BPR螯合树脂分离偶氮胂Ⅲ光度法测定岩石中微量锆（铪）

在酒石酸介质中,BPR螯合树脂可选择性地吸附Zr、Hf、Nb、Ta而与岩石中常见的伴生元素如Fe、Al、Ca、Mg、Cu、Pb、Cd、Co等以及U、Th、Sc等微量元素分离。Zr、Hf、Nb、Ta均可被2-4mol/LHCI溶液洗脱。在此基础上提出了一个测定岩石中微量Zr(Hf)的新方法。     

小兴安岭二龙山林场堆晶辉长岩地球化学特征及构造环境

小兴安岭北部二龙山林场辉长岩的主量、微量和稀土元素的测试分析结果显示: 二龙山辉长岩为钙碱性系列、偏铝质岩石; δEu 正异常,Sr 元素含量富集明显,具有堆晶辉长岩特征; Rb /Sr、Nb / Ta、LILE/HFSE、Th /Ta、Nb /U 和Nb /La 比值特征均显示,辉长岩岩浆来自受到俯冲流体交代的地幔源区。Nb /Zr、Th /Nb、Th /Ta 和Ta /Hf 比值特征及对Th /Hf --Ta /Hf 构造环境判别图解投点表明,二龙山辉长岩形成于陆内拉张环境。     

青海泽库赛日迪印支期中基性岩体地球化学特征及构造背景

青海泽库东南赛日迪附近产出的印支期中基性岩体前人研究较少.对该岩体进行地球化学、构造背景及岩浆演化方面研究,结果表明,赛日迪岩体硅量中等、高镁铁、低铝、低钾钠,属准铝质钙碱性系列.富集Rb,K,Pb等大离子亲石元素(LILE)和Th,U,Ta,Nb,Hf等高场强元素(HFSE).普遍贫Ba,Sr等大离子亲石元素(LILE)和P,Zr,Ti等高场强元素(HFSE).稀土元素含量较低,轻稀土元素相对富集,轻稀土元素较重稀土元素分馏明显.Eu略显负异常,表现为同源岩浆成分特征.LREE与SiO2相关性不强,Nb/U、Nb/La远低于全球MORB、OIB值,Nb/Ta和Zr/Hf与原始地幔值相当,低Sm/Yb值,La/Nb和La/Ta指数指示赛日迪中基性岩可能为地幔源,岩浆经历部分熔融岩浆演化过程,上升过程中未受地壳物质混染.构造环境判别赛日迪中基性岩为钙碱性玄武岩,形成于板内环境,与板块碰撞作用有一定联系.     

超高压榴辉岩金红石中高场强元素变化的控制因素及其地球动力学意义

利用LA-ICP-MS对CCSD-MH超高压榴辉岩中金红石进行了详细的原位微区微量元素组成分析.金红石中高场强元素Nb和Ta含量主要受全岩Nb、Ta和TiO₂含量控制, Zr、Hf含量比较稳定基本不受全岩含量影响.粒间金红石中, 同一颗粒金红石核部Zr含量系统高于边部, 而边部则出现了明显的Pb和Sr富集特征.CCSD-MH榴辉岩中金红石与全岩的Nb/Ta比值呈现明显的不一致性.全岩Nb/Ta比值明显低于金红石且与全岩TiO₂含量负相关, 而金红石的Nb/Ta比值与全岩Nb、Ta含量和Nb/Ta比值没有明显的相关关系.金红石和全岩之间非完全耦合的Nb/Ta组成表明, 金红石并非形成于原岩的结晶过程中而是在超高压变质作用过程中形成, 尽管金红石是榴辉岩中Nb、Ta含量的主要载体矿物, 但金红石的Nb/Ta比值并不一定能完全代表全岩的特征, 而与全岩Nb、Ta和TiO₂的含量有关.粒间金红石核部Zr含量所记录的温度与粒径之间具有明显的正相关性, 反映金红石中的Zr在其形成后没有封闭.粒间金红石所表现出的明显的边部富集Pb和Sr的特征, 反映了后期流体活动对金红石组成的影响.这些研究结果为金红石中Zr在高温下的扩散作用和后期流体活动的影响提供了重要证据, 这可能是利用金红石Zr含量地质温度计计算的苏鲁-大别榴辉岩变质温度(598~827℃) 偏低的主要原因.      

黔中猫场铝土矿地球化学研究

猫场铝土矿位于黔中清镇—修文铝土矿区,矿体产于下石炭统九架炉组,上覆摆佐组白云岩,下伏中上寒武统娄山关群白云岩,矿床成因类型为古风化壳沉积型.为了探讨猫场铝土矿成矿环境和成矿物质来源,为猫场矿区乃至黔中地区铝土矿资源的开发利用提供基础研究资料,我们对矿区铝土矿、顶底板铝土岩或粘土岩及围岩白云岩进行了主量元素、微量元素和稀土元素地球化学研究.结果显示,矿石成分主要为Al2O3、SiO2、Fe2O3和TiO2,含矿岩系富集Li、V、Ga、Sc、Nb、Ta、Th、Hf、Zr、Y和REE等微量元素.微量元素含量和比值(Th、Sr/Ba、Th/U)分析表明,矿区铝土矿形成于海陆交替的沉积环境,以陆相沉积为主,成矿过程为氧化还原交替的沉积环境.通过稳定元素(Al2O3/TiO2、Al2O3/Zr、TiO2/Nb、Zr/Nb、Zr/Ta、Zr/Hf和Ta/Nb)相关性分析和稀土球粒陨石标准化配分模式判断,矿区物源可能为下伏中上寒武统娄山关群白云岩.     

川西可尔因地区伟晶岩型锂矿地球化学指标定位矿体的方法

可尔因地区是松潘?甘孜成矿带的大型稀有金属矿集区之一,围绕可尔因岩体分布了大量花岗伟晶岩脉,如何在数百平方千米伟晶岩田中定位稀有金属矿脉一直是该区伟晶岩型锂稀有金属矿找矿难点之一。通过对可尔因岩体二云母花岗岩、伟晶相微斜钠长花岗岩、不同类型伟晶岩及典型矿床开展系统的岩石地球化学分析,总结了可尔因地区伟晶岩地球化学元素空间分布和变化规律,提出了寻找锂矿的特征元素指标、指示指标和品位指标等地球化学指标。特征元素指标包括Li、B、Sn、Rb、Be、Nb、Ta等元素;平面指示指标包括Cs、Tl、F、Zr、Y、ΣREE等元素及TiO₂/Ta、Zr/Hf、Ta/Zr、Nb/Ta、K/Na等值;垂向指示指标包括B、U、Zr、Be、Sn、Rb、Sr、Ba、Tl、In等元素。通过特征元素指标及指示指标的值和变化规律,可辅助定位稀有金属矿化伟晶岩位置,指示矿体深部延伸情况。品位指标主要包括铝饱和指数（A/CNK、A/NK）、里特曼指数（σ）、K+Na和K/Na值等,Li品位与铝饱和度呈正相关、与碱度呈负相关,品位指标的变化趋势指示了矿体中锂的富集部位。      

西天山特克斯县北乌孙山大哈拉军山组火山岩地球化学特征及构造意义

对西天山特克斯西北乌孙山中部地区出露的火山岩进行了地球化学研究,结果表明玄武岩、安山岩均为拉斑质火山岩,LREE较富集[(La/Yb)N介于3.44~11.36之间],具有弱的Eu负异常(δEu=0.79~1.13),安山岩与流纹岩明显富集强不相容元素(如Cs、Rb、Ba、Th、U)和LREE。玄武岩与中酸性岩样品具有轻微的差异,但所有样品具有较明显的Nb、Ta、Ti负异常,并且除了活动性较强的元素(Cs、Rb、Ba)外,其余微量元素均接近于下地壳的含量,(Th/Nb)N介于2.02~8.12之间,(Nb/La)N介于0.40~0.45之间,远远小于1,La/Ba值低(0.01~0.07),Ba/Nb值高(90~410);Zr/Nb值平均为16.48,最为接近原始地幔(15.71)的比值;而Ta/Nb、Hf/Ta、Th/Yb值平均为0.10、3.77、0.64,较为接近上地壳(0.10、3.50、0.48)的比值,Zr含量大于90×10-6,Zr/Y值在4左右,显示了板内玄武岩的特征。结合区域上地质特征,认为该地区在石炭纪时碰撞结束进入碰撞后伸展阶段,局部具有裂谷化特征。样品的Nb、Ta、Ti负异常应为地壳混染引起,火山岩的形成环境为碰撞后伸展的构造环境。     

新疆博格达东缘色皮口一带辉绿岩地球化学、锆石U-Pb年龄及地质意义

博格达造山带内出露的晚石炭世辉绿岩,为研究博格达裂谷演化末期地球动力学背景提供了重要信息.色皮口地区辉绿岩主量元素以低TiO2、较高Al2O3、较低MgO、贫P2O5,较低的K2O/Na2O比值(0.12~0.53),ΣREE较高,LREE/HREE为2.45~3.56,铕负异常不明显(δEu=0.82~1.02)等为特征.与原始地幔相比,其不相容元素K,Rb, U,Ba富集,高场强元素Nb,Ta,Zr,Hf无富集,Ti亏损不明显,Nb,Ta,Th表现为明显负异常.U富集可能指示与地壳物质的加入有关,较低的Nb/Zr比值(0.02~0.06),暗示岩浆源区可能为受地壳混染的亏损地幔.辉绿岩LA-ICP-MS锆石U-Pb定年结果为(300.5±1.7) Ma(MSWD=2.3,Th/U比值为0.36~1.3),为晚石炭世晚期,代表了博格达裂谷闭合后地球动力学环境由挤压变为拉张的转折期.     

佛冈高分异I型花岗岩的成因:来自Nb-Ta-Zr-Hf等元素的制约

华南南岭地区发育有大面积的与钨锡成矿相关的侏罗纪花岗岩,然而其中有些花岗岩的成因类型却难以确定。本文以佛冈岩体为例,结合前人已发表数据,对佛冈花岗岩体中Nb、Ta、Zr和Hf等元素的迁移特征及其原理进行探讨,并对佛冈花岗岩的成因类型进行了厘定。随着分异程度增加,佛冈花岗岩Nb和Ta含量增加,Nb/Ta(3.6~15.3)和Zr/Hf(17.3~38.9)比值降低并发生分异。随着Zr含量的降低,佛冈花岗岩的Zr/Hf比值降低,这一特征表明锆石的分离结晶作用使得佛冈花岗岩的Zr/Hf比值分异。Nb/Ta比值分异可能与角闪石和黑云母的分离结晶作用有关。随着Nb/Ta比值降低,Y/Ho比值增加,这一特征表明佛冈花岗岩Nb/Ta比值的分异也和岩浆演化后期的流体有关。佛冈花岗岩不含原生的富铝矿物,为准铝质到弱过铝质岩石。随着分异程度增加,佛冈花岗岩P2O5含量降低,表明它不是S型花岗岩。随着Y/Ho比值增加和Nb/Ta和Zr/Hf比值降低,佛岗花岗岩Ga/Al和Fe OT/Mg O比值增加,从典型I型花岗岩特征演化到类似A型花岗岩的地球化学特征。因此,我们认为佛冈花岗岩不是A型花岗岩而是高分异的I型花岗岩。区域上与成矿相关的流体和花岗质岩浆的相互作用和分离结晶作用,使得华南南岭地区的花岗岩地球化学特征复杂,所以其成因类型也变的难以确定。     

南秦岭城口火山岩锆石LA-ICP-MS U-Pb定年和地球化学研究

南秦岭大巴山城口断裂带出露一套玄武安山岩、安山岩组合,火山岩锆石LA-ICP-MS U-Pb定年测试结果为716±4Ma,表明其为新元古代岩浆产物;岩石地球化学研究表明火山岩富集轻稀土元素,原始地幔标准化微量元素蛛网图显示以富集大离子亲石元素Cs、Ba、Th、U及高场强元素分异为特征,Nb、Ta强烈亏损以及低的Ti(Ti O_20.85%)含量,与典型的岛弧火山岩相似;微量元素La/Nb、Th/Yb及Hf/Ta比值特征也显示岛弧岩浆属性,相对高的Zr/Y、Ta/Yb和低的Zr/Nb比值区别于大洋岛弧火山岩,具有明显的大陆亲缘性,表明城口火山岩形成于陆缘岛弧环境。综合已有的地质、地球化学及同位素年代学研究表明新元古代晚期扬子板块北缘及南秦岭地区为一活动陆缘岩浆杂岩弧,暗示中国华南板块很可能位于Rodinia超大陆的边缘部位。     

Geochemistry and Radioactive Potentiality of Um Naggat Apogranite, Central Eastern Desert, Egypt

Abstract: The northern part of Um Naggat granite massif (UNGM) has suffered extensive post-magmatic metasomatic reworking which results into the development of (Zr, Hf, Nb, Ta, U, Th, F)– and albite-enriched and greisenized apogranite body (UNAP) of 600 m thick, and more than 3 km in the strike length.
Albitization produced an enrichment in Zr (av. 2384 ppm), Hf (61), Nb (419), and U (43). The Th/U ratio ranges between 1. 33 and 1. 90. Extreme albitization (i. e. the albitite rock) is characterized by sharp decrease in the rare metals contents. However, extreme greisenization (i. e. endogreisen bodies) is characterized by a considerable enrichment in Zr (av. 5464 ppm), Hf (143), Nb (2329), Ta (152), U (66) and Th (178). The Th/U ratio ranges between 1. 57 and 3. 60. In contrast to extreme greisenization, it seems that extreme albitization does not apparently change the fluid pH and therefore poor amounts of rare metals are localized in the albitites.
It is suggested that the presence of Na⁺, H⁺ and F^- in the ore fluids was essential to stablize complexes of Zr, Hf, Nb, Ta, U, Th, and HREE during extraction and transportation. In contrast, contemporaneous decrease of temperature and increasing pH due to decreasing pressure are considered the essential factors for localization of disseminated mineralization of Zr and Nb in the apical parts of the UNAP. The enhanced uranium content in the alteration facies of UNAP coupled with the absence of significant uranium mineralization may indicate the metalliferous rather than mineralized nature for the UNAP. The high uranium contents are stabilized in refractory accessory minerals. However, with repect to Zr and Nb, the UNAP especially the albitized and greisen facies, can be categorized as a mineralized productive granite.     

丹宁棉分离富集—发射光谱法同时测定地质样品中微量铌钽锆铪

采用丹宁棉对地质样品溶液中的铌、钽、锆、铪进行分离富集，将写信后的丹宁棉在600℃灼烧30min，灰分用发射光谱法同时测定四元素。检出限与通常的发射光谱法相比降低约2个数量级，经国家级标准物质检验，结果与标准值相符，精密度试验，各元素的RSD（n＝20）为2.6％－7.9％。     

THE GEOCHEMISTRY OF TANTALUM AND NIOBIUM

Ta and Nb are associated in nature. Both are oxyphile and are related geochemically to Fe, Mn, Ti, rare earths U, Th, Zr, W, Sn, Bi, and Sb. Both accompany the alkali metals,especially Na and Li. Their close relationship explains their isomorphism in mineral-forming processes. Zr, W, and Sn entrain Ta and Nb in the crystal lattices of their minerals in limited amounts. The concentration of Ta and Nb increases in the course of magma evolution from ultrabasic to alkalic. Nb predominates over Ta in the main kinds of rocks by from 5:1 to 17:1. Only in granite pegmatites is Ta dominant. In granitic rocks Ta and Nb are associated with Fe, Mn, Bi, Sb, W, and Sn. In granosyenitic complexes they form complex minerals with Ti, rare earths of the Y subgroup, U, and Th. Concentrations of Ta and Nb in granitic and granosyenitic complexes increase toward the end of the magmatic and pegmatitic processes, and afterward diminish toward the end of the pneumatolytic-hydrothermal processes. In alkalic complexes Ta and Nb are associated with Ti, rare earths of the Ce group, and Th. Concentrations of Ta and Ni in alkalic massifs are caused by magmatic differentiation. In alkalic ultrabasic complexes, in magmatic and pegmatitic processes, Ta and Nb do not form independent minerals but enter into minerals of Ti and Fe, i. e. perovskite, titanomagnitite, and pyroxenes. --M. Russell.     

Biogeochemical behavior of Ampelozizyphus amazonicus Ducke in the Pitinga mining district, Amazon, Brazil

The vegetal species Ampelozizyphus amazonicus Ducke (Rhamnaceae Family) was chosen as a sampling medium for the lateritic surfaces of the Pitinga Mine in the Amazon region, in order to study the biogeochemical behavior of this species and compare it with the chemical composition of a reference plant. The Pitinga mining district is one of the largest producers of tin in the world. This district contains unique deposits of cryolite and rare metals such as Zr, Nb, Ta, Y and REEs related to granitic bodies that intrude into the volcanic and acid pyroclastic rocks. The results showed that the species A. amazonicus predominantly concentrates significant levels of Zr, Nb, Ta, Th, Be, Sc over U, Hf, Ga and In. These elements are characteristic of the mineral paragenesis for the region, suggesting that this plant can provide a representative sampling medium future geochemical exploration programs in the region.     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

X射线荧光光谱法同时测定地质样品中铌钽锆铪铈镓钪铀等稀有元素

采用粉末压片法制样,选用标准样品,以经验α系数和散射线内标法校正基体效应和元素谱线重叠干扰,使用ZSXPrimusⅡX射线荧光光谱仪对一般地质样品中的铌、钽、锆、铪、铈、镓、钪、铀等稀有元素进行测定,分析结果与标准值和参考值吻合,12次测定的相对标准偏差(RSD)小于10%。     

Mechanisms of Archean crust formation inferred from high-precision HFSE systematics in TTGs

It has been proposed that Archean tonalitic-trondhjemitic-granodioritic magmas (TTGs) formed by melting of mafic crust at high pressures. The residual mineralogy of the TTGs (either (garnet)-amphibolite or rutile-bearing eclogite) is believed to control the trace element budget of TTGs. In particular, ratios of high-field-strength elements (HFSE) can help to discriminate between the different residual lithologies. In order to place constraints on the source mineralogy of TTGs, we performed high-precision HFSE measurements by isotope dilution (Nb, Ta, Zr, Hf) together with Lu-Hf and Sm-Nd measurements on representative, ca. 3.85-2.8 Ga TTGs and related rock types from southern West Greenland, W-India and from the Superior Province. These measurements are complemented by major and trace element data for the TTGs. Texturally homogeneous early Archean (3.85-3.60 Ga old) and Mesoarchean (ca. 3.1-2.8 Ga old) TTGs have both low Ni (<11 ppm) and Cr contents (<20 ppm), indicating that there was little or no interaction with mantle peridotite during ascent. Ratios of Nb/Ta in juvenile Eoarchean TTGs range from ca. 7 to ca. 24, and in juvenile Mesoarchean TTGs from ca. 14 to ca. 27. Even higher Nb/Ta (14-42) were obtained for migmatitic TTGs and intra-crustal differentiates, most likely mirroring further fractionation of Nb from Ta as a consequence of partial melting, fluid infiltration and migmatisation. In the juvenile TTGs, positive correlations between Nb/Ta and Gd/Yb, La/Yb, Sr/Y, Zr/Sm and Zr/Nb are observed. These compositional arrays are best explained by melting of typical Isua tholeiites in both, the rutile-bearing eclogite stability field (>15 kbar, high Nb/Ta) and the garnet-amphibolite stability field (10-15 kbar, low Nb/Ta). With respect to the low end of Nb/Ta found for TTGs, there is currently some uncertainty between the available experimental datasets for amphibole. Independent of these uncertainties, the TTG compositions found here still require the presence of both endmember residues. A successful geological model for the TTGs therefore has to account for the co-occurrence of both low- and high-Nb/Ta TTGs within the same geologic terrane. An additional feature observed in the Eoarchean samples from Greenland is a systematic co-variation between Nb/Ta and initial εHf(t), which is best explained by a model where TTG-melting occured at progressively increasing pressures in a pile of tectonically thickened mafic crust. The elevated Nb/Ta in migmatitic TTGs and intra-crustal differentiates can shed further light on the role of intra-crustal differentiation processes in the global Nb/Ta cycle. Lower crustal melting processes at granulite facies conditions may generate high-Nb/Ta domains in the middle crust, whereas mid-crustal melting at amphibolite facies conditions may account for the low Nb/Ta generally observed in upper crustal rocks.