吉林省中东部地区侏罗纪钼矿床的地质、地球化学特征与成矿机理研究
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摘要
吉林省中东部地区是我国重要内生钼金属成矿区，继新中国成立初期发现超大型大黑山钼矿床以来，近十年来再度相继发现并勘探了季德屯、大石河大型斑岩型钼矿，福安堡、一心屯、刘生店、东风等中型钼矿以及小型钼矿6处，并发现30余处矿点、矿化点。截止2008年累计探明资源储量200余万吨，已成为我国第二大钼矿资源地和被关注与研究的热点地区。为了深入揭示该区钼矿的成矿规律和资源潜力，本论文在前人研究成果基础上，开展了各类钼矿床的矿床地质、流体性质、矿床地球化学和成岩成矿年代学研究，深入揭示了成岩成矿时代、成矿专属性、动力学背景，反演了成岩成矿机理，建立了成岩成矿模式和动力学模型，取得的主要成果与进展如下。
1．通过对研究区各类内生钼矿床的矿床地质特征研究，将该区内生钼矿床划分为斑岩型、接触交代热液型和中温热液石英脉型三种成因类型。斑岩型钼矿床矿体主要呈不规则状、透镜状，产于二长花岗（斑）岩或花岗闪长（斑）岩的岩体内，围岩蚀变主要有钾化、硅化、绢云母化、绿泥石化及碳酸盐化等，矿化经历了石英-黄铁矿阶段（Ⅰ）、石英-磁黄铁矿-黄铁矿阶段（Ⅱ）、石英-辉钼矿阶段（Ⅲ）、石英-多金属硫化物阶段（Ⅳ）和石英-碳酸盐阶段（Ⅴ）五个阶段。中温热液石英脉型钼矿床矿体以脉状为主，产在花岗岩的断裂体系中，围岩蚀变主要有硅化、绢云母化和钾化等，矿化基本经历了无矿石英脉阶段（Ⅰ）、石英-辉钼矿-黄铁矿阶段（Ⅱ）和石英-碳酸盐阶段（Ⅲ）三个阶段；接触交代热液型钼矿床矿体以脉状、扁豆状和透镜状为主，产于花岗岩岩体与古生代地层接触带上，围岩蚀变主要为绿泥石化、绿帘石化、矽卡岩化、绢云母化、碳酸盐化、硅化等，矿化基本经历了干矽卡岩阶段（Ⅰ）、湿矽卡岩阶段（Ⅱ）、石英-辉钼矿阶段（Ⅲ）、石英-多金属硫化物阶段（Ⅳ）和石英-碳酸盐阶段（Ⅴ），即：两期五个阶段。三类矿床之间具有明显的时空性，常构成斑岩或中温热液石英脉-接触交代成矿系统。
2．矿床的矿物流体包裹体研究揭示，斑岩型钼矿床以气液两相和含子矿物三相包裹体为特征，各矿化阶段的均一温度分别为＞420～400℃、360～350℃、340～230℃、220～210℃、180～160℃，盐度依次为＞41.05%～9.8%NaCleq、38.16%～4.48%NaCleq、35.78%～4.49%NaCleq、7.43%NaCleq、7.8%～9.5%NaCleq；接触交代热液型钼矿床主要发育气液两相包裹体、少量含CO_2三相包裹体，各矿化阶段均一温度分别为＞337～280℃、260～200℃、190～101℃，盐度分别为＞18.5%～9.3%NaCleq、20.5%～9.98%NaCleq、22.9%～7.33%NaCleq；中温热液石英脉型钼矿床主要发育气液两相包裹体，各矿化均一温度分别为＞330～300℃、280～170℃、160～120℃，盐度分别为＞12.07%～8.81%NaCleq、9.86%～3.37%NaCleq、9.21%～4.63%NaCleq。
3．将流体测温与流体包裹体气相成分分析和氢-氧同位素地球化学特征相结合，进一步揭示斑岩型钼矿床的初始流体为富CO_2和少量CH_4、N_2、H_2S的CO_2-H2O-NaCl多相岩浆流体体系，成矿晚期有大气降水混入；中温热液石英脉型钼矿床成矿初始流体为H2O-CO_2-NaCl多相岩浆流体，成矿阶段亦有大气降水加入；接触交代热液型钼矿床初始流体为中高温、中高盐度含CO_2、少量CH_4、N_2的H2O-CO_2-NaCl岩浆流体，主成矿阶段有大气降水混合。初步得出斑岩型钼矿床含矿流体成矿过程发生了强烈的流体不混溶作用；而中温热液石英脉型和接触交代热液型钼矿床流体演化过程中发生了混合作用。
4．成岩成矿年代学研究表明，研究区钼矿床的成岩成矿主要发生在200～165Ma之间；其中，斑岩型矿床成矿作用发生在186～167Ma，与成矿密切相关的花岗岩为花岗闪长（斑）岩和二长花岗（斑）岩，成矿发生在岩浆演化期后（189～167Ma）；中温热液石英脉型矿床成矿作用发生在176.4Ma，成矿与中侏罗世二长花岗岩岩浆活动关系密切；接触交代热液型矿床形成于196.6Ma，成矿与早侏罗世岩浆活动、庙岭组碳酸盐类岩石及碎屑岩关系密切。
5．上述与成矿密切的花岗杂岩的元素地球化学特征揭示，与斑岩型钼床有关的花岗闪长（斑）岩-二长花岗（斑）岩为高硅、高铝、富碱、准铝质/弱过铝质的高钾钙碱性系列（SiO_2=62.59～73.5%，Na_2O=2.61～5.38%，K_2O=3.03～5.74%，K_2O/Na_2O=0.81～2.17，A/CNK=0.92～1.22，A/NK=1.14～1.64），富集Rb、Ba、Th、K等大离子亲石元素，亏损Nb、Ta、P等高场强元素，具有弱的负Eu异常、强烈稀土分馏为特征（其∑REE=100.42～154.27ppm，LREE/HREE=10.91～16.52，（La/Yb）N=1.49～14.56，δEu=0.85～1.08）；与中温热液石英脉型钼矿床成矿相关的二长花岗岩为高硅、高铝、富碱、弱过铝质的高钾钙碱性系列（SiO_2=76.47～76.6%，均值为76.54%，Na_2O=3.15～3.17%，K_2O=5.35～5.42%，K_2O/Na_2O=1.68～1.72，A/CNK=1.01～1.02，A/NK=1.12～1.13），富集大离子亲石元素，亏损高场强元素，具有明显的负Eu异常、强烈稀土分馏为特征（其∑REE=91.43～99.22ppm，LREE/HREE=14.9～15.32，（La/Yb）N=4.68～7.94，δEu=0.5）；与接触交代热液型钼矿床成矿相关的花岗闪长岩为高硅、高铝、富碱的准铝质/弱过铝质的钙碱性系列（SiO_2=63.98～71.14%，Na_2O=4.02～4.76%，K_2O=2.11～4.29%，K_2O/Na_2O=0.52～0.95，均值为0.71，A/CNK=0.99～1，A/NK=1.21～1.81）；富集Rb、Ba、Th、K等大离子亲石元素，亏损Nb、Ta、P等高场强元素，具有弱的负Eu异常、强烈稀土分馏为特征（其∑REE=128.24～159.48ppm，LREE/HREE=12.8～15.41，（La/Yb）N=17.26～24.01，δEu=0.99～1.04）。
6．与成矿密切的花岗杂岩的Sr-Nd-Pb同位素地球化学特征显示，与斑岩型钼床成矿密切的花岗闪长（斑）岩-二长花岗（斑）岩的(~(87)Sr/~(86))i、εNd(t)值分别为0.70404～0.70554、-0.9～2.4，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(2040Pb分别为18.4576～19.2028，15.5623～15.6144，38.2591～38.8874；与接触交代热液型钼矿床成矿相关的花岗岩闪长岩的(87Sr/86)i、εNd(t)值分别为0.70413～0.70474、3.3～3.6，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(2040Pb分别为18.5199～18.6146，15.5698～15.5805，38.3686～38.4782；与中温热液石英脉型钼矿床成矿相关的二长花岗岩的(~(87)Sr/~(86))i、εNd(t)值分别为0.70656～0.70721、1.6～1.8，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(204)Pb分别为18.6488～18.6631，15.5884～15.5922，38.6708～38.6762。三类矿床均具有较低的初始锶和高初始钕的特征，表明与成矿有关的花岗岩经历了壳幔混合作用。
7．将成岩成矿年代、Sr-Nd同位素、含矿流体、物源区属性相结合，进一步厘定斑岩型、接触交代热液型、中温热液石英脉型钼矿床的成矿热动源为古太平洋板块俯冲过程中流体交代元古代次生岩石圈地幔发生部分熔融形成的玄武质岩浆。其中，斑岩型矿床成矿过程至少有2种：第一种为早侏罗世玄武质岩浆以底侵作用诱发下地壳熔融形成岩浆房，继而岩浆发生分异结晶作用，形成含矿流体，上升过程中伴随着温压降低，发生沸腾，导致金属元素大量卸载，形成角砾状、细脉浸染状矿体等。另一种是中侏罗世玄武质岩浆底侵引发下地壳熔融形成岩浆房，少部分玄武质岩浆内侵与下地壳熔融岩浆混合，导致含矿流体形成，流体上升过程中发生沸腾，形成角砾状、细脉浸染状矿体等；接触交代热液型钼矿床成矿过程为早侏罗世玄武质岩浆底侵诱发下地壳熔融形成岩浆房，岩浆房发生分异结晶作用，形成含矿流体，在上升过程中与大气降水混合，并与上部古生代含钼的碳酸盐岩地层交代，形成接触交代热液钼矿床；中温热液石英脉型钼矿床成矿过程为中侏罗世玄武质岩浆底侵引发下地壳熔融形成岩浆房，少量玄武质岩浆内侵与下地壳熔融岩浆混合，导致含矿流体形成，含矿流体沿着断裂上升并与大气降水发生混合后，引起流体温度、压力等物理化学条件改变，从而造成辉钼矿大量沉淀，形成中温热液石英脉型钼矿床。
The Mid-East area of Jilin province is an important polymetallic metallogenic district since theDaheishan Mo deposit was discovered, a number of deposits have been discovered in the region, includingthe Jidetun, Dashihe, Fuanpu, Yixintun, Liushengdian, Dongfeng medium scale Mo deposits, as well as sixsmall sized Mo deposits and more than30occurrences in recent ten years. More than200million tons ofproven reserve had been confirmed until2008, it makes the study area to be the second-richestconcentration of Mo resource in China, a fact that attracted a large amount of interest to research in themineralization of this area. In order to further reveal the Mo mineralization regularity and resourcepotential, this study focuses on the geological characteristics, fluid property, geochemistry andgeochronology to deeply reveal that diagenesis and mineralization age, metallogenetic specialization,tectonic settings, petrogenetic-metallogenic mechanism, and then establish metallogenic model anddynamical model. The main advance achievements from this study are as followings.
According to geological features of endogenic Mo deposits in the region are mainly divided intoporphyry type, contact-metasomatic hydrothermal type and medium temperature hydrothermal quartz veintype. The orebodies for porphyry Mo deposits are hosted by monzonitic granite (porphyry) or granodiorite(porphyry), which are lenticular and irregular forms in shape. Wall-rock alteration includesK-feldspathization, silicification, sericitization, epidotization and carbonation. The mineralization can bedivided into a quartz–pyrite stage (I), a quartz–pyrrhotite-pyrite stage (II), a quartz–molybdenite stage (III),a quartz–polymetallic sulphides stage (IV), and a quartz–carbonate phase (V). The medium temperaturehydrothermal quartz vein type deposits are distributed in granite fracture, and the orebodies are vein formin shape. Wall-rock alteration includes silicification, sericitization, K-feldspathization. The mineralizationcan be divided into a quartz stage (I), a quartz–molybdenite-pyrite stage (II), and a quartz–carbonate phase(III). The contact-metasomatic hydrothermal type deposits are hosted by contact zone between granites andthe Paleozoic stratum, and the orebodies are vein and lenticular forms in shape. Wall-rock alterationincludes chloritization, epidotization, sericitization, carbonation and silicification. The mineralization can be divided into a dry skarn stage (I), a wet skarn stage (II), a quartz–molybdenite stage (III), aquartz–polymetallic sulphides stage (IV), and a quartz–carbonate phase (V). Three types of deposits haveobvious relativity in space-time, and often constitute porphyry or medium temperature hydrothermal quartzvein type-contact-metasomatic hydrothermal type mineralization system.
The mineral fluid inclusions reveal that fluid inclusions from porphyry deposits mainly are aqueoustwo-phase inclusions and minor daughter minerals bearing polyphase inclusions. The homogenizationtemperatures are＞420～400℃,360～350℃,340～230℃,220～210℃and180～160℃, respectively.Salinity are＞41.05%～9.8%NaCleq,38.16%～4.48%NaCleq,35.78%～4.49%NaCleq,7.43%NaCleqand7.8%～9.5%NaCleq, respectively. The mineral fluid inclusions from contact-metasomatichydrothermal deposit mainly are aqueous two-phase inclusions and minor CO_2bearing three-phaseinclusions. The homogenization temperatures are＞337～280℃,260～200℃and190～101℃,respectively. Salinity are＞18.5%～9.3%NaCleq,20.5%～9.98%NaCleq and22.9%～7.33%NaCleq,respectively. The mineral fluid inclusions from medium temperature hydrothermal quartz vein deposit areaqueous two-phase inclusions. The homogenization temperatures are＞330～300℃,280～170℃and160～120℃, respectively. Salinity are＞12.07%～8.81%NaCleq,9.86%～3.37%NaCleq and9.21%～4.63%NaCleq, respectively.
Combining with temperature measurement, gas phase composition for fluid inclusions and hydrogenand oxygen isotope characteristics for group inclusions indicate that the initial ore-forming fluid for theporphyry Mo deposits is CO_2-H2O-NaCl magmatic fluid of CO_2-bearing with minor CH_4, N_2and H_2S, andparticipation of meteoric waters in the late ore-forming stage. The medium temperature hydrothermalquartz vein Mo deposit is H2O-CO_2-NaCl multiphase fluid, and participation of meteoric waters in the lateore-forming stage. The initial ore-forming fluid for the contact-metasomatic hydrothermal Mo deposit ischaracterized by medium to high temperature, medium to high salinity H2O-CO_2-NaCl fluid ofCO_2-bearing with minor CH_4and N_2, and influxing of meteoric waters in the ore-forming stage. We candraw a conclusion that the porphyry Mo deposits undergo strongly fluid immiscibility in the mineralizationprocess, while mixing of fluid happened in the evolution of fluid in the contact-metasomatic hydrothermaland medium temperature hydrothermal quartz vein Mo deposits.
Studies on diagenetic and metallogenetic epoch show that Mo mineralization in the study area mainlyoccurred in200～165Ma. Porphyry Mo deposits mineralization occurred in186～167Ma, and the relatedmagmato-thermal event for the Porphyry Mo deposits are closely related to the magmatic evolution of themonzonitic granite (porphyry) and granodiorite (porphyry). The metallogenesis occurred in the late stageof magmatic evolution (189~167Ma). The medium temperature hydrothermal quartz vein Mo depositoccurred in176.4Ma, and the mineralization is associated with the Middle Jurassic monzonitic granite.The contact-metasomatic hydrothermal Mo deposit occurred in196.6Ma, and the mineralization is associated with the Early Jurassic magmation, carbonate rocks and clastic rocks.
Element geochemical characteristics for granite complex associated with mineralization shows thatmonzonitic granite (porphyry) and granodiorite (porphyry) associated with mineralization of porphyrydeposits have high-Si, K, Al and alkali-rich, and belong to quasi-aluminous/weakly peraluminous high-Kcalc-alkaline series（SiO_2=62.59～73.5%, Na_2O=2.61～5.38%, K_2O=3.03～5.74%, K_2O/Na_2O=0.81～2.17, A/CNK=0.92～1.22, A/NK=1.14～1.64）, enrichment of LREE（∑REE=100.42～154.27ppm，LREE/HREE=10.91～16.52，（La/Yb）N=1.49～14.56）, weak or negligible Eu anomalies (Eu=0.85～1.08),enrichment of the large ion lithophile element (LILE) and depletion of the high field-strength element(HFSE). Monzonitic granite associated with mineralization for medium temperature hydrothermal quartzvein Mo deposits have high-Si, K, Al and alkali-rich, as well as weakly peraluminous high-K calc-alkalineseries （SiO_2=76.47～76.6%, Na_2O=3.15～3.17%, K_2O=5.35～5.42%, K_2O/Na_2O=1.68～1.72,A/CNK=1.01～1.02, A/NK=1.12～1.13）, obvious LREE enrichment, negative Eu anomalies（∑REE=91.43～99.22ppm, LREE/HREE=14.9～15.32,（La/Yb）N=4.68～7.94, δEu=0.5）, enrichmentof LILE and depletion of the HFSE. Granodiorite associated with mineralization for contact-metasomatichydrothermal Mo deposits have high-Si, K, Al and alkali-rich, as well as quasi-aluminous/weaklyperaluminous calc-alkaline series (SiO_2=63.98～71.14%, Na_2O=4.02～4.76%, K_2O=2.11～4.29%,K_2O/Na_2O=0.52～0.95, A/CNK=0.99～1, A/NK=1.21～1.81), LREE enrichment(∑REE=128.24～159.48ppm, LREE/HREE=12.8～15.41,（La/Yb）N=17.26～24.01), weak or negligible Eu anomalies(δEu=0.99～1.04), enrichment of the LILE and depletion of the HFSE.
Sr-Nd-Pb isotopic geochemistry compositions for granite complex associated with mineralizationindicate that monzonitic granite (porphyry) and granodiorite (porphyry) associated with mineralization forthe porphyry Mo deposits have (~(87)Sr/~(86)Sr)iratios range from0.70404to0.70554, εNd(t) values range from-0.9to2.4.~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.4576～19.2028,15.5623～15.6144,38.2591～38.8874, respectively. Granodiorite associated with mineralization for the contact-metasomatichydrothermal Mo deposits have (~(87)Sr/~(86)Sr)iratios range from0.70413to0.70474, εNd(t) values range from3.3to3.6.~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.5199～18.6146,15.5698～15.5805,38.3686～38.4782, respectively. Monzonitic granite associated with mineralization for the mediumtemperature hydrothermal quartz vein Mo deposits have (87Sr/86Sr)iratios range from0.70656to0.70721,εNd(t) values range from1.6to1.8.206Pb/204Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.6488～18.6631,15.5884～15.5922,38.6708～38.6762, respectively. The three types of granites have low value of initialSr and high value of initial εNd(t), which indicate that the granite is the product of crust-mantle mixing.
Combing with diagenetic and metallogenic epoch, Sr-Nd isotope, ore-bearing fluid and provenanceproperty, we further confirm that metallogenic thermal source for porphyry type, contact-metasomatichydrothermal type and medium temperature hydrothermal quartz vein type Mo deposit is derived from basaltic magma derived from partial melting of secondary lithospheric mantle, and incentive is subductionof the Pacific Palte. There are two kinds of mineralization process for porphyry Mo deposits. The first isthat the magma formed by melt of the lower curst, which induced by underplating of the Early Jurassicbasaltic magma, and then the lower crust melt and form magma chamber through underplating, and thenformed ore-forming fluid by magmatic fractional crystallization. The ore-forming fluid rises with reducingof temperature and pressure, and boiling, which lead to unload ore-forming elements and formedbrecciated and veinlet disseminated orebodies.
The other is that magma chamber formed by underplating of the Middle Jurassic basaltic magma, anda few basaltic magma mixing with the lower curst formed ore-forming fluid. The ore-forming fluid riseswith boiling and formed brecciated and veinlet disseminated orebodies. The magma related to thecontact-metasomatic hydrothermal Mo deposit is derived from basaltic magma underpalting the lowermafic crust in the Early Jurassic, and ore-forming fluid formed by crystal fractionation of magma chamber.The ore-forming fluid mixed with meteoritic water, and metasomatism carbonate rocks during rising, andthen formed the hydrothermal contact metasomatic Mo deposit. The mineralization process of the mediumtemperature hydrothermal quartz vein Mo deposit is that magma chamber formed by underplating of theMiddle Jurassic basaltic magma, and a few basaltic magma mixing with the lower curst formedore-forming fluid. The ore-forming fluid rising along fracture and mixing with meteoritic water, which leadtransform of physical and chemical conditions. Thus molybdenum precipitated and formed the mediumtemperature hydrothermal quartz vein Mo deposit.
1．通过对研究区各类内生钼矿床的矿床地质特征研究，将该区内生钼矿床划分为斑岩型、接触交代热液型和中温热液石英脉型三种成因类型。斑岩型钼矿床矿体主要呈不规则状、透镜状，产于二长花岗（斑）岩或花岗闪长（斑）岩的岩体内，围岩蚀变主要有钾化、硅化、绢云母化、绿泥石化及碳酸盐化等，矿化经历了石英-黄铁矿阶段（Ⅰ）、石英-磁黄铁矿-黄铁矿阶段（Ⅱ）、石英-辉钼矿阶段（Ⅲ）、石英-多金属硫化物阶段（Ⅳ）和石英-碳酸盐阶段（Ⅴ）五个阶段。中温热液石英脉型钼矿床矿体以脉状为主，产在花岗岩的断裂体系中，围岩蚀变主要有硅化、绢云母化和钾化等，矿化基本经历了无矿石英脉阶段（Ⅰ）、石英-辉钼矿-黄铁矿阶段（Ⅱ）和石英-碳酸盐阶段（Ⅲ）三个阶段；接触交代热液型钼矿床矿体以脉状、扁豆状和透镜状为主，产于花岗岩岩体与古生代地层接触带上，围岩蚀变主要为绿泥石化、绿帘石化、矽卡岩化、绢云母化、碳酸盐化、硅化等，矿化基本经历了干矽卡岩阶段（Ⅰ）、湿矽卡岩阶段（Ⅱ）、石英-辉钼矿阶段（Ⅲ）、石英-多金属硫化物阶段（Ⅳ）和石英-碳酸盐阶段（Ⅴ），即：两期五个阶段。三类矿床之间具有明显的时空性，常构成斑岩或中温热液石英脉-接触交代成矿系统。
2．矿床的矿物流体包裹体研究揭示，斑岩型钼矿床以气液两相和含子矿物三相包裹体为特征，各矿化阶段的均一温度分别为＞420～400℃、360～350℃、340～230℃、220～210℃、180～160℃，盐度依次为＞41.05%～9.8%NaCleq、38.16%～4.48%NaCleq、35.78%～4.49%NaCleq、7.43%NaCleq、7.8%～9.5%NaCleq；接触交代热液型钼矿床主要发育气液两相包裹体、少量含CO_2三相包裹体，各矿化阶段均一温度分别为＞337～280℃、260～200℃、190～101℃，盐度分别为＞18.5%～9.3%NaCleq、20.5%～9.98%NaCleq、22.9%～7.33%NaCleq；中温热液石英脉型钼矿床主要发育气液两相包裹体，各矿化均一温度分别为＞330～300℃、280～170℃、160～120℃，盐度分别为＞12.07%～8.81%NaCleq、9.86%～3.37%NaCleq、9.21%～4.63%NaCleq。
3．将流体测温与流体包裹体气相成分分析和氢-氧同位素地球化学特征相结合，进一步揭示斑岩型钼矿床的初始流体为富CO_2和少量CH_4、N_2、H_2S的CO_2-H2O-NaCl多相岩浆流体体系，成矿晚期有大气降水混入；中温热液石英脉型钼矿床成矿初始流体为H2O-CO_2-NaCl多相岩浆流体，成矿阶段亦有大气降水加入；接触交代热液型钼矿床初始流体为中高温、中高盐度含CO_2、少量CH_4、N_2的H2O-CO_2-NaCl岩浆流体，主成矿阶段有大气降水混合。初步得出斑岩型钼矿床含矿流体成矿过程发生了强烈的流体不混溶作用；而中温热液石英脉型和接触交代热液型钼矿床流体演化过程中发生了混合作用。
4．成岩成矿年代学研究表明，研究区钼矿床的成岩成矿主要发生在200～165Ma之间；其中，斑岩型矿床成矿作用发生在186～167Ma，与成矿密切相关的花岗岩为花岗闪长（斑）岩和二长花岗（斑）岩，成矿发生在岩浆演化期后（189～167Ma）；中温热液石英脉型矿床成矿作用发生在176.4Ma，成矿与中侏罗世二长花岗岩岩浆活动关系密切；接触交代热液型矿床形成于196.6Ma，成矿与早侏罗世岩浆活动、庙岭组碳酸盐类岩石及碎屑岩关系密切。
5．上述与成矿密切的花岗杂岩的元素地球化学特征揭示，与斑岩型钼床有关的花岗闪长（斑）岩-二长花岗（斑）岩为高硅、高铝、富碱、准铝质/弱过铝质的高钾钙碱性系列（SiO_2=62.59～73.5%，Na_2O=2.61～5.38%，K_2O=3.03～5.74%，K_2O/Na_2O=0.81～2.17，A/CNK=0.92～1.22，A/NK=1.14～1.64），富集Rb、Ba、Th、K等大离子亲石元素，亏损Nb、Ta、P等高场强元素，具有弱的负Eu异常、强烈稀土分馏为特征（其∑REE=100.42～154.27ppm，LREE/HREE=10.91～16.52，（La/Yb）N=1.49～14.56，δEu=0.85～1.08）；与中温热液石英脉型钼矿床成矿相关的二长花岗岩为高硅、高铝、富碱、弱过铝质的高钾钙碱性系列（SiO_2=76.47～76.6%，均值为76.54%，Na_2O=3.15～3.17%，K_2O=5.35～5.42%，K_2O/Na_2O=1.68～1.72，A/CNK=1.01～1.02，A/NK=1.12～1.13），富集大离子亲石元素，亏损高场强元素，具有明显的负Eu异常、强烈稀土分馏为特征（其∑REE=91.43～99.22ppm，LREE/HREE=14.9～15.32，（La/Yb）N=4.68～7.94，δEu=0.5）；与接触交代热液型钼矿床成矿相关的花岗闪长岩为高硅、高铝、富碱的准铝质/弱过铝质的钙碱性系列（SiO_2=63.98～71.14%，Na_2O=4.02～4.76%，K_2O=2.11～4.29%，K_2O/Na_2O=0.52～0.95，均值为0.71，A/CNK=0.99～1，A/NK=1.21～1.81）；富集Rb、Ba、Th、K等大离子亲石元素，亏损Nb、Ta、P等高场强元素，具有弱的负Eu异常、强烈稀土分馏为特征（其∑REE=128.24～159.48ppm，LREE/HREE=12.8～15.41，（La/Yb）N=17.26～24.01，δEu=0.99～1.04）。
6．与成矿密切的花岗杂岩的Sr-Nd-Pb同位素地球化学特征显示，与斑岩型钼床成矿密切的花岗闪长（斑）岩-二长花岗（斑）岩的(~(87)Sr/~(86))i、εNd(t)值分别为0.70404～0.70554、-0.9～2.4，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(2040Pb分别为18.4576～19.2028，15.5623～15.6144，38.2591～38.8874；与接触交代热液型钼矿床成矿相关的花岗岩闪长岩的(87Sr/86)i、εNd(t)值分别为0.70413～0.70474、3.3～3.6，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(2040Pb分别为18.5199～18.6146，15.5698～15.5805，38.3686～38.4782；与中温热液石英脉型钼矿床成矿相关的二长花岗岩的(~(87)Sr/~(86))i、εNd(t)值分别为0.70656～0.70721、1.6～1.8，~(206)Pb/~(204)Pb、~(207)Pb/~(204)Pb和~(208)Pb/~(204)Pb分别为18.6488～18.6631，15.5884～15.5922，38.6708～38.6762。三类矿床均具有较低的初始锶和高初始钕的特征，表明与成矿有关的花岗岩经历了壳幔混合作用。
7．将成岩成矿年代、Sr-Nd同位素、含矿流体、物源区属性相结合，进一步厘定斑岩型、接触交代热液型、中温热液石英脉型钼矿床的成矿热动源为古太平洋板块俯冲过程中流体交代元古代次生岩石圈地幔发生部分熔融形成的玄武质岩浆。其中，斑岩型矿床成矿过程至少有2种：第一种为早侏罗世玄武质岩浆以底侵作用诱发下地壳熔融形成岩浆房，继而岩浆发生分异结晶作用，形成含矿流体，上升过程中伴随着温压降低，发生沸腾，导致金属元素大量卸载，形成角砾状、细脉浸染状矿体等。另一种是中侏罗世玄武质岩浆底侵引发下地壳熔融形成岩浆房，少部分玄武质岩浆内侵与下地壳熔融岩浆混合，导致含矿流体形成，流体上升过程中发生沸腾，形成角砾状、细脉浸染状矿体等；接触交代热液型钼矿床成矿过程为早侏罗世玄武质岩浆底侵诱发下地壳熔融形成岩浆房，岩浆房发生分异结晶作用，形成含矿流体，在上升过程中与大气降水混合，并与上部古生代含钼的碳酸盐岩地层交代，形成接触交代热液钼矿床；中温热液石英脉型钼矿床成矿过程为中侏罗世玄武质岩浆底侵引发下地壳熔融形成岩浆房，少量玄武质岩浆内侵与下地壳熔融岩浆混合，导致含矿流体形成，含矿流体沿着断裂上升并与大气降水发生混合后，引起流体温度、压力等物理化学条件改变，从而造成辉钼矿大量沉淀，形成中温热液石英脉型钼矿床。
The Mid-East area of Jilin province is an important polymetallic metallogenic district since theDaheishan Mo deposit was discovered, a number of deposits have been discovered in the region, includingthe Jidetun, Dashihe, Fuanpu, Yixintun, Liushengdian, Dongfeng medium scale Mo deposits, as well as sixsmall sized Mo deposits and more than30occurrences in recent ten years. More than200million tons ofproven reserve had been confirmed until2008, it makes the study area to be the second-richestconcentration of Mo resource in China, a fact that attracted a large amount of interest to research in themineralization of this area. In order to further reveal the Mo mineralization regularity and resourcepotential, this study focuses on the geological characteristics, fluid property, geochemistry andgeochronology to deeply reveal that diagenesis and mineralization age, metallogenetic specialization,tectonic settings, petrogenetic-metallogenic mechanism, and then establish metallogenic model anddynamical model. The main advance achievements from this study are as followings.
According to geological features of endogenic Mo deposits in the region are mainly divided intoporphyry type, contact-metasomatic hydrothermal type and medium temperature hydrothermal quartz veintype. The orebodies for porphyry Mo deposits are hosted by monzonitic granite (porphyry) or granodiorite(porphyry), which are lenticular and irregular forms in shape. Wall-rock alteration includesK-feldspathization, silicification, sericitization, epidotization and carbonation. The mineralization can bedivided into a quartz–pyrite stage (I), a quartz–pyrrhotite-pyrite stage (II), a quartz–molybdenite stage (III),a quartz–polymetallic sulphides stage (IV), and a quartz–carbonate phase (V). The medium temperaturehydrothermal quartz vein type deposits are distributed in granite fracture, and the orebodies are vein formin shape. Wall-rock alteration includes silicification, sericitization, K-feldspathization. The mineralizationcan be divided into a quartz stage (I), a quartz–molybdenite-pyrite stage (II), and a quartz–carbonate phase(III). The contact-metasomatic hydrothermal type deposits are hosted by contact zone between granites andthe Paleozoic stratum, and the orebodies are vein and lenticular forms in shape. Wall-rock alterationincludes chloritization, epidotization, sericitization, carbonation and silicification. The mineralization can be divided into a dry skarn stage (I), a wet skarn stage (II), a quartz–molybdenite stage (III), aquartz–polymetallic sulphides stage (IV), and a quartz–carbonate phase (V). Three types of deposits haveobvious relativity in space-time, and often constitute porphyry or medium temperature hydrothermal quartzvein type-contact-metasomatic hydrothermal type mineralization system.
The mineral fluid inclusions reveal that fluid inclusions from porphyry deposits mainly are aqueoustwo-phase inclusions and minor daughter minerals bearing polyphase inclusions. The homogenizationtemperatures are＞420～400℃,360～350℃,340～230℃,220～210℃and180～160℃, respectively.Salinity are＞41.05%～9.8%NaCleq,38.16%～4.48%NaCleq,35.78%～4.49%NaCleq,7.43%NaCleqand7.8%～9.5%NaCleq, respectively. The mineral fluid inclusions from contact-metasomatichydrothermal deposit mainly are aqueous two-phase inclusions and minor CO_2bearing three-phaseinclusions. The homogenization temperatures are＞337～280℃,260～200℃and190～101℃,respectively. Salinity are＞18.5%～9.3%NaCleq,20.5%～9.98%NaCleq and22.9%～7.33%NaCleq,respectively. The mineral fluid inclusions from medium temperature hydrothermal quartz vein deposit areaqueous two-phase inclusions. The homogenization temperatures are＞330～300℃,280～170℃and160～120℃, respectively. Salinity are＞12.07%～8.81%NaCleq,9.86%～3.37%NaCleq and9.21%～4.63%NaCleq, respectively.
Combining with temperature measurement, gas phase composition for fluid inclusions and hydrogenand oxygen isotope characteristics for group inclusions indicate that the initial ore-forming fluid for theporphyry Mo deposits is CO_2-H2O-NaCl magmatic fluid of CO_2-bearing with minor CH_4, N_2and H_2S, andparticipation of meteoric waters in the late ore-forming stage. The medium temperature hydrothermalquartz vein Mo deposit is H2O-CO_2-NaCl multiphase fluid, and participation of meteoric waters in the lateore-forming stage. The initial ore-forming fluid for the contact-metasomatic hydrothermal Mo deposit ischaracterized by medium to high temperature, medium to high salinity H2O-CO_2-NaCl fluid ofCO_2-bearing with minor CH_4and N_2, and influxing of meteoric waters in the ore-forming stage. We candraw a conclusion that the porphyry Mo deposits undergo strongly fluid immiscibility in the mineralizationprocess, while mixing of fluid happened in the evolution of fluid in the contact-metasomatic hydrothermaland medium temperature hydrothermal quartz vein Mo deposits.
Studies on diagenetic and metallogenetic epoch show that Mo mineralization in the study area mainlyoccurred in200～165Ma. Porphyry Mo deposits mineralization occurred in186～167Ma, and the relatedmagmato-thermal event for the Porphyry Mo deposits are closely related to the magmatic evolution of themonzonitic granite (porphyry) and granodiorite (porphyry). The metallogenesis occurred in the late stageof magmatic evolution (189~167Ma). The medium temperature hydrothermal quartz vein Mo depositoccurred in176.4Ma, and the mineralization is associated with the Middle Jurassic monzonitic granite.The contact-metasomatic hydrothermal Mo deposit occurred in196.6Ma, and the mineralization is associated with the Early Jurassic magmation, carbonate rocks and clastic rocks.
Element geochemical characteristics for granite complex associated with mineralization shows thatmonzonitic granite (porphyry) and granodiorite (porphyry) associated with mineralization of porphyrydeposits have high-Si, K, Al and alkali-rich, and belong to quasi-aluminous/weakly peraluminous high-Kcalc-alkaline series（SiO_2=62.59～73.5%, Na_2O=2.61～5.38%, K_2O=3.03～5.74%, K_2O/Na_2O=0.81～2.17, A/CNK=0.92～1.22, A/NK=1.14～1.64）, enrichment of LREE（∑REE=100.42～154.27ppm，LREE/HREE=10.91～16.52，（La/Yb）N=1.49～14.56）, weak or negligible Eu anomalies (Eu=0.85～1.08),enrichment of the large ion lithophile element (LILE) and depletion of the high field-strength element(HFSE). Monzonitic granite associated with mineralization for medium temperature hydrothermal quartzvein Mo deposits have high-Si, K, Al and alkali-rich, as well as weakly peraluminous high-K calc-alkalineseries （SiO_2=76.47～76.6%, Na_2O=3.15～3.17%, K_2O=5.35～5.42%, K_2O/Na_2O=1.68～1.72,A/CNK=1.01～1.02, A/NK=1.12～1.13）, obvious LREE enrichment, negative Eu anomalies（∑REE=91.43～99.22ppm, LREE/HREE=14.9～15.32,（La/Yb）N=4.68～7.94, δEu=0.5）, enrichmentof LILE and depletion of the HFSE. Granodiorite associated with mineralization for contact-metasomatichydrothermal Mo deposits have high-Si, K, Al and alkali-rich, as well as quasi-aluminous/weaklyperaluminous calc-alkaline series (SiO_2=63.98～71.14%, Na_2O=4.02～4.76%, K_2O=2.11～4.29%,K_2O/Na_2O=0.52～0.95, A/CNK=0.99～1, A/NK=1.21～1.81), LREE enrichment(∑REE=128.24～159.48ppm, LREE/HREE=12.8～15.41,（La/Yb）N=17.26～24.01), weak or negligible Eu anomalies(δEu=0.99～1.04), enrichment of the LILE and depletion of the HFSE.
Sr-Nd-Pb isotopic geochemistry compositions for granite complex associated with mineralizationindicate that monzonitic granite (porphyry) and granodiorite (porphyry) associated with mineralization forthe porphyry Mo deposits have (~(87)Sr/~(86)Sr)iratios range from0.70404to0.70554, εNd(t) values range from-0.9to2.4.~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.4576～19.2028,15.5623～15.6144,38.2591～38.8874, respectively. Granodiorite associated with mineralization for the contact-metasomatichydrothermal Mo deposits have (~(87)Sr/~(86)Sr)iratios range from0.70413to0.70474, εNd(t) values range from3.3to3.6.~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.5199～18.6146,15.5698～15.5805,38.3686～38.4782, respectively. Monzonitic granite associated with mineralization for the mediumtemperature hydrothermal quartz vein Mo deposits have (87Sr/86Sr)iratios range from0.70656to0.70721,εNd(t) values range from1.6to1.8.206Pb/204Pb,~(207)Pb/~(204)Pb and~(208)Pb/~(204)Pb ratios are18.6488～18.6631,15.5884～15.5922,38.6708～38.6762, respectively. The three types of granites have low value of initialSr and high value of initial εNd(t), which indicate that the granite is the product of crust-mantle mixing.
Combing with diagenetic and metallogenic epoch, Sr-Nd isotope, ore-bearing fluid and provenanceproperty, we further confirm that metallogenic thermal source for porphyry type, contact-metasomatichydrothermal type and medium temperature hydrothermal quartz vein type Mo deposit is derived from basaltic magma derived from partial melting of secondary lithospheric mantle, and incentive is subductionof the Pacific Palte. There are two kinds of mineralization process for porphyry Mo deposits. The first isthat the magma formed by melt of the lower curst, which induced by underplating of the Early Jurassicbasaltic magma, and then the lower crust melt and form magma chamber through underplating, and thenformed ore-forming fluid by magmatic fractional crystallization. The ore-forming fluid rises with reducingof temperature and pressure, and boiling, which lead to unload ore-forming elements and formedbrecciated and veinlet disseminated orebodies.
The other is that magma chamber formed by underplating of the Middle Jurassic basaltic magma, anda few basaltic magma mixing with the lower curst formed ore-forming fluid. The ore-forming fluid riseswith boiling and formed brecciated and veinlet disseminated orebodies. The magma related to thecontact-metasomatic hydrothermal Mo deposit is derived from basaltic magma underpalting the lowermafic crust in the Early Jurassic, and ore-forming fluid formed by crystal fractionation of magma chamber.The ore-forming fluid mixed with meteoritic water, and metasomatism carbonate rocks during rising, andthen formed the hydrothermal contact metasomatic Mo deposit. The mineralization process of the mediumtemperature hydrothermal quartz vein Mo deposit is that magma chamber formed by underplating of theMiddle Jurassic basaltic magma, and a few basaltic magma mixing with the lower curst formedore-forming fluid. The ore-forming fluid rising along fracture and mixing with meteoritic water, which leadtransform of physical and chemical conditions. Thus molybdenum precipitated and formed the mediumtemperature hydrothermal quartz vein Mo deposit.
引文
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