牦牛坪矿-(Ce):一种新发现的稀土元素矿物

牦牛坪矿- (Ce)属硅钛铈矿亚族的新成员,发现于四川牦牛坪稀土矿床的碳酸岩、伟晶碳酸岩和碱性岩等矿脉中。与已知的同亚族矿物相比,新矿物要么是chevkinite - (Ce)B位上的Fe3 + 类似物,要么同时是polyakovite- (Ce)B位和C位上的Fe3 + 类似物。牦牛坪矿- (Ce)直接从一类富F、水和REE的岩浆 热液过渡阶段的成矿流体中结晶所成。新矿物得名于产地和稀土元素中Ce居优。牦牛坪矿- (Ce)及其命名,已获国际矿物协会新矿物及矿物命名委员会投票批准。     

牦牛坪矿-(Ce):一种新发现的稀土元素矿物

牦牛坪矿-(Ce)属硅钛铈矿亚族的新成员,发现于四川牦牛坪稀土矿床的碳酸岩、伟晶碳酸岩和碱性岩等矿脉中.与已知的同亚族矿物相比,新矿物要么是chevkinite-(Ce)B位上的Fe3 类似物,要么同时是polyakovite-(Ce)B位和C位上的Fe3 类似物.牦牛坪矿-(Ce)直接从一类富F、水和REE的岩浆-热液过渡阶段的成矿流体中结晶所成.新矿物得名于产地和稀土元素中Ce居优.牦牛坪矿-(Ce)及其命名,已获国际矿物协会新矿物及矿物命名委员会投票批准.     

C2/m丁道衡矿-(Ce)的发现与研究

丁道衡矿-(Ce)是在白云鄂博REE-Nb-Fe矿发现的一种新的稀土元素矿物,被视为是真正的珀硅铈钛矿(Perrierite)的同质多象体和硅钛铈矿(Chevkinite)亚族C(1)位上的钛类似物。同时,它还是自然界发现的首例硅钛铈矿亚族具P21/a空间群的天然产物。之后,在攀枝花V-Ti-Fe矿红格矿区找到一种几可全方位同白云鄂博产原型丁道衡矿-(Ce)对比,但空间群为C2/m的丁道衡矿-(Ce)变体,并作了全面、系统的矿物学研究。自此,参照先例,攀枝花产具C2/m空间群的丁道衡矿-(Ce)宜称C2/m丁道衡矿-(Ce);而白云鄂博原型丁道衡矿-(Ce)宜称P21/a丁道衡矿-(Ce)。C2/m丁道衡矿-(Ce)的发现与研究揭示,已有的硅钛铈族矿物何以具有C2/m变体和P21/a变体的成因解释,尚不能圆满诠释2种变体的形成。     

牦牛坪稀土矿区氟碳铈矿与氟碳钙铈矿矿物学

四川省牦牛坪稀土矿区钙稀土氟碳酸盐矿物有氟碳铈矿、氟碳铈矿以及笔者发现并命名的牦牛矿。本文旨在简述氟碳铈和氟碳钙铈矿的矿物学特征。牦牛坪钙稀土氟酸盐类矿物具有强选择轻稀土的特点。     

钡-稀土氟碳酸盐族矿物的研究

近几年来,在我国先后发现了一系列钡-稀土氟碳酸盐族矿物——黄河矿、氟碳钡铈矿和氟碳铈钡矿,其中氟碳铈钡矿为最近在我国发现的一种新矿物。本族矿物,由于非常稀少,自1900年G.弗林克(Flink)于格陵兰南部纳萨苏克(Narsarsuk)的碱性伟晶岩中     

Crichtonite族矿物在我国的研究进展与冕宁铀矿的发现

回顾了锶铁钛矿(crichtonite)族矿物在我国的研究历史,从产状、物理性质、化学成分以及晶体结构等方面重点介绍了锶铁钛矿族新成员——冕宁铀矿。锶铁钛矿族矿物属三方晶系,结构通式为A~ⅫB~ⅥC_(18)~ⅥT_2~Ⅳ(Φ)_(38)。冕宁铀矿是锶铁钛矿族第15个成员,产自牦牛坪稀土矿包子山煌斑岩破碎带中(N28°24'20″,E101°59'3″),经验化学式为[□_(0.322)(Pb_(0.215)Ba_(0.037)Sr_(0.036)Ca_(0.010))_(0.298)(Ce_(0.128)La_(0.077)Nd_(0.012))_(0.217)(Na_(0.127)K_(0.036))_(0.163)]_(1.000)(U_(0.447)~(4+)Mn_(0.293)U_(0.112)~(6+)Y_(0.091)Zr_(0.023)Th_(0.011))_(0.977)(Fe_(1.224)~(3+)Fe_(0.243)~(2+)Mg_(0.023)P_(0.008)Si_(0.006_□_(0.496))_(2.000)(Ti_(12.464)Fe_(5.292)~(3+)V_(0.118)~(5+)Nb_(0.083)Al_(0.026)Cr_(0.017)~(3+))_(18.000)O_(38.000);晶胞参数为a=1.03462(5)nm,c=2.08372(2)nm,V=1.93165(20)nm~3,Z=3,空间群R3;晶体多呈半自形板状,粒径1~2 mm,黑色,条痕黑色,半金属光泽,不透明,性脆,贝壳状断口,解理、裂开和荧光性均不发育;莫氏硬度约为6,密度为4.62(8)g/cm~3。由于铀等放射性元素的辐射,冕宁铀矿发育有不同程度的非晶质化。冕宁铀矿是锶铁钛矿族第一个A位以空位为主的矿物种。该矿物以其产地命名,已获得了国际矿物学会新矿物及矿物分类命名委员会(CNMNC-IMA)的正式批准(IMA 2014-072)。     

新矿物丁道衡矿-（Ce）：珀硅钛铈矿的同质多象体和硅钛铈矿亚族C（1）位上的钛类似矿物

丁道衡矿-(Ce):(Ce,La)4Fe2 (Ti,Fe2 ,Mg,Fe3 )2Ti2Si4O22,理想的结构化学式Ce2Ce2Fe2 Ti2Ti2Si4O22单斜晶系,α=1.34656(15)nm,b=0.57356(6)nm,c=1.10977(12)nm,β=100.636(2)°,V=0.84239(46)nm3,空间群P21/a(假C2/m),Z=2.作为硅钛铈矿(chevkinite)族矿物的新成员,它产于举世闻名的白云鄂博铁.稀土.铌矿床镁夕卡岩中,多数单晶体长0.2～1.0 cm,最大者长大于1.5 cm.共生矿物有透辉石、透闪石、钠透闪石、褐帘石-(Ce)、磁铁矿、尖晶石、烧绿石、氟金云母、氟磷灰石、石英和萤石等.矿物具有褐色条痕和半金属一金属光泽的黑色,其褐黑色碎片半透明.性脆、具有贝壳状断口、无解理和裂开.显微硬度(VHN25g)为606.0～717.4 kg/mm/12(相当于摩氏硬度约5.9).矿物实测密度4.83(7)g/cm3,计算密度值4.88(0)g/cm3.丁道衡矿-(ce)的反射色为带灰色的浅黄色,多色性为不同色调的灰色.平均反射率(λ=589nm)为11.4%～12.5%.矿物为二轴晶负光性.作过结构精测的丁道衡矿-(Ce)晶体的电子探针测值:SiO2:19.29,TiO2:18.26,A12O3:0.04,FeO:8.49,Fe2O3,:1.67,ThO2:0.16,MgO:1.32,CaO:2.17,Nb2O5:0.47,Ta2O5:0.00,La2O3:19.53,Ce2O3:28.08,Y2O3:0.00,Na1O:0.01,总量99.46%;其中Fe3 /Fe2 的比值依穆斯堡尔谱换算.根据结构精测每个单位分子式中O=22和C(1)位上Ti优先占位,计算的矿物晶体化学式为(Ce2.13,La1.49Ca0.48Th0 01)Σ4.11Fe2 (Tin0.88Fe2 0.47Mg0.41 Fe0.0)Σ2.03(Ti1.96Nb0 04)Σ2.00(Si2O7)2O3.分别用P21/a和C2/m对丁道衡矿-(Ce)的晶体结构作了精测.结果表明,丁道衡矿-(Ce)的真空间群是P20/a.换言之,它才是真正珀硅钛铈矿[perrierite-(Ce)]的同质多象体.显而易见,硅钛铈矿族矿物既可以有P21/a空间群,又可以有C2/m空间群.     

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。     

山东金伯利岩中新发现的柱红石亚族矿物──K-Cr柱红石──上地幔含大阳离子Cr、Ti、Fe氧化物矿物研究之二

在山东蒙阴金伯利宕的副矿物蒙山矿中，首次发现了成分为柱红石类的新矿物相。对其成分进行探针分析，其一般晶体化学式可写为：A1.499～1.787B1.548～2,317C5.675～6.354O16。其中，A＝K、Ba、Na、La；B＝Cr、Fe、Mg、V；C＝Ti、Zr、Nb等，平均计算化学式为：（K1.256Ba0.241Na0.085La0.046）1.628（Cr1.817Fe0.321Mg0.085V0.093）1.816（Ti6.015Zr0.075Nb0.039）6.119O16．理想化学式K2Cr2Ti6O16；相当于Redledgeite（BaCr2Ti6O16）[1]的K端元，且与南非OrangeFree州StarMine及NewEland新发现的K－Ba－Vtitanates（钛酸盐）[2，3]具有成分上的可比性。为使柱红石亚族矿物的命名系统化，本文采用主要大阳离子（K、Ba）与变价元素（Fe、Cr、V）为端元组分的命名原则，将新种命名为K－Cr柱红石。根据国外资料对柱红石亚族矿物Redlcdgeite的成分修正[1,4]建议将其原中文译名“硅镁铝钛矿”[5,6]更正为“Ba－Cr柱红石”。新种与蒙阴近年来发现的沂蒙矿、蒙山矿一起，组成了含大阳离子及硅酸盐不相容元素的复杂钛铬铁氧化物组合，皆以K、Cr为特征，从而与南非以Ba为主，含V的这类矿物形成区域对比。     

Phosinaite,a new rare-earth mineral

Using geophysical data, we studied the mechanism of deep-seated magmatic and volcanic activity in the region of the island arcs and associated structures. Data on magmatic activity below the volcanic belt of East Kamchatka, obtained during geophysical investigations, mainly during detailed seismological investigations and deep seismic sounding, provide evidence for an association between the volcanoes and the processes in the Pacific Ocean focal layer of earthquakes, and for the accumulation of magmas below the volcanic belt at depths less than 60 km. We found anomalous columnar bodies more than 5 to 7 km across, linking the volcanoes with the focal layer, and a very large concentration of convective heat flow and volatiles in the magma columns feeding the volcanoes. As to the role of different forces in the uprise of magmas into the volcanoes, hydrostatic forces probably predominate in the asthenosphere, supplemented by tectonic pressure in the lithosphere and forces associated with boiling of magmas during release of volatiles in the crust, especially in its upper layers.—Author.     

EXAFS study of rare-earth element coordination in calcite

Extended X-ray absorption fine-structure (EXAFS) spectroscopy is used to characterize the local coordination of selected rare-earth elements (Nd³⁺, Sm³⁺, Dy³⁺, Yb³⁺) coprecipitated with calcite in minor concentrations from room-temperature aqueous solutions. Fitting results confirm substitution in the Ca site, but first-shell Nd-O and Sm-O distances are longer than the Ca-O distance in calcite and longer than what is consistent with ionic radii sums for sixfold coordination in the octahedral Ca site. In contrast, first-shell Dy-O and Yb-O distances are shorter than the Ca-O distance and are consistent with ionic radii sums for sixfold coordination. Comparison of Nd-O and Sm-O bond lengths with those in lanthanide sesquioxides and with ionic radii trends across the lanthanide series suggests that Nd³⁺ and Sm³⁺ have sevenfold coordination in a modified Ca site in calcite. This would require some disruption of the local structure, with an expected decrease in stability, and possibly a different charge compensation mechanism between Nd and Sm vs. Yb and Dy. A possible explanation for the increased coordination for the larger rare-earth elements involves bidentate ligation from a CO₃ group. Because trivalent actinides such as Am³⁺ and Cm³⁺ have ionic radii similar to Nd³⁺, their incorporation in calcite may result in a similar defect structure.     

The luminescence properties of rare-earth ions in natural fluorite

For the first time, the luminescence properties of Pr³⁺, Nd³⁺ and Tm³⁺ and Yb³⁺ ions in fluorite crystal have been obtained by steady-state measurements. In addition, the luminescence spectra of Ce³⁺, Sm²⁺, Sm³⁺, Dy³⁺, Er³⁺ and Yb³⁺ were measured. It was pointed out that λ_exc.?=?415?nm is most suitable for measuring the Ho³⁺ emission beside the Er³⁺. The emission of trivalent holmium and erbium ions was measured independently using time-resolved measurements and tentative assignment of luminescence lines to C _3v and C _4v symmetry sites was proposed. Besides for natural fluorite crystal, the transitions between Stark energy levels of lanthanide ions were presented.     

Fine structures of mutually normalized rare-earth patterns of chondrites

REE abundances in ten chondrites (nine falls and one find) were determined very accurately by mass-spectrometric stable isotope dilution techniques. All of the chondrites have different relative and absolute REE patterns. Except for Eu and, rarely, for Ce, the REE abundances in chondrites are smoothly fractionated from sample to sample. Notwithstanding differences in the abundances of common REE, four of five L6 chondrites have very similar absolute Eu abundances; their mutually-normalized REE patterns are not curved, but are composed of two rectilinear segments.The Leedey-normalized REE pattern for St. Séverin (LL6) is composed of two concave curves. Yonozu's (H4,5) pattern shows negligibly concave curvature on both sides of Eu. Kesen's (H4) pattern is unusual in its overall pattern but also in irregularities for particular elements. The irregularity may be connected with the unusually high vapor pressure of metallic Yb. The REE pattern for the Allende bulk sample shows a discontinuity, presumably reflecting its considerable heterogeneity of composition and structure. It is evident that any pattern of ordinary chondrites cannot be produced from the Allende bulk pattern. A comparison is also made with the results on the chondrite composites previously investigated.     

白云鄂博REE—Fe—Nb矿床稀土氟碳酸盐矿物激光拉曼光谱特征及流体包裹体内稀土子矿物的鉴定

白云鄂博REE－Fe-Nb矿床典型稀土氟碳酸盐矿物都具有碳酸根离子最特征的拉曼振动频率，并普遍出现有氟化物的拉曼光谱振动峰。利用子矿物的激光拉曼峰特征，结合矿物晶形和扫描电镜能谱分析结果，可以确定这些矿物可能为氟碳铈矿和氟碳铈钡矿，说明初始成矿热液中极富含稀土元素，矿脉内多相包裹体中含稀土元素的子矿物是从被包裹体捕获的流体中结晶出来的，是真正的子矿物，激光拉曼光谱仪可以作为鉴定流体包裹体中未知子矿物的较为可靠手段之一。     

Mobility of rare-earth elements and copper during shear-zone-related retrograde metamorphism

In Mid Proterozoic crystalline rocks of the Mount Isa Inlier, around Cloncurry, Australia, 2000 km² of alteration and brecciation are the product of high-temperature (> 450 °C) concentrated saline solution activity. During retrogression, this fluid was locally responsible for mobility of V, Y, Nb and light rare-earth elements (15 × enrichment). Copper and S were leached during alteration and this may have been a significant source of components in nearby Cu-Au deposits. Similar rare-earth-element behaviour has been observed in the hematite breccias which host Cu-sulfides at the giant Olympic Dam Cu-Au deposit.     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

Aqueous geochemistry of rare-earth elements in karst lakes, southwestern China

Due to the unique chemical properties that are similar but still progressively change, the rare earth elements （REEs） are useful tracers of various geochemical processes in the lithosphere and hydrosphere. However, despite many studies of REE geochemistry in the ocean, the aqueous geochemistry of REEs in lake waters has been poorly documented. In the present study, two special karst lakes are chosen as case studies to investigate the distributions of dissolved REEs in lake water. Although the two lakes, Hongfeng and Aha, are both alkaline and have high pH from 7.9 to 8.7 and high carbonate concentrations, the Aha Lake has been more severely affected by acidic mining drainage with high Fe, Mn and SO42 concentrations. In the present study, the concentrations of dissolved rare-earth elements in lake waters were determined by inductively coupled plasma mass spectrometry. The result shows that the concentrations of dissolved REEs in the studied alkaline karst lakes, as compared to the concentrations of REEs in seawater, are much lower than the other investigated terrestrial surface waters in previous studies. The key factor controlling dissolved REE distributions is pH value which is negatively correlated with REE concentrations. Due to high concentration of carbonate ion and alkaline character of water chemistry, the shale （PAAS） normalized patterns of dissolved REEs show marked HREE enrichment in all water samples. This is primarily the result of the preferential formation of stronger carbonate complexes with the HREEs. In alkaline or intermediate waters, REE-carbonate complexes are the dominant and typical species, which account for about more than 90% of the total dissolved REEs.