比研究显示,南、北2条钼成矿带的成矿岩浆与古生代斑岩铜成矿岩浆以及中生代的碱性岩浆均具有相似的特征,为脱水熔融的产物,并与古老陆下岩石圈地幔包体、新生代软流圈地幔玄武岩具有显著的差别。研究认为,南钼矿带的岩浆源区是亏损金属和水的古老岩浆源区在古生代洋片俯冲过程脱水交代改造后的产物,北钼矿带的岩浆源区是古生代洋片俯冲增生形成的富水源区。成(含)矿岩石Sr同位素研究显示,南、北2条钼成矿带成矿源区均启动于Rb/Sr比值较低的源区,受到上部高Rb/Sr比值地壳的混染;Nd同位素特征的对比研究显示,二者初始Nd值差别极大,但是Sm/Nd比值非常相似,显示放射性成因Nd的积累在三叠纪以后是一致的,也说明初始Nd值的差别是成矿源区塑造前所形成和继承的,同时也说明初始Nd值的差异可能掩盖了Mo成矿岩浆形成的真正原因。通过与世界范围内其他典型钼成矿带的对比研究,认为南、北2条钼成矿带成矿的岩浆源区位于陆下岩石圈地幔,古生代期间古亚洲洋向南、北两侧的俯冲在其形成过程中具有重要作用,主要体现在塑造富集型源区、水化造山带和增厚岩石圈等几个方面。俯冲改造、加厚并富集了水和大离子亲石元素的陆下岩石圈获得了地球化学上的不稳定性,在伸展构造环境(可能有多期伸展)驱动下,脱水熔融以达到稳定的趋势,在这个过程中,其化学成分将逐渐与古老陆下岩石圈地幔的化学成分趋于一致。因此,水化的陆下岩石圈地幔在伸展过程中的低程度批式脱水部分熔融,形成的富含金属和水的高分异型岩浆构成了成矿岩浆,并在岩石圈的不同尺度经过多阶段结晶分异-同化混染后,就位成为近矿岩浆房。陆下岩石圈脱水熔融的结束也意味着巨型热液钼矿化作用的结束,并决定了俯冲后巨型热液成矿带总的生命周期,这也与兴蒙造山带及华北板块北缘钼矿化(甚至其他热液型矿化)在早白垩世(约130 Ma)趋于减弱并熄灭的现象一致,也使得新生代的碱性岩浆岩不具有显著的脱水熔融特征。综上,笔者认为兴蒙造山带及华北板块北缘的斑岩钼矿化为一个统一的整体,属于古亚洲洋俯冲作用水化的源区在后期强烈伸展环境下部分熔融的产物,是古亚洲洋俯冲成矿作用的延续和发展,也是古生代塑造的富集型源区在中生代伸展构造驱动下的复合成矿作用。