东秦岭地区一种富稀土热液型钡解石的发现及其意义

对东秦岭地区河南嵩县一带进行地质调查,发现了一系列具有一定规模的含稀土碱性碳酸岩矿脉并在其中发现一种特殊的钡解石矿物。依据该钡解石主量元素组成,计算分子式为Ba_1._(04) Ca_0._(81)Sr_(0.14)(CO_3)_2,为锶钡解石,LA-ICP-MS分析表明其富Na、K、Mn、Pb、REE、Y等元素,稀土元素总量最高为4 080×10-6,总体表现为轻稀土元素富集、重稀土元素亏损。该矿物与常见于沉积岩中的钡解石存在显著差别。钡解石呈现出与霓辉石共生(钡解石正晶型,霓辉石围绕钡解石生长;霓辉石正晶型,钡解石围绕霓辉石生长),或与石英、方解石、磷灰石共生(它形)两种状态。早期方解石与钡解石共生,形成于碱性岩演化早期的碳酸盐与硅酸盐不混溶阶段;晚期方解石则以布丁状分布于钡解石和霓辉石中,为碳酸盐交代阶段产物。霓辉石、钾长石、钠长石、辉石、磷灰石、方解石、石英和钡解石共生的组合与已知火成碳酸岩的矿物组合相似。该区碳酸岩富集REE、Ba和Sr,与已知大型富稀土碳酸岩矿床(如牦牛坪稀土矿)特征一致。结合已发现矿脉地质特征,认为该区有较大的成矿潜力,为东秦岭地区寻找火成岩型稀土矿提供了依据。     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Petrography and mineral chemistry of Alkaline-Carbonatite Complex in Singhbhum Crustal Province,Purulia region,Eastern India

The variant rock types of an Alkaline-Carbonatite Complex (ACC) comprising alkali pyroxenite, nepheline syenite, phoscorite, carbonatite, syenitic fenite and glimmerite along with REE and Nb-mineralization are found at different centres along WNW-ESE trending South Purulia Shear Zone (SPSZ) in parts of Singhbhum Crustal Province. The ACC occurs as intrusions within the Mesoproterozoic Singhbhum Group of rocks. Alkali pyroxenite comprises of aegirine augite, magnesiotaramite, magnesiokatophorite as major constituents. Pyrochlore and eucolite are ubiquitous in nepheline syenite. Phoscorite contains fluorapatite, dahllite, collophane, magnetite, hematite, goethite, phlogopite, calcite, sphene, monazite, pyrochlore, chlorite and quartz. Coarse fluorapatite shows overgrowth of secondary apatite (dahllite). Secondary apatite is derived from primary fluorapatite by solution and reprecipitation. The primary fluorapatite released REE to crystallize monazite grains girdling around primary apatite. Carbonatite is composed dominantly of Srcalcite along with dolomite, tetraferriphlogopite, phlogopitic biotite, aegirine augite, richterite, fluorapatite, altered magnetite, sphene and monazite. The minerals comprising of the carbonatite indicate middle stage of carbonatite development. Fenite is mineralogically syenite. Glimmerite contains 50–60% tetraferriphlogopite. An alkali trend in the evolution of amphiboles (magnesiotaramite-magnesiokatophorite-richterite) and chinopyroxenes (aegirine augite, aegirine) during the crystallization of the suite of rocks is noted. Monazite is the source of REE in phoscorite and carbonatite. Fluorapatite has low contents of REE, PbO, ThO₂ and UO₂. Pyrochlore reflects Nb-mineralization in nepheline syenite and it is enriched in Na₂O, CaO, TiO₂, PbO and UO₂. Pyrochlore containing UO₂ (6.605%) and PbO (0.914%) in nepheline syenite has been chemically dated at 948 ± 24 Ma by EPMA.     

Mineralogical and geochemical studies of brecciated ores in the Dalucao REE deposit,Sichuan Province,southwestern China

The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (⁴⁰Ar/³⁹Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO₂ derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ¹⁸O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ¹⁸O_V-SMOW from 8.0‰ to 11.6‰, and δ¹³C _V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite.     

黔西南灰家堡金矿田热液方解石稀土元素与C-O-Sr同位素地球化学特征

为探讨灰家堡金矿田矿化剂和成矿物质来源,系统开展了热液方解石的稀土元素和C-O-Sr同位素研究。结果表明,热液方解石的稀土元素具有"上凸型"配分模式,低的(La/Sm)N值(0.003~0.580),较高的(Gd/Yb)_N值(1.21~15.73),Eu正异常,显示成矿流体的壳源特征;产于龙潭组(P3l)的矿体中的方解石δ13CPDB为-9.3‰~1.7‰(均值为-3.93‰);产于构造蚀变体(SBT)的矿体中的方解石δ¹³CPDB为-7.8‰~3.3‰(均值为1.04‰),C-O同位素组成介于地幔碳酸岩与海相碳酸盐岩之间,在δ¹³CPDB-δ¹⁸OSMOW图解上呈近水平分布,与矿体全岩及围岩碳同位素组成相似,表明成矿流体的C可能具有多来源特征。成矿流体与围岩之间的水-岩反应并未改变矿石的碳、氧同位素组成,流体-岩石相互作用不是导致热液方解石沉淀的主要机制,而更可能与CO₂的脱气作用有关;方解石的⁸⁷Sr/⁸⁶Sr值接近碳酸盐岩围岩、明显高于幔源物质的平均值,表明成矿热液中的Sr可能主要来自碳酸盐岩围岩。     

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。     

川西冕宁-德昌稀土矿带霓长岩的地球化学特征及地质意义

霓长岩化作用是指碳酸岩(或碱性岩)流体对围岩的交代蚀变,它是碳酸岩型稀土(REE)矿床常见的蚀变类型,其所形成的岩石即为霓长岩。对霓长岩的深入研究可以鉴别碳酸岩体的存在,厘定碳酸岩岩浆(或流体)的地球化学性质及源区特征,这对于找寻碳酸岩相关的矿产资源(尤其是REE)以及剖析矿床成因机制有着重要的地质意义。川西冕宁-德昌稀土矿带是中国最重要的轻稀土矿带之一,包括牦牛坪超大型、大陆槽大型、木落寨和里庄中小型REE矿床以及一系列矿点。REE矿化与碳酸岩-碱性岩杂岩体密切相关,受一系列新生代走滑断裂的控制。该矿带广泛发育霓长岩化蚀变带,尤以大陆槽及里庄矿床为显著。岩相学分析表明,大陆槽和里庄霓长岩中的矿物多呈他形粒状结构,主要由长石、黑云母、霓辉石以及少量副矿物组成;主微量元素分析表明,霓长岩的碱质(K_2O+Na_2O)、MgO、Fe_2O_3T含量较高,且富集REE、Sr、Ba等微量元素;电子探针分析表明,霓长岩中的霓辉石Fe OT含量较高,长石Na_2O及K_2O含量较高,Ca O含量极低。An-Ab-Or三角图解显示长石主要为透长石和钠长石,属碱性长石系列;黑云母的地球化学成分图解表明云母的成因类型为交代型且具有相对富镁、贫铁等特征,属镁质黑云母。霓长岩化作用的交代流体含有较高的CO_2组分,且富含碱质、Mg、Fe及REE、Sr、Ba等元素。对比霓长岩与原岩的主微量元素发现:相比于正长岩原岩,在主量元素中,霓长岩的Fe、Mg、Ca等元素含量增加,Si、Al等元素含量降低;微量元素中,霓长岩的REE及Sr、Ba等元素显著增加。这意味着交代流体含有的Fe_2O_3T、MgO、CaO等组分在霓长岩化过程中被带进了围岩,而SiO_2和Al_2O_3等从围岩中被逐出。大陆槽及里庄矿区发育的角砾岩指示了矿区曾经历过频繁的角砾岩化事件,这提高了霓长岩作用的强度,并且为矿脉的穿插及REE矿物的沉淀提供了空间。在霓长岩化过程中,流体-围岩的组分交换反复发生,这削弱了REE络合物的稳定性,伴随多期次的热液活动及构造事件,最终完成REE活化→迁移→沉淀的过程。     

芙蓉锡矿方解石稀土元素地球化学特征及其对成矿流体来源的指示

方解石是芙蓉锡矿田重要的脉石矿物。根据芙蓉矿田白蜡水矿区和狗头岭矿区不同产状(云英岩型、蚀变岩体型和构造蚀变带-矽卡岩型)矿石中方解石稀土元素地球化学特征研究表明:两矿区成矿期热液方解石具有两种稀土模式,LREE(轻稀土元素)富集型和相对平坦型。其中,蚀变岩体型方解石所具有的相对平坦型稀土模式代表了LREE带出后残余热液的稀土模式特征,而云英岩型和构造蚀变带—矽卡岩型方解石的LREE富集型稀土模式与骑田岭新鲜花岗岩类似,表明成矿过程中没有LREE明显带出的迹象,残余热液继承了岩浆期后热液的特征。成矿流体来源于骑田岭花岗岩岩浆期后热液。     

白云鄂博矿床成因——矿体内霓长岩化成矿作用与赋矿白云岩的联系

通过对组成赋矿白云岩的白云石矿物系统的显微结构和化学成分的研究表明,赋矿白云岩是碳酸岩质次火山岩,因此白云鄂博矿床是与火成碳酸岩有关的矿床。赋矿白云岩属于镁质碳酸岩(MgOFeO+MnO)和铁质碳酸岩(MgOFeO+MnO)系列,FeO、MnO和SrO含量高,这与FeO、MnO和SrO含量很低的沉积碳酸岩完全不同。赋矿白云岩的这一特点还表明它来自经历过分异结晶后的白云质碳酸岩浆而不是初始白云质碳酸岩浆。赋矿白云岩复杂的矿物组合表明,其母岩浆是富含F、Cl、P和S这些挥发分以及REE,Na、K和Fe这些元素的。在碳酸岩浆上升和侵位的过程中由于温度压力的降低,碳酸岩浆释放的含上述组分的流体会向上部地壳集中并对其接触的围岩进行交代,这就形成了矿体内呈不对称带状分布的霓长岩化矿石带。在大量的萤石和稀土氟碳酸盐矿物形成以后(其对应于萤石-稀土条带状矿石),流体的成分仍相对富钠和CO_2,钠可以和围岩中的硅结合形成钠辉石,流体较高的比值,有利于稀土的富集,此时形成的钠辉石型矿石的稀土含量是相当高的,仅次于条带状矿石。随着流体继续迁移和交代,流体中CO_2浓度下降而H_2O含量增加,温度也有所下降,但是流体中的钠依然活跃,所以出现了含有结构水的钠闪石,形成了钠闪石型矿石。流体中H_2O的增加,比值的下降,不利于稀土的大量富集,因此,钠闪石型矿石的稀土含量明显低于钠辉石型矿石。这说明,从碳酸岩浆中外逸的流体,在迁移交代围岩的过程中其成分、温度和氧逸度都是有变化的。从初期富CO_2,温度和氧逸度较高,到后期富H_2O,温度和氧逸度都有所降低。不同矿石类型的形成与这种变化有直接的关系。不同矿石类型中的磁铁矿的生成方式虽然不同于白云岩中的磁铁矿,但前者的氧同位素继承了后者的特点,表明了它们的亲缘关系和成因上的联系。稀土分布型式表明,不同矿石类型的稀土分布型式与赋矿白云岩的大体一致,有明显的LREE富集和明显的HREE亏损,且总稀土含量越高,轻重稀土分离程度越高。但是,不同矿石类型在轻稀土含量上有一定程度的差别,表明在霓长岩化过程中轻稀土活动性更强。总之,氟、钠和铁的交代作用在主东矿最强,稀土、铌和铁资源也最为富集,这里的白云岩厚度也最大,表明白云鄂博矿的霓长岩化成矿作用与赋矿白云岩衍生的流体的大量聚集以及流体对围岩广泛强烈的交代作用直接相关。     

The Paleoproterozoic Montviel carbonatite-hosted REE–Nb deposit,Abitibi, Canada: Geology,mineralogy, geochemistry and genesis

The Montviel 250 Mt carbonatite-hosted REE–Nb deposit is hosted in a Paleoproterozoic alkaline suite located in the Sub-Province of Abitibi, in the Archean Province of the Superior. The alkaline intrusion consists of biotite clinopyroxenites, melano- to leucosyenites, a melteigite–ijolite–urtite series, riebeckite granite, a series of carbonatites and a carbonatite polygenic breccia. The carbonatite series includes silicocarbonatites, calciocarbonatites, rare magnesiocarbonatites, ferrocarbonatites and mixed carbonatites and are cut by a late, high-energy carbonatite polygenic breccia. Diamond drill hole assays and microscope observations indicate that Nb is hosted in pyrochlore from silicocarbonatite whereas the REE mineralization is mainly hosted in ferrocarbonatite, late mixed carbonatites and polygenic breccia, in REE-bearing carbonates and fluorocarbonate minerals. Diamond drill hole underground mapping and systematic assays have shed light on zones enriched in Nd and LREE with preferential Ba and Sr hydrothermal precipitation and zones enriched in Dy, Y and HREE displaying preferential F and P bearing hydrothermal precipitation. Petrographic observations, electron microprobe analyses, LA-ICPMS and X-ray diffraction were used to study the mineralization processes and to identify and quantify the REE-bearing burbankite–(Ce), carbocernaite–(Ce), ewaldite–(Y), huanghoite–(Nd), cordylite–(Ce), cordylite–(Nd), kukharenkoite–(Ce) and synchysite–(Ce). Most minerals are enriched in total LREE with values around 19.3 wt.%, have total MREE values around 2.2 wt.% and extremely variable total HREE values, with very high contents of Dy and Y averaging around 0.3 wt.% and 1.0 wt.%, respectively, and with total HREE reaching up to 10.0 wt.%. A paragenetic sequence is proposed that consists of: (1) a silicocarbonatite Nb stage, and (2) a calciocarbonatite stage, dominated by magmatism but accompanied by hydrothermal fluids, (3) a main ferrocarbonatite stage, dominated by episodes of Ba- and Sr-hydrothermalism and LREE mineralization, F- and P-hydrothermalism and HREE mineralization and evolved ferrocarbonatitic magmatism, (4) a renewed, mixed carbonatite magmatic stage with minor but increasing hydrothermalism, and (5) a terminal stage of fluid pressure buildup and explosion, leading to the creation of a HREE-enriched polygenic breccia. Globular melt inclusions of Ba–Cl–F (± Si–O) may indicate the presence and contribution of barium-bearing chlorofluoride melts during hydrothermal activity and mineralization of the carbonatite.     

REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits, Yunnan, China: Implications for the Ore Genesis

<正>The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb+Zn reserves of more than 5 million tons at Pb+Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element(REE) and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows(La)_N(Ce)_N(Pr)_N≈(Nd)_N with Eu/Eu~*1,the patch calcite has(La)_N(Ce)_N(Pr)_N≈(Nd)_N with Eu/Eu~*1,and the vein calcite displays(La)_N(Ce)_N(Pr)_N(Nd)_N with Eu/Eu~*1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ~(13) C_(PDb) andδ~(18)O_(Smow) values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ~(13)C_(PDb) vsδ~(18)O_(Smow) diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.     

甘肃干沙鄂博稀土矿床地质特征及矿床成因分析

干沙鄂博稀土多金属矿床位于北祁连加里东褶皱带东段,成矿与干沙鄂博碱性斑岩体有关。干沙鄂博斑岩体为一小型岩株,地表出露面积约0.29km^2,岩性以霓辉正长斑岩为主,其次为霓辉碱长石英正长斑岩。岩体具全岩面型蚀变矿化特征,与稀土矿化关系密切的围岩蚀变主要为萤石化、碳酸盐化和硅化。矿化范围大,矿带长约800m,延深大于420m,5个主矿体长70-260m,平均厚度12-29m。矿石品位较低,稀土氧化物平均品位1.39%-1.65%,矿石中伴生金属元素有Cu、Pb、Mo。矿石矿物以氟碳钙铈矿为主,其他金属矿物有黄铜矿、方铅矿、斑铜矿及辉钼矿等。含矿斑岩体为一套准铝质和碱性岩石,总体具有高硅低钛、富钾低钠的特点。岩石富集K、Rb、Sr、Ba等不相容元素,亏损Ta、Nb、Zr、Ti等高场强元素;轻重稀土分馏强烈,显著富集轻稀土,具Eu负异常。以上地球化学特征表明干沙鄂博碱性斑岩体的成因可能与华力西晚期后造山伸展环境下富集地幔的部分熔融有关,并经历了显著的分离结晶作用。通过与国内外典型稀土矿床的对比分析认为,干沙鄂博稀土矿矿床成因类型为碱性斑岩岩浆期后热液型多金属稀土矿床,与冕宁牦牛坪和美国加里诺斯稀土矿的矿床成因类似。     

REE fractionation,mineral speciation,and supergene enrichment of the Bear Lodge carbonatites,Wyoming, USA

The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing δ¹⁸O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO₄³⁻/CO₃²⁻ and F⁻/CO₃²⁻ ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.     

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。     

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.     

白云鄂博地区碳酸岩脉侵位序列与稀土元素富集机制

白云鄂博地区发育大量的火成碳酸岩脉。按照矿物组成,碳酸岩脉可分为白云石型、白云石-方解石共存型和方解石型。野外穿插关系表明,白云石型碳酸岩脉形成得早,而方解石型碳酸岩脉形成得晚。白云鄂博地区的碳酸岩浆存在由白云石型到共存型再到方解石型的先后结晶顺序和演化趋势。碳酸岩脉的主量、稀土和微量元素组成特征表明,随着碳酸岩脉中方解石矿物组分的增加,轻稀土元素的含量呈明显富集趋势,而长期的结晶分异作用正是稀土元素,尤其是轻稀土元素在晚期岩浆中强烈富集的内在机制。     

Geochemical characteristics of the Bayan Obo giant REE–Nb–Fe deposit: Constraints on its genesis

Geochemical characteristics of different dolomites in the Bayan Obo giant REE–Nb–Fe deposit in Inner Mongolia have been studied. Intensively REE-mineralized dolomites (total REE over 800 ppm) show similar geochemical characteristics to associated carbonatite dykes, with Ba, Th, REE enrichments and Sr, Nb, Ti, Cu depletions, which is different from those of dolomites in the deposit with low REE contents (total REE less than 800 ppm). The low REE dolomites display some transitional characteristics between carbonatite dyke and sedimentary carbonate, with La depletion and Nb enrichment. This indicates that the genesis of the REE-mineralized dolomites might be related to both carbonatite magma and sedimentary carbonates. Sulfur isotope data indicates two sulfur sources, a mantle source (δ³⁴S c.a. 0‰) and seawater (δ³⁴S c.a. +25‰). It is proposed that mineralized dolomites in the Bayan Obo giant REE–Nb–Fe deposit are the product of sedimentary carbonate hydrothermally metasomatised by carbonatite magma and/or associated fluids. These dolomites formed the large-scale rare earth mineralization in the unique Bayan Obo REE–Nb–Fe deposit.     

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.     

白云鄂博含矿碱性火山岩建造及其地球化学

白云鄂博矿床历经几十年的研究,主要集中在矿区H8岩性段矿化白云岩成因的认识,许多研究显示含矿白云岩是岩浆碳酸岩,本文主要从岩石学和地球化学方面进一步分析其属于火山喷发环境形成的火山碳酸熔岩。H8含矿白云岩段和H9板岩段作为一套含矿岩系主要由含矿白云岩、霓闪钠长岩、钾长板岩3类岩石组成,白云岩和霓闪钠长岩都具有的碎屑结构及角砾状构造、条带构造,显示为火山熔岩和火山碎屑岩特征,而钾长板岩则主要显示致密微晶火山熔岩特征。工业矿物主要是磁铁矿、赤铁矿、稀土矿物和铌铁矿物,其重要特征是出现大量原生赤铁矿,反映岩石氧化系数高,与火山喷发环境一致。霓闪钠长岩、钾长板岩岩石化学显示碱性特征,稀土元素与CaO、F相关系数在0.7以上,并与Fe2O3高氧化物相关,而与硅酸盐矿物组分反相关,表示碳酸岩与稀土成矿密切相关,并显示为表生氧化环境形成。稀土地球化学特征显示白云岩∑REE最高,钾长板岩∑REE最低,相应的岩脉∑REE低于喷发岩。各种岩石均表现为明显的轻重稀土分异,但是以白云岩LREE/HREE比值最大,霓闪钠长岩LREE/HREE比值最小,而纯钠长石岩脉和含稀土磁铁矿LREE/HREE明显高于其他岩石。白云岩和霓闪钠长岩均表现出不同的铕、铈负异常,但是碳酸岩脉和钾长板岩则显示弱正铈异常,霓闪钠长岩和钾长板岩铕异常不明显。矿化白云岩和碳酸岩脉的δ18O、δ13C值介于沉积灰岩与已知碳酸岩的δ18O、δ13C值之间,碳酸岩中白云石的δ18O低于方解石的δ18O,而δ13C高于方解石的δ13C,稀土矿物的δ13C、δ18O与碳酸岩脉δ13C、δ18O接近。归纳这些特征,含矿白云岩与霓闪钠长岩、钾长板岩是碱性火山岩组合,与一系列同期的碳酸岩、霓闪钠长岩碱性岩脉一起,构成一套完整碱性火山岩系。