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稀土元素、同位素地球化学

萤石是四川牦牛坪稀土矿床最重要的脉石矿物之一，本身已具有工业价值。根据稀土元素含量、有关参数及分布模式，将矿区萤石分为LREE富集型、LREE平坦型和LREE亏损型三种。不同REE类型中的萤石稀土元素地球化学特征具有连续变化的规律。萤石与围岩REE、同位素分析对比结果表明，LREE富集型、LREE平坦型和LREE亏损型萤石为同源不同阶段形成的产物；萤石成矿流体具有地幔特征，与矿区正长岩－碳酸岩密切相关。     

萤石Sr、Nd同位素地球化学研究评述

本文通过大量实例综述了近年萤石Sr、Nd同位素在定年和示踪方面取得的进展，结果表明：萤石Sm－Nd同位素可以用于测定成矿作用的时代，但由于萤石Nd同位素初始值存在不均一性和受次生干扰的影响，所获数据最好用其它测年方法获得的数据加以验证；萤石Sr、Nd同位素组成是示踪成矿流体来源的有效方法，利用Sr、Nd同位素组成还可定量估算出形成成矿流体不同端元所占的比例。     

湖南芙蓉锡矿床中萤石的Sr－Nd同位素研究

芙蓉锡矿床是一个新探明的超大型锡矿床，产于湘南的骑田岭花岗岩体中。本次研究测试了该矿床中与锡石硫化物共生的萤石的Sr和Nd同位素组成。各矿脉中萤石的87Sr/86Sr比值并不相同，变化从0.70770～0.71484，反映了成矿流体的初始87Sr/86Sr比值并不均一。萤石的Sm－Nd同位素组成并没有构成很好的等时线，计算的ENd（t）值变化在－6.6～－9.8之间。萤石的Sr－Nd同位素组成并不同于花岗岩，成矿流体中的Sr和Nd有很大一部分来自围岩的碳酸盐岩地层。     

青藏高原东部碳酸岩-正长岩杂岩体型REE矿床成矿模式——以大陆槽REE矿床为例

冕宁-德昌稀土(REE)矿带位于青藏高原东部,受川西一系列走滑断裂控制,大陆槽矿床是矿带中唯一位于南部的大型REE矿床。在前人研究基础上,结合近年来对整个稀土矿带地质填图和室内研究,重点对大陆槽矿床的成矿特征、赋矿围岩及其蚀变、矿石类型、成矿流体来源和流体包裹体演化等方面与同一矿带内的其它矿床进行了详细对比,进一步总结了碳酸岩型(含碳酸岩-正长岩杂岩体)REE矿床的成矿过程。大陆槽矿床的No.1号和No.3号矿体均位于碳酸岩-正长岩杂岩体内,分别由不同隐爆角砾岩筒所控制。以往研究认为两个矿体的碳酸岩-正长岩杂岩体侵位的年龄都在12Ma左右,本次研究发现在26.49±0.63Ma已经存在碳酸岩-正长岩杂岩体岩浆活动。大陆槽REE矿床受隐爆角砾岩构造活动和风化作用的影响,矿石类型以角砾岩型和风化型为主,脉石矿物和矿石矿物在手标本尺度和镜下很难辨认。通过野外观察、镜下矿物共生组合、包裹体显微测温等研究发现,大陆槽矿化过程和牦牛坪矿床相似,只是矿化规模较小,矿化阶段分为岩浆岩阶段-伟晶岩阶段(600℃)-高温热液阶段(450~350℃)-低温热液阶段(350℃),氟碳铈矿形成于热液阶段的晚期。根据伟晶岩阶段至热液阶段氟碳铈矿中流体包裹体的特征,发现多期次隐爆角砾活动导致大气降水和碳酸岩中脱出的CO_2的加入,使得成矿流体的密度(0.732~0.631g/cm~3)、压力(2436~101bar)逐渐降低,直至成矿。此外,岩相学观察和拉曼测试分析也表明包裹体从熔融包裹体过渡到含重晶石、萤石、天青石子晶的富CO_2包裹体、气液两相包裹体,显示了成矿流体由岩浆至热液的转化过程。大陆槽矿床中的包裹体阴离子以SO_4~(2-)为主,气体以CO_2为主,成矿流体中阳离子主要为K~+、Na~+、Ca~(2+)、Sr~(2+)、Ba~(2+)和稀土元素阳离子,表明流体属于SO_4~(2-)-CO_2-H_2O体系,与矿带中其它矿床的成矿流体体系一致。成矿流体的主要成分是岩浆水、大气水和碳酸岩脱碳作用形成的CO_2,后者导致热液方解石和氟碳铈矿的O同位素(氟碳铈矿和方解石:δ~(18)O=5.8‰~12.5‰)值升高。已有研究显示矿带中不同矿床的脉石矿物如重晶石、天青石的Sr-Nd-Pb同位素与碳酸岩-正长岩杂岩体的相关数值基本一致,表明这些脉石矿物来源于碳酸岩-正长岩杂岩体。多期次隐爆角砾岩化作用及大陆槽断裂相关的构造活动促进了成矿流体的循环,直接或间接导致了大陆槽隐爆角砾岩型和风化型矿石的形成。尽管在大陆槽和牦牛坪矿床可以识别出表生氧化阶段,但这一过程并不伴随稀土矿化,热液阶段才是稀土沉淀的主要阶段。研究还强调了碳酸岩发育的大陆槽No.3矿体和里庄矿床主要出现的霓长岩化与矿化无关,而牦牛坪矿床地表并无霓长岩化蚀变。在以往和本次研究的基础上,建立了川西碳酸岩-正长岩型稀土矿床的成矿模式。     

四川牦牛坪轻稀土矿床地幔流体特征——铅锶钕和氦氩同位素及稀土元素证据

四川牦牛坪稀土矿床是中国第二大轻稀土矿床。笔者对该矿床进行了较系统的Pb—Sr—Nd同位素、稀有气体同位素地球化学以及稀土元素地球化学研究。稀土元素地球化学特征研究显示,矿区萤石、方解石、氟碳铈矿稀土元素分布模式与区内英碱正长岩相似,表明牦牛坪稀土矿床成矿与英碱正长岩岩浆活动有关以及石英包裹体流体REE曲线平直,Eu与Ce无明显异常,曲线规律性较强,可以认为牦牛坪轻稀土矿床成矿流体稀土元素是深源的。Pb—Sr—Nd同位素组成表明成矿物质来自富集地幔,具深源甚至幔源特征。稀有气体同位素地球化学研究也在一定程度上揭示了牦牛坪轻稀土矿化与地幔过程之间存在着成因关系。     

四川大陆槽稀土矿床碳酸岩-英碱正长岩锆石U-Pb年代学和Hf同位素性质及其地质意义

川西冕宁-德昌稀土成矿带是中国最重要的稀土成矿带之一,所有稀土矿床均与碳酸岩-正长岩杂岩体有关.前人研究表明,牦牛坪、木落寨和里庄碳酸岩-碱性杂岩体成岩年龄与其相应矿床的成矿年龄基本一致,而大陆槽正长岩年龄与REE矿床的成矿年龄相差甚远.本文对大陆槽碳酸岩、英碱正长岩进行了SHRIMP U-Pb锆石年代学和LA-MC-ICPMS锆石Hf同位素原位测量,它们的形成年龄分别为12.99±0.94Ma、14.53±0.31Ma,表明两者是同时形成的,且与其成矿年龄基本一致.碳酸岩和正长岩的εHf(t)值、Hf模式年龄与它们的εNd(t)值、Nd模式年龄所展现出来的特征一致,说明在其形成过程中有地壳物质的加入.     

湘中锡矿山超大型锑矿床的碳、氧同位素体系

本文系统地研究了锡矿山锑矿床的围岩、蚀变围岩和热液成因方解石的碳、氧同位素组成。研究表明，相对于区域地层，矿区灰岩明显亏损^18O；围岩蚀变过程中，围岩的δ^18O值趋于减小并有明显的空间变化趋势。不同期次方解石的碳、氧同位素特征明显不同：成矿早期显示出深特征；成矿晚期方解石的碳、氧同位素组成呈正相关，为水－岩反应和温度降低耦合作用所致；成矿期后方解石的碳、氧同位素组成呈明显的负相关，这种方解石的沉淀介质成成矿流体明显不同。水－岩反应的理论模拟显示，成矿流体不可能为未经深部循环的大气降水；成矿流体中的可溶性碳以H2CO3为主；早期成矿流体的δ^13C、δ^18O分别为－6‰、＋10‰，晚期成矿流体的δ^13C、δ^18O分别为0‰、4‰。     

稀有气体同位素示踪成矿古流体研究进展

稀有气体（特别是He、Ar）是一种研究成矿古流体来源的灵敏示踪剂。地球不同圈层的稀有气体同位素具有不同的特征同位素比值。测试样品流体包裹体中的稀有气体同位素值，从测试值中排除掉包裹体形成后各种后生过程对流体初始同位素组成的影响。把得到的结果与前人研究总结的特征值进行比较分析，可以示踪成矿流体来源，从而探讨各种矿床的成矿机制与成矿作用。归纳了近年来用稀有气体同位素来示踪成矿流体的研究进展，概括了其在不同类型矿床中的应用现状，并指出当前该方法存在的问题及发展趋势。     

滇东北矿集区茂租铅锌矿床地球化学特征

茂租铅锌矿床位于扬子地台西南缘,是滇东北矿集区内的一个大型矿床,矿体主要呈似层状产于震旦系灯影组白云岩中;矿石矿物以闪锌矿为主,次为方铅矿;脉石矿物主要为白云石、方解石和萤石。本文对该矿床中与铅锌矿密切共生的团块状白云石、方解石和萤石以及围岩灯影组白云岩的REE地球化学特征和C、O、Sr同位素进行了对比研究。结果表明:团块状白云石和方解石的稀土配分模式、C同位素和Sr同位素比值与围岩灯影组白云岩比较接近,表明形成团块状白云石和方解石的成矿流体主要来源于围岩灯影组白云岩的溶解;但这两种矿物的稀土总量ΣREE高于灯影组白云岩,说明成矿流体除了主要由围岩提供REE外,还有部分其他富含REE流体的加入。萤石则具有LREE亏损和分配曲线相对平缓的稀土配分模式特征,表明萤石形成于成矿的晚阶段,有更多的外部流体的加入。团块状白云石、方解石和萤石表现出明显的Eu正异常,且团块状白云石和方解石的O同位素低于灯影组白云岩,反映了存在较高温度的流体活动,这3种脉石矿物是由高温热液流体形成的。灯影组白云岩和3种脉石矿物都具有明显的Ce负异常,说明成矿流体可能主要来源于地层循环水,继承了围岩的Ce负异常特征。方解石和萤石的Sr同位素比值高于围岩震旦系灯影组白云岩和峨眉山玄武岩,但小于基底岩石昆阳群和会理群,说明成矿流体主要由赋矿围岩等沉积地层中的循环流体与流经了基底岩石的深部流体混合形成。     

http://www.sciencedirect.com/science/article/pii/S1674987110000125

<正>Carbonatites are commonly related to the accumulation of economically valuable substances such as REE.Cu,and P.The debate over the origin of carbonatites and their relationship to associated silicate rocks has been ongoing for about 45 years.Worldwide,the rocks characteristically display more geochemical enrichments in Ba,Sr and REE than sedimentary carbonate rocks.However,carbonatite's geochemical features are disputed because of secondary mineral effects.Rock-forming carbonates from carbonatites at Qinling.Panxi region,and Bayan Obo in China show REE distribution patterns ranging from LREE enrichment to flat patterns.They are characterized by a Sr content more than 10 times higher than that of secondary carbonates.The coarse- and fine-grained dolomites from Bayan Obo H8 dolomite marbles also show similar high Sr abundance,indicating that they are of igneous origin.Some carbonates in Chinese carbonatites show REE(especially HREE) contents and distribution patterns similar to those of the whole rocks.These intrusive carbonatites display lower platinum group elements and stronger fractionation between Pt and Ir relative to high-Si extrusive carbonatite.This indicates that most intrusive carbonatites may be carbonate cumulates.Maoniuping and Daluxiang in Panxi region are large REE deposits.Hydrothermal fluorite ore veins occur outside of the carbonatite bodies and are emplaced in wallrock syenite.The fiuorite in Maoniuping has Sr and Nd isotopes similar to carbonatite.The Daluxiang fiuorite shows Sr and REE compositions different from those in Maoniuping.The difference is reflected by both the carbonatites and rock-forming carbonates,indicating that REE mineralization is related to carbonatites.The cumulate processes of carbonate minerals make fractionated fluids rich in volatiles and LREE as a result of low partition coefficients for REE between carbonate and carbonatite melt and an increase from LREE to HREE.The carbonatite-derived fluid has interacted with wallrock to form REE ore veins.The amount of carbonatite dykes occurring near the Bayan Obo orebodies may support the same mineralization model,i.e.that fluids evolved from the carbonatite dykes reacted with H8 dolomite marble,and thus the different REE and isotope compositions of coarse- and fine-grained dolomite may be related to reaction processes.     

REE Geochemistry of Fluorite from the Maoniuping REE Deposit, Sichuan Province, China： Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit,Sichuan Province,China.Fluorite with different colors occurs not only within various orebodies,but also in wallrocks of the orefield.Based on REE geochemistry,fluorite in the orefield can be classified as the LREE-rich,LREE-flat and LREE-depleted types.The three types of fluorite formed at different stages from the same hydrothermal fluid source,with the LREE-rich fluorite forming at the relatively early stage,the LREE-flat fluorite in the middle,and the LREE-depleted fluorite at the latest stage.Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color.The mineralization of the Maoniuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.     

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。     

白云鄂博矿区碱性基性岩—碳酸岩岩墙岩石学研究

白云鄂博地区广泛发育碳酸岩墙 -碱性基性岩墙,通过对其岩石学、矿物学、岩石化学、稀土元素、微量元素的系统研究表明,碳酸岩墙为火成碳酸岩,部分碳酸岩墙的REE含量高达14 6 75 %,与赋矿白云石碳酸岩体的REE含量(最高达 10 % )相近,两者均为富稀土矿石。矿区基性岩墙的K2 O +Na2 O含量( >5 % )高于普通基性岩石(4 % ),表明它们属于碱性岩类,是碱性基性岩墙。碳酸岩墙 -碱性基性岩墙的REE与微量元素的分配型式近似,Sr、Nd、Pb同位素特征亦相近,表明它们形成于一个比较特殊的、近似的源区,两者有一定的成因关系。     

四川冕宁里庄稀土元素矿床矿石类型及金云母Ar-Ar年龄

四川冕宁-德昌稀土元素成矿带长约270 km,宽15 km,该成矿带包括牦牛坪超大型、大陆槽大型、木落寨中型和里庄小型稀土元素矿床及一系列矿点和矿化点。里庄稀土元素矿床作为矿带中唯一矿化特征以细脉浸染状为主的矿床,该矿床细脉浸染状矿化特征的成因和围岩蚀变特征尚未得到详细研究。文章将通过详细野外调查和室内研究,总结矿石类型和碳酸岩、正长岩蚀变特征,揭示细脉浸染状矿化特征的成因。研究表明,里庄矿床矿石类型以细脉浸染状为主,兼有少量角砾状。细脉浸染状矿石呈致密块状,矿物共生组合主要为氟碳铈矿+方解石+萤石+天青石+金云母,大规模的氟碳铈矿形成于热液阶段晚期并叠加在早期方解石、萤石和天青石等脉石矿物之上。细脉浸染状矿石全岩稀土元素配分显示LREE富集(33430×10~(-6)～46530×10~(-6)),HREE亏损(160×10~(-6)～192×10~(-6)),稀土元素总量高(33620×10~(-6)～46690×10~(-6)),全岩稀土元素配分特征与碳酸岩和正长岩相似,但后两者稀土元素总量较低。与牦牛坪发育脉状矿化系统、大陆槽角砾岩筒系统相比,里庄矿化特征以细脉浸染状为主,其可能是由于张性裂隙不发育造成的。区内正长岩-碳酸岩杂岩体广泛发育强烈的蚀变作用。正长岩发育典型霓长岩化,这种蚀变以钾长石被钠长石交代为特征,并形成次生鳞片状黑云母,少量半自形氟碳铈矿叠加在钠长石和黑云母之上。碳酸岩广泛发育红化,其原生表面洁净的方解石被流体交代,大量氟碳铈矿叠加在蚀变方解石之上。矿区矿体赋存在正长岩-碳酸岩杂岩体中,BSE图像及显微镜观察显示氟碳铈矿叠加在蚀变碳酸岩-正长岩之上,结合已有数据发现矿石及部分脉石矿物与碳酸岩-正长岩在微量元素和Sr-Nd-Pb同位素组成特征的一致,表明碳酸岩-正长岩杂岩体提供了本矿床稀土元素矿化的物质来源。此次研究中发现,在里庄矿床中大量发育与氟碳铈矿密切共生的金云母。文章对该金云母进行了Ar-Ar同位素测年,获得金云母形成年龄为(26.0±1.1)Ma,误差范围内与已报道的氟碳铈矿SIMS Th-Pb年龄和正长岩的锆石SHRIMP U-Pb年龄一致,进一步说明REE成矿与正长岩-碳酸岩在成因上具有一致性。     

A model for carbonatite hosted REE mineralisation — the Mianning–Dechang REE belt,Western Sichuan Province,China

The Mianning–Dechang (MD) REE belt of Sichuan, China is one of the most important REE belt in China, which includes Maoniuping, the third largest REE deposit in the world and a series of large to small REE deposits. Mineralization styles varied across the belt, as well as within different parts of the same deposit. Styles include vein-stockworks, pegmatites, breccias and disseminated REE mineralization. Based on geological, geochemical and inclusion studies, this paper proposes a new model for carbonatite hosted REE mineralization. The results show that ore-forming fluid is derived from carbonatite magma, which has high temperature, pressure and density, and is characterized by high K, Na, Ca, Sr, Ba, REE and SO₄ contents. The supercritical ore fluid underwent a distinctive evolution path including phase separation, exolution of sulfate melt and unmixing between aqueous fluid and liquid CO₂. Rapid geochemical evolution of a dense carbonatite fluid causes REE mineralization and associated alteration to occur within or proximal to the source carbonatite. Veins, pegmatites and carbonatite comprise a continuum of mineralization styles. Veins occur in the outer zone of the upper levels of the deposit. Pegmatites occur in the inner zone of upper levels, whereas disseminated REE ore occurs at the base of the carbonatite. High water solubility in the carbonatite magma and low water, high REE in the exsolved ore-forming fluids, imply that a giant carbonatite body and deep magma chamber are not necessary for the formation of giant REE deposits.     

Geochemical constraints on the genesis of the Bayan Obo Fe-Nb-REE deposit in Inner Mongolia, China

Trace element and isotopic compositions of carbonate from ore bodies, country rock which hosts the ore bodies (H8 dolomite), a carbonatite dyke exposed in Dulahala near Bayan Obo, and rare earth element (REE)-rich dolomite in Bayan Obo have been determined to understand the genesis of the Bayan Obo Fe-Nb-REE ore deposit, the world’s largest resource of REE. The REE and trace element distribution patterns of samples from the REE-rich carbonatite dykes are identical to those of mineralized carbonate rocks, indicating a genetic linkage between the REE-rich carbonatite and mineralization in this region. By contrast, carbon and oxygen isotopes in the mineralized carbonate varied significantly, δ¹³C = −7.98‰ to −1.12‰, δ¹⁸O = 8.60-25.69‰, which are distinctively different from those in mantle-derived carbonatite. Abnormal isotopic fractionations between dolomite and calcite suggest that these two minerals are in disequilibrium in the carbonatite dyke, ore bodies, and H8 marble from Bayan Obo. This isotopic characteristic is also found in mineralized sedimentary marine micrite from Heinaobao, ∼25 km southeast of the Bayan Obo Fe-Nb-REE ore deposit. These facts imply that the carbonate minerals in the Bayan Obo deposit have resulted from sedimentary carbonate rocks being metasomatised by mantle-derived fluids, likely derived from a REE-enriched carbonatitic magma. The initial Nd isotope values of ore bodies and carbonatite dykes are identical, indicating that ore bodies, carbonatite dykes and veins may have a similar REE source.     

The Ribeira fluorite district,southern Brazil

The origin and evolution of different ore deposits grouped in the same district are often complex and may involve inheritance from crustal or mantle geochemical anomalies, remobilization of former ore deposits and a polyphase hydrothermal history. Localized in a Proterozoic basement in the Parana state, the Ribeira fluorite district is such an example composed of three deposit types with distinct geological and geochemical characters. Emplaced at different periods from the late Proterozoic to the Cretaceous, they are roughly aligned along a belt nearly 10 km in width and 50 km in length, the southern boundary of which is a transcurrent fault. Two main ore facies are present: (1) microcrystalline ore (< 0.1 mm grains) and (2) macrocrystalline ore (with a grain size of several millimetres). The former results from the replacement of metalimestones or internal karstic sediments and the latter from microcrystalline ore dissolution and pore precipitation or recrystallization. At least two different groups of source rocks can be proposed for the trapped REE in CaF₂: (1) fluorite samples associated with the Mato Preto carbonatitic rocks display a slightly negative ɛNd compatible with a mantle source and a REE pattern with the higher ΣREE and La/Yb ratio in the district; (2) other fluorites have a strongly negative ɛNd (− 14 to − 20) which indicates a crustal source. That fluorine and REE have the same source is possible in strata-bound and fracture-filling deposits, but is doubtful at Mato Preto, the only economic fluorite deposit associated with carbonatite rocks in Brazil. This occurrence within a Precambrian fluorite belt suggests that remobilization of a former strata-bound deposit was a more significant metallogenic process than magmatic differentiation. Editorial handling: DR     

四川德昌大陆槽稀土矿床地质特征

为查明德昌大陆槽稀土矿床的成矿地质特征和稀土元素的赋存状态,通过对大量岩石、矿石光(薄)片的观察鉴定以及对矿体形态、矿石的物质组分、结构构造的研究,表明该矿床受喜马拉雅期富稀土碱性杂岩的构造控制,成矿地质特征与牦牛坪矿床极为相似。大陆槽稀土矿床为攀西稀土成矿带上最年轻的稀土矿床,矿床类型新,稀土品位高,主要稀土矿物氟碳铈矿粒度较粗,可选冶。