A Special Orogenic-type Rare Earth Element Deposit in Maoniuping, Sichuan, China: Geology and Geochemistry

Abstract: The Maoniuping REE deposit is the second largest light rare earth elements deposit in China, explored recently in the northern Jinpingshan Mountains, a Cenozoic intracontinental orogenic belt in southwestern China. It is a vein-type deposit hosted within, and genetically related to, carbonatite-alkalic complex. Field investigation and new geochemical data of the carbonatites from the carbonatite-alkalic complex support an igneous origin for the Maoniuping carbonatites and related REE mineralization. Carbonatite itself carries rare earth elements which were enriched by hydrothermal solution.
It is known that most of the REE deposits related to carbonatite-alkalic complexes were formed in relatively stable tectonic setting such as cratonic or rifting environment. The Maoniuping deposit, however, was formed during the processes of Cenozoic orogeny. Although the Maoniuping deposit is located in the north sector of the Panxi paleo-rift zone, the rift had been closed before early Cenozoic and evolved into an intracontinental orogenic belt, i.e., the Jinpingshan Orogen, which was formed since later Mesozoic to early Cenozoic. Geochronological and geochemical data also prove that the Maoniuping REE deposit was formed in an intracontinental orogenic belt instead of rift system or stationary block.
The Maoniuping REE deposit is similar to the Mountain Pass REE deposit in many respects such as the high contents of bastnaesite and barite, the low content of niobium, and the common occurrence of sulfides. The discovery of the Maoniuping deposit and other REE deposits during the past two decades suggest a good potential for prospecting REE deposits along the alkalic complex belt located on the eastern side of the Qinghai–Xizang–West Sichuan Plateau.     

应用电感耦合等离子体质谱技术研究牦牛坪矿床霓长岩化蚀变矿物微量元素特征

近年来全岩电感耦合等离子体质谱（ICP-MS）和原位激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）微量元素地球化学测试在地球科学领域的应用越来越广泛。霓长岩化是碳酸岩型稀土矿常见的蚀变类型,但其中的蚀变矿物微量元素特征与稀土矿化关系并不清楚。本文对川西牦牛坪矿床两期霓长岩化脉（无矿脉和含矿脉）中的霓辉石、钠铁闪石同时开展ICP-MS和LA-ICP-MS微量元素测试。结果表明：同期次的霓长岩化脉中,霓辉石、钠铁闪石全岩ΣREE含量远高于单矿物原位ΣREE含量,背散射图像显示霓辉石、钠铁闪石矿物中叠加了一些氟碳铈矿、重晶石微矿物。不同期次霓长岩化脉中霓辉石原位微量对比,含矿脉中的霓辉石具有更高的La/Nd值（0.19~0.23）、LREE/HREE值（6.58~7.79）、Ce/Nd值（0.95~1.11）、La_N/Yb_N值（2.07~2.33）。对比全岩微量组成,含矿脉中高含量的La、Ce、LREE、ΣREE,强烈的轻重稀土分异,可能代表了高稀土通量的霓长岩化流体。霓长岩化脉的出现以及脉体中霓辉石、钠铁闪石这些全岩微量、原位微量地球化学指标,可为碳酸岩型稀土矿床找矿勘查提供参考。     

碳酸岩岩浆演化过程中REE富集与分异的研究进展及碳酸岩中的矿物学分带

稀土元素(REE)作为"三稀资源"之一,是中国重要的战略性矿产资源,碳酸岩型稀土矿床是世界稀土的主要来源.成矿碳酸岩的岩浆演化以及稀土元素的富集和分异机理一直是碳酸岩型稀土矿床研究的热点和难点,国内外学者对碳酸岩的岩浆起源、岩浆演化过程中稀土元素富集与分异的机理进行了大量的研究与探讨,但仍存在较多的争议,限制了碳酸岩型稀土元素成矿理论的发展及国内外碳酸岩型稀土矿床的找矿勘查工作.文章重点对稀土成矿碳酸岩的起源、岩浆演化过程及在此过程中REE的富集与分异行为进行了详细的文献调研和评述,同时,基于笔者在冕宁牦牛坪稀土矿床前期的研究工作和最新发现,认为碳酸岩中普遍存在矿物学分带,它是岩浆演化过程的最佳记录,是不同成分矿物结晶分异作用的体现.对牦牛坪稀土矿床碳酸岩的矿物学分带特征及其中的熔体、熔流体和流体包裹体进行了初步描述与探讨,以期为研究碳酸岩的岩浆演化、岩浆-流体转化过程及稀土元素的富集与分异机理提供新的思路,促使对稀土碳酸岩矿物学分带及其对REE富集与分异的研究引起更多的关注和重视.     

S, C, O, H Isotope Data and Noble Gas Studies of the Maoniuping LREE Deposit, Sichuan Province, China： A Mantle Connection for Mineralization

The Maoniuping REE deposit, located about 22 km to the southwest of Mianning, Sichuan Province, is the second largest light REE deposit in China, subsequent to the Bayan Obo Fe-Nb-REE deposit in the Inner Mongolia Autonomous Region. Tectonically, it is located in the transitional zone between the Panxi rift and the Longmenshan-Jinpingshan orogenic zone. It is a carbonatite vein-type deposit hosted in alkaline complex rocks. The bastnaesite-barite, bastnaesite-calcite, and bastnaesite-microcline lodes are the main three types of REE ore lodes. Among these, the first lode is distributed most extensively and its REE mineralization is the strongest. Theδ34Sv-CDT values of the barites in the ore of the deposit vary in a narrow range of +5.0 to +5.1‰in the bastnaesite-calcite lode and +3.3 to +5.9‰in the bastnaesite-barite lode, showing the isotopic characteristics of magma-derived sulfur. Theδ13Cv-PDB values and theδ518OV-SMOW values in the bastnaesite-calcite lode range from -3.9 to -6.9‰and from +7.3 to +9.7‰, respectively, which fall into the range of "primary carbonatites", showing that carbon and oxygen in the ores of the Maoniuping deposit were derived mainly from a deep source. Theδ13Cv-PDB values of fluid inclusions vary from -3.0 to -5.6‰, with -3.0 to -4.0‰in the bastnaesite-calcite lode and -3.0 to -5.6‰in the bastnaesite-barite lode, which show characteristics of mantle-derived carbon. TheδDv-SMOW values of fluid inclusions range from -57 to -88‰, with -63 to -86‰in the bastnaesite-calcite lode and -57 to -88‰in the bastnaesite-barite lode, which show characteristics of mantle-derived hydrogen. Theδ18OH2OV-SMOW values vary from +7.4 to +8.6‰in the bastnaesite calcite lode, and +6.7 to +7.8‰in the bastnaesite-barite lode, almost overlapping the range of +5.5 to +9.5‰for magmatic water. The 4He content, R/Ra ratios are (13.95 to 119.58×10-6 (cm3/g)STP and 0.02 to 0.11, respectively, and 40Ar/36Ar is 313±1 to 437±2. Considering the 4He increase caused by high contents of radioactive elements, a mantle-derived fluid probably exists in the inclusions in the fluorite, calcite and bastnaesite samples. The Maoniuping deposit and its associated carbonatite-alkaline complex were formed in 40.3 to 12.2 Ma according to K-Ar and U-Pb data. All these data suggest that large quantities of mantle fluids were involved in the metallogenic process of the Maoniuping REE deposit through a fault system.     

四川牦牛坪稀土矿床碳酸岩Sm—Nd等时线年龄及其地质意义

川西冕宁-德昌REE成矿带是中国最重要的REE成矿带之一,包括牦牛坪超大型REE矿床、大陆槽大型REE矿床：木落寨中型REE矿床和里庄小型REE矿床等。REE成矿作用与碳酸岩-碱性杂岩体有关,受印度-亚洲大陆碰撞带的一系列新生代走滑断裂系统控制。碳酸岩-碱性岩杂岩体主要侵位于元古代结晶基底岩石和古生代-中生代沉积盖层。碳酸岩主要为方解石碳酸岩,碱性正长岩以英碱正长岩为主,两者微量元素分布模式及Sr-Nd同位素组成特征相一致,表明两者为岩浆不混溶产物,因此两者的成岩时代应该基本相近。然而,前人研究成果表明,牦牛坪碳酸岩中钠铁闪石K-Ar年龄为31．7Ma,正长岩全岩K—Ar年龄为40．8Ma,两者相差10Ma。此外,研究表明,大陆槽、木落寨和里庄REE矿床碳酸岩-正长岩杂岩体成岩年龄与其相应的成矿年龄基本一致,而牦牛坪REE矿床两者相差甚远。本文利用碳酸岩中方解石进行了Sm—Nd等时线年龄测定,结合前人资料,重新厘定了牦牛坪REE矿床碳酸岩的成岩年龄和矿床的成矿年龄,分别为29．9Ma和26～27Ma,两者在误差范围内相一致。     

牦牛坪稀土矿床成矿模式及找矿方向探讨

本文概略介绍了牦牛坪稀土矿床特征,讨论了成矿时代,分析了成矿条件,初步总结了成矿规律,探讨了成矿物质来源、成矿过程及成矿机理,提出该矿床为上地幔部分熔融基性—超基性岩浆多期多阶段分异演化高侵位云煌岩-霓石碱性花岗岩-碱性基性伟晶岩-方解石碳酸岩型单一氟碳铈矿稀土矿床。初步建立了北北东向断裂系统加帽源碱性含矿杂岩体二元成矿模式,指出了进一步找矿远景区段。     

四川牦牛坪稀土矿床成矿流体来源与演化初探——萤石稀土地球化学的证据

萤石是四川牦牛坪稀土矿最重要的脉石矿物之一。根据稀土含量、有关参数及配分模式，矿区萤石可分为LREE富集型、KLEE平坦型和LREE亏损型3种，不同类型萤石之间以及每种类型萤石的稀土地球化学特征具有连续变化规律。分析结果表明：矿区3种类型的萤石为同源不同阶段形成的产物；矿床成矿流体主要来源于本区正长岩－碳酸岩岩浆演化分异的相对富集LREE的流体；矿床成矿过程中较少再有相对富集LREE的流体参与；成矿环境由相对氧化向相对还原变化。     

四川牦牛坪稀土矿床萤石Sr、Nd同位素对地幔成矿流体的指示意义

萤石是四川牦牛坪稀土矿床主要的脉石矿物之一，其形成贯穿了整个稀土成矿过程，因此同位素的研究对探讨萤石和稀土成矿流体的来源具有重要的价值。矿区6件萤石样品的Sr、Nd同位素组成没有明显差异，结合围岩（碳酸岩－正长岩，花岗岩）同位素组成特征研究表明，不同颜色、来自不同矿石类型、具有不同REE类型的萤石为同源产物，稀土成矿流体来源于富集地幔，与区内碳酸岩－正长岩岩浆活动密切相关。     

四川牦牛坪外围龙家沟稀土矿体第一阶段找矿突破及启示

围绕加强国内稀土资源勘探和增储上产的迫切需求,笔者在综合研究前期地质资料的基础上,对攀西牦牛坪外围龙家沟开展了以稀土找矿为主的多学科交叉综合调查评价工作。经钻探验证,龙家沟ZK001孔深部发育厚大高品位稀土矿体,科研指导找矿取得突破性进展。161件岩芯样品电感耦合等离子体发射光谱分析结果表明：钻孔ZK001总稀土氧化物（TREO）平均含量达4.87%,见矿视厚度125.76 m,核心部位高品位矿段超过60%。牦牛坪外围龙家沟厚大隐伏稀土矿体的发现与钻探验证,扩大了牦牛坪稀土矿外围的成矿前景,是科技创新指导找矿突破的又一典型实践。随着冕宁-德昌稀土成矿带成矿机制、精准勘查理论技术难题的突破、交叉学科以及模拟技术的应用,将进一步带动该区稀土找矿工作。今后,有必要持续开展牦牛坪外围稀土矿产综合地质调查工作,大幅提升中国第二大稀土资源基地的资源保障能力,对确保中国稀土资源的绝对优势地位具有重要现实意义。     

四川牦牛坪稀土矿床成因研究——来自包裹体的证据

四川牦牛坪稀土矿床是中国的第二大轻稀土矿床。碳酸岩-正长岩杂岩体是矿区主要的围岩,萤石是主要的脉石矿物。在四川冕宁牦牛坪稀土矿床霓辉重晶石型矿体早期萤石中笔者发现了大量的流体-熔体包裹体,对萤石矿物包裹体研究结果表明,牦牛坪矿床的晚期萤石矿物中至少存在6种类型包裹体：（1）气液包裹体（V-L）;（2）含CO2三相包裹体（L-L-V）;（3）含有少量子晶的多相包裹体（L-V-D或L-L-V-D）;（4）流体-熔体包裹体或多子晶包裹体（L-L-V-MS）;（5）固体包裹体（S）和（6）已经爆裂的高压包裹体等。各种类型的包裹体代表了不同的成岩阶段,并存在成因上的内在联系。气液包裹体（V-L）初融温度为-24．5--22．0℃,冰点温度为-2．5～-6．0℃,盐度为4．2％～9．2％。均一温度集中在142-146℃。含CO2三相包裹体（L—L—V）Tm-CO2为-56．6℃,Tm-clathe为＋2．1-＋10．0℃,盐度为0．1％～13．0％;Th-CO2为＋25～＋30．3℃,均一温度为230～265℃。含子晶的多相包裹体（L—V—D或L-L—V—D）子晶溶化温度在260～285℃之间,与前两类包裹体具有明显的成因上联系。流体-熔体包裹体或多子晶包裹体（L—L—V—MS）CO2含量约为10vol％;固相成分含量30vol％到90vol％,为长板状或立方体子晶,有些子晶呈圆形,正高突起,一轴负晶,可能为稀土碳酸盐矿物;Tm-CO2为-65．0～-58．0℃,初熔温度为-55．0--52．0℃,Th-CO2为＋26．5～＋28．3℃,气体水合物溶解温度为＋26．0～＋31．0℃;CO2相在220～276℃均一到水溶液相。固体组分一般会出现4次明显的溶解过程,即200～240℃、240—300℃、270～370℃和370～720℃四个阶段。包裹体的显微测温和拉曼成分分析结果显示早期流体中富含H2O、CO2、H2S和心等挥发分,并富含大量的重晶石、氟碳铈矿的子矿物,晚期成矿流体中则以H2O和CO2为主。根据矿床地质特征和矿物包裹体的研究结果,我们认为源区地幔岩石的低程度部分熔融形成富集稀土的碱性碳酸岩岩浆,侵位过程中产生液态不混熔现象,分异出携带大量高度富集REE的富F和CO2的高温流体,并主要以气相形式迁移稀土元素,在气成热液阶段REE富集成矿。矿床的成矿作用是由碳酸岩岩浆气液流体的沸腾、充填和交代过程而实现的。萤石的形成经历了气相迁移、深部成岩、上升交代、侵位成岩的过程。萤石的形成与稀土矿化有密切的关系。