阿尔泰可可托海3号脉伟晶岩型稀有金属矿床云母和长石的矿物学研究及意义

可可托海3号脉伟晶岩型稀有金属矿床是阿尔泰造山带产出的规模最大的伟晶岩脉,其完美的同心环状结构分带举世闻名。云母和长石作为3号脉9个结构带的贯通性矿物,由外向内表现不同的结构和成分特征。其中,云母由白云母系列向锂云母系列演化,白云母呈黄-绿色中细粒→白色或绿色中粗粒-巨晶→白色或绿色书状集合体→白色或绿色中粗粒-巨晶,锂云母呈玫瑰紫中细粒鳞片状或楔状集合体,BSE图像下云母表现出成分分带及不平衡和交代结构;长石主要为钾长石和钠长石,及少量斜长石,钾长石主要呈块体产出,钠长石呈细粒→叶片状→薄片状产出。本次研究通过电子探针(EMPA)和激光剥蚀等离子质谱(LA-ICP-MS)获得3号脉各结构带云母和长石的主微量成分。3号脉云母具有高Li(249×10^-6~35932×10^-6)、Rb(1240×10^-6~22825×10^-6)、Cs(35.9×10^-6~13980×10^-6)、Ta(13.3×10^-6~447×10^-6)含量、低K/Rb值(4.23~59.4)和K/Cs值(6.53~2368),钾长石具有低K/Rb值(35.4~1865),且由外向内,随K/Rb值降低,云母的Li、Rb、Cs、F、Ta含量升高,表明3号脉是一个由外向内结晶的分异演化程度较高的伟晶岩脉。另外,连续相邻结构带中云母和长石的主微量成分呈振荡变化,该现象主要受熔体不混溶过程的控制,也受矿物结晶不平衡影响,而熔体不混溶过程也是控制3号脉结构分带的机制之一。外部带(I-IV带)和内部带(V-VIII带)的云母和碱性长石在成分(FeO、Li、Rb、Cs、F、Ta含量和K/Rb值及K/Cs值)和结构(不平衡和交代结构)上具有明显差异,内部带演化程度明显加大,流体组分比例升高,表明体系由以熔体为主的阶段(外部带)进入以熔流体为主相对不稳定的阶段(外部带)。结合野外观察的证据,促使体系在IV带和V带间发生突然转变而进入熔流体阶段的是一个泄压事件。     

湖南仁里稀有金属矿田206号锂辉石伟晶岩脉地球化学特征及成矿时代

湖南仁里稀有金属矿田是中国近年来新发现的一处重要的花岗伟晶岩型铌、钽、锂等稀有金属矿产地,文章针对矿田含锂伟晶岩地球化学特征、成矿时代及其与花岗岩的关系,选取传梓源锂铌钽矿床内规模最大的206号锂辉石伟晶岩脉开展地球化学和白云母Ar-Ar定年工作,并与区内其他伟晶岩、花岗岩的地球化学特征、成岩时代对比分析.传梓源206号锂辉石伟晶岩属高分异稀有金属伟晶岩,形成时代为(135.4±1.4)Ma,岩石地球化学表现为高硅、高铝、低钙、相对富碱、钙碱性及过铝质特征;稀土元素总量很低,以轻稀土元素为主;微量元素富集Cs、Rb、U、Ta、Nb、Zr、Hf,相对亏损Ba、Ti,Zr/Hf、Nb/Ta比值低且集中.幕阜山地区稀有金属成矿可分为2期:第1期稀有金属成矿时代约145 Ma,与燕山早期岩浆活动有关;第2期稀有金属成矿时代135～125 Ma,为主成矿期,该期稀有金属伟晶岩与燕山晚期的二云母二长花岗岩存在成因联系,两者为同源岩浆连续结晶分异过程中不同阶段的产物.稀有金属富集成矿经历了岩浆-热液两阶段作用,Be、Nb、Ta、Li、Rb、Cs等稀有元素的富集多发生于岩浆结晶分异晚期,热液作用使Ta、Li、Rb、Cs再次富集.     

Crystallization of the Little Three layered pegmatite-aplite dike, Ramona District, California

Subhorizontally layered pegmatite-aplite bodies are characterized by fine-grained, sodic to granitic aplite that is usually juxtaposed abruptly above by much coarser-grained, commonly graphic potassic pegmatite. Although well studied, there currently is little concensus as to how such dikes form. The Little Three dike near Ramona, California, is representative of such zoned bodies in this and other regions, and contains discontinuous miarolitic pockets near the base of the graphic pegmatite zone. Tourmaline, garnet, biotite, and muscovite show no changes in major- or minor-element compositions indicative of progressive magmatic fractionation until the immediate vicinity of the main miarolitic zone, where they record abrupt and extreme enrichments in Li, F, and Mn. There is no correlation of chemical changes in the dike with the appearance of small miarolitic vugs well below the main miarolitic zone, nor is there any indication that the aplite, graphic pegmatite, or miarolitic pockets represent separate magma injections. The chemistries of tourmaline, garnet, and micas, however, preclude conventional models of Rayleigh fractionation or traditional zone refining. Textural features and modeled cooling histories indicate that the dike cooled quickly and might have solidified partially or totally to glass before crystallization commenced. Geothermometry based on the compositions of coexisting plagioclase and homogeneous, nonperthitic K-feldspar indicates inward crystallization of the dike, from ∼400–435 °C at the margins to ∼350–390 °C within 20–30 cm of the pocket horizon, then a sharp decrease to 240–275 °C in the pockets where K-feldspar is perthitic. We interpret the feldspar geothermometry (except perhaps in the miarolitic cavities) to reflect the temperatures at crystallization fronts that advanced into the pegmatite, first from the foot wall and eventually joined by a similar front downward from the hanging wall. Crystallization down from the hanging wall may have commenced after ∼70–80% of the foot wall aplite had crystallized. The very abrupt increases of Li, Mn, and F in tourmaline and garnet near the miarolitic zone appear to be explained best by the process of constitutional zone refining, in which a fluxed crystallization front sweeps an incompatible element-enriched boundary layer through a solid or semi-solid. After these two highly fluxed boundary layers merged near the main miarolitic zone, compositional evolution could have proceeded by crystal-melt fractionation. Received: 24 March 1998 / Accepted: 10 March 1999     

The Kenticha rare-element pegmatite,Ethiopia: internal differentiation,U–Pb age and Ta mineralization

The Kenticha rare-element pegmatite, a globally important tantalite source in the Neoproterozoic Adola Belt of southern Ethiopia, is a highly fractionated, huge (2,000 m long and up to 100 m thick), subhorizontal, sheet-like body, discordantly emplaced in ultramafic host rock. It corresponds to the spodumene subtype of the rare-element pegmatite class and belongs to the lithium–cesium–tantalum petrogenetic family. The Kenticha pegmatite is asymmetrically zoned from bottom to top into granitic lower zone, spodumene-free intermediate zone, and spodumene-bearing upper zone. A monomineralic quartz unit is discontinuously developed within the upper zone. Whole-rock data indicate an internal geochemical differentiation of the pegmatite sheet proceeding from the lower zone (K/Rb ~36, K/Cs ~440, Al/Ga ~2,060, Nb/Ta ~2.6) to the upper zone (K/Rb ~19, K/Cs ~96, Al/Ga ~1,600, Nb/Ta ~0.7). The latter one is strongly enriched in Li₂O (up to 3.21%), Rb (up to 4,570 ppm), Cs (up to 730 ppm), Ga (up to 71 ppm), and Ta (up to 554 ppm). Similar trends of increasing fractionation from lower zone to upper zone were obtained in muscovite (K/Rb 23–14, K/Cs 580–290, K/Tl 6,790–3,730, Fe/Mn 19–10, Nb/Ta 6.5–3.8) and columbite–tantalite (Mn/Mn + Fe 0.4–1, Ta/Ta + Nb 0.1–0.9). The bottom-to-top differentiation of the Kenticha pegmatite and the Ta mineralization in its upper part are principally attributed to upward in situ fractionation of a residual leucogranitic to pegmatitic melt, largely under closed system conditions. High MgO contents (up to 5.05%) in parts of the upper zone are the result of postmagmatic hydrothermal alteration and contamination by hanging wall serpentinite. U–Pb dating of Mn-tantalite from two zones of the Kenticha pegmatite gave ages of 530.2 ± 1.3 and 530.0 ± 2.3 Ma. Mn-tantalite from the Bupo pegmatite, situated 9 km north of Kenticha, gave an age of 529.2 ± 4.1 Ma, indicating coeval emplacement of the two pegmatites. The emplacement of the pegmatites is temporally related to postorogenic granite magmatism, producing slightly peraluminous, I-type plutons in the area surrounding the Kenticha pegmatite field. Fractionated members of this suite might be envisaged as potential parental magmas.     

Geochemical characteristics and spectrometric prospecting in the muscovite-bearing pegmatites and granites,southeastern Aswan,Egypt

Rare metal mineralization of Sn, Nb-Ta and W is encountered in the Gebel Dihmit area （GDA）, southeastern Aswan, Egypt. The mineralization is related to muscovite granites and their pegmatite derivatives. The pegmatites are divided into three types according to their main mineral assemblages： K-feldspar-muscovite-tourmaline, K-feldspar-albite-muscovite and albite-K-feldspar-lepidolite veins. Petrogenetic studies indicate that Sn and Nb-Ta mineralization extends from the late-magmatic stage to the pegmatite and hydrothermal stages of the （GDA） suite. The albite-K-feldspar-lepidolite granite is composed dominantly of albite, lepidolote, and quartz, with topaz, K-feldspar and amblygonite. The accessory minerals are zircon, monazite, pollucite, columbite-tantalite, microlite and Ta-rich cassiterite. Phenocrysts of quartz, topaz and K-feldspar contain abundant inclusions of albite laths and occasional lepidolite crystals along growth zones （snowball texture）, indicating simultaneous crystallization from a subsolvus, residual magma. The origin of the pegmatites is attributed to extreme differentiation by fractional crystallization of a granitic magma. The economic potential for rare metals was evaluated in the geochemical discrimination diagrams. Accordingly, some of the pegmatites are not only highly differentiated in terms of alkalis, but also the promising targets for small-scale Ta and, to a less extent, Sn. The pegmatites also provide the first example of Fe-Mn and Nb-Ta fractionation in successive generations of granites to cassiterite-bearing pegmatites, which perfectly ex- hibit similar fractionation trends established for primary columbite-tantalite in the corresponding categories of pegmatites. Uranium and Th of magmatic origin are indicated by the presence of thorite and allanite, whereas evidence of hydrothermal mineralization is the alteration of rock- foring minerals such as feldspar and the formation of secondary minerals such as uranophane..     

In situ analyses of micas in the Yashan granite,South China: Constraints on magmatic and hydrothermal evolutions of W and Ta–Nb bearing granites

Most rare-metal granites in South China host major W deposits with few or without Ta–Nb mineralization. However, the Yashan granitic pluton, located in the Yichun area of western Jiangxi province, South China, hosts a major Nb–Ta deposit with minor W mineralization. It is thus important for understanding the diversity of W and Nb–Ta mineralization associated with rare-metal granites. The Yashan pluton consists of multi-stage intrusive units, including the protolithionite (-muscovite) granite, Li-mica granite and topaz–lepidolite granite from the early to late stages. Bulk-rock REE contents and La/Yb ratios decrease from protolithionite granite to Li-mica granite to topaz–lepidolite granite, suggesting the dominant plagioclase fractionation. This variation, together with increasing Li, Rb, Cs and Ta but decreasing Nb/Ta and Zr/Hf ratios, is consistent with the magmatic evolution. In the Yashan pluton, micas are protolithionite, muscovite, Li-mica and lepidolite, and zircons show wide concentration ranges of ZrO₂, HfO₂, UO₂, ThO₂, Y₂O₃ and P₂O₅. Compositional variations of minerals, such as increasing F, Rb and Li in mica and increasing Hf, U and P in zircon are also in concert with the magmatic evolution from protolithionite granite to Li-mica granite to topaz–lepidolite granite. The most evolved topaz–lepidolite granite has the highest bulk-rock Li, Rb, Cs, F and P contents, consistent with the highest contents of these elements and the lowest Nb/Ta ratio in mica and the lowest Zr/Hf ratio in zircon. Ta–Nb enrichment was closely related to the enrichment of volatile elements (i.e. Li, F and P) in the melt during magmatic evolution, which raised the proportion of non-bridging oxygens (NBOs) in the melt. The rims of zoned micas in the Li-mica and topaz–lepidolite granites contain lower Rb, Cs, Nb and Ta and much lower F and W than the cores and/or mantles, indicating an exotic aqueous fluid during hydrothermal evolution. Some columbite-group minerals may have formed from exotic aqueous fluids which were originally depleted in F, Rb, Cs, Nb, Ta and W, but such fluids were not responsible for Ta–Nb enrichment in the Yashan granite. The interaction of hydrothermal fluids with previously existing micas may have played an important role in leaching, concentrating and transporting W, Fe and Ti. Ta–Nb enrichment was associated with highly evolved magmas, but W mineralization is closely related to hydrothermal fluid. Thus these magmatic and hydrothermal processes explain the diversity of W and Ta–Nb mineralizations in the rare-metal granites.     

一种特殊类型的云英岩:湘南香花岭地区癞子岭云英岩成岩成矿特征

癞子岭岩体具有极好的垂向分带性,从下部到顶部包括了花岗岩、云英岩和伟晶岩,其中云英岩以其厚度巨大,云母类型属于铁锂云母,黄玉含量高,W-Sn-Nb-Ta含量高,而区别于其他地区云英岩。通过对癞子岭云英岩进行岩石学、地球化学和矿物学的研究,本文得出:癞子岭云英岩是高硅的强过铝质岩石类型,全碱含量低(3~4.3 wt%),富集挥发组分,全岩Zr/Hf(~8)和Nb/Ta(~1.7)比值低。造岩矿物铁锂云母中Nb(~74×10~(-6))、Ta(~66×10~(-6))、W(~23×10~(-6))、Sn(~75×10~(-6))等成矿元素含量较高。副矿物锆石自形且成分均一,含有HfO_2约10 wt%,Zr/Hf比值最低为5,与云英岩下部的癞子岭钠长花岗岩中的锆石成分有连续过渡的关系。这些特征与南岭地区高演化稀有金属花岗岩或伟晶岩相当,体现了相近的演化程度。癞子岭云英岩中有明显的Nb-Ta-W-Sn成矿作用发生,主要形成铌铁矿族矿物、锡石和黑钨矿,成分和结构均具有岩浆成因特征。花岗质熔体中含有大量挥发组分Li和F,结晶出黄玉和Li-F云母,F在稀有金属的成矿作用和云英岩的成岩过程中发挥了非常重要的作用,成矿作用发生在岩浆演化的晚期并伴随有流体作用。因此,云英岩可能是钠长花岗岩高度分异演化之后的特殊产物,这为研究花岗岩岩浆-热液体系成岩成矿过程提供了新的窗口。     

The Durulgui rare-metal granite‒pegmatite system in the eastern Transbaikal region: Petrological and geochronological aspects

The Durulgui granite?pegmatite system unites the Dedova Gora granite massif and pegmatite field with the Chalotskoe beryl deposit. New geochronological data on micas from porphyric biotite granites, fine-grained biotite granites, two-mica granites, and Be-bearing pegmatites are discussed. The plateau age of 128.5(±1.5)–131.2(±1.5) should be considered as indicating the formation time of the granite?pegmatite system as a whole. The age of the system implies the possibility of its formation owing to several magmatic pulses. This assumption concerns porphyric and fine-grained biotite granites and two-mica and muscovite granites, the contact between which is locally sharp. At the same time, the succession “two-mica granites → muscovite granites → granite?pegmatites → microcline pegmatites → microcline?albite pegmatites → albite pegmatites” demonstrates gradual facies transitions between rocks, which indicates their emplacement during a single magmatic pulse.     

Formation Age and Evolution Time Span of the Koktokay No. 3 Pegmatite,Altai, NW China: Evidence from U–Pb Zircon and 40Ar–39Ar Muscovite Ages

The Koktokay No. 3 pegmatite is the largest Li–Be–Nb–Ta–Cs pegmatitic rare‐metal deposit of the Chinese Altai orogenic belt, and is famous for its concentric ring zonation pattern (nine internal zones). However, the formation age and evolution time span have been controversial. Here, we present the results of LA‐ICP–MS zircon U–Pb dating and muscovite ⁴⁰Ar–³⁹Ar dating. Four groups of zircon U–Pb ages (～210 Ma, ～193–198 Ma, ～186–187 Ma and ～172 Ma) for Zones II, V, VI, VII, and VIII, and a weighed mean ²⁰⁶Pb/²³⁸U age of 965 ± 11 Ma for Zone IV are identified. Also, Zones II, IV, and VI have muscovite ⁴⁰Ar–³⁹Ar plateau ages of 179.7 ± 1.1 Ma, 182.1 ± 1.0 Ma, and 181.8 ± 1.1 Ma, respectively. Considering previous U–Pb age studies (Zones I, V, and VII), the ages of emplacement, Li mineralization peak, hydrothermal stage of the No. 3 pegmatite are in ranges of 193–198 Ma, 184–187 Ma and 172–175 Ma, with weighted mean ²⁰⁶Pb–²³⁸U ages of 194.8 ± 2.3 Ma, 186.6 ± 1.3 Ma and 173.1 ± 3.9 Ma, respectively. The No. 3 pegmatite formed in the early Jurassic. The results of xenocrysts suggest that there is another pegmatite forming event of around 210 Ma in the mining district and the old zircon U–Pb ages imply that Neoproterozoic crustal rocks pertain to sources of the No. 3 pegmatite. Including the previous muscovite ⁴⁰Ar–³⁹Ar age studies (Zones I and V), a cooling age range of 177–182 Ma is considered as the time of hydrothermal stage and end of formation. The evolution process of the No. 3 pegmatite lasted 16 Ma. Therein, the magmatic stage continued for 9–11 Myr and the magmatic–hydrothermal transition and hydrothermal stages were sustained at 5–7 Ma. These time spans are long because of huge scale, cupola shape, large formation depth, and complex internal zoning patterns and formation processes. Considering some pegmatite dikes in the Chinese Altai, there is an early Jurassic pegmatite forming event.     

Cs-dominant polylithionite in the Koktokay#3 pegmatite,Altai, NW China: in situ micro-characterization and implication for the storage of radioactive cesium

Except forming two Cs-rich minerals like pollucite and londonite, cesium generally occurs in trace amounts in potassium-bearing minerals owing to its very low Clarke value and large ionic radius. However, in the Koktokay#3 pegmatite (Altai, NW China), lepidolite is extremely enriched in cesium (typically 21–26 wt% Cs₂O). Cs-enriched lepidolite is restricted to the inner of the pegmatite, where four types of occurrence are characterized by using in situ techniques (EMP: electron microprobe, micro-XRD: micro-area X-ray diffractometer and Raman probe: micro-area Raman spectrometer) as: (1) outer zones on Cs-poor lepidolite cores; (2) fine overgrowths on muscovite veinlets; (3) veinlets in Cs-poor lepidolite and (4) veinlets in elbaite. There is an inverse correlation between K and Cs and in terms of ^VIAl versus Cs/(K+Cs), the Cs-dominant micas are an analog of the Li-rich mica polylithionite. Micro-XRD patterns and micro-Raman spectra indicate that Cs-dominant polylithionite structurally corresponds to minerals of the lepidolite series. According to its distribution and compositional characteristics, the Cs-dominant polylithionite seems to have formed at the magmatic to hydrothermal transition stage of pegmatitic magma evolution as a result of marginal replacement of early-formed lepidolite by Cs-rich fluids. Alternatively, it may have formed through direct precipitation from Cs-rich fluids. The results of the present study have important implications for the storage of nuclear waste in that Li mica such as polylithionite is a good candidate for immobilizing high-level radioactive cesium waste.     

新疆阿尔泰可可托海伟晶岩型稀有金属矿床中磷灰石地球化学特征及意义

磷灰石可以记录和保存岩浆和热液活动的信息。可可托海伟晶岩型稀有金属矿床磷灰石发育,为研究该矿床伟晶岩成岩成矿过程提供了优良的条件。已有对可可托海伟晶岩型稀有金属矿床磷灰石的研究集中在其稀土元素特征,较少讨论其对伟晶岩成岩成矿过程的制约。本文选取可可托海伟晶岩型稀有金属矿床富矿伟晶岩脉(3号脉)和相对贫矿伟晶岩脉(1号、2b号和3a号脉)中的磷灰石作为研究对象,进行磷灰石岩相学和地球化学研究。岩相学分析表明,磷灰石主要与钠长石、石英、白云母、锰铝榴石等伴生。EPMA分析显示,磷灰石F含量为3.67%～4.41%,Cl含量小于0.67%,较低的Cl含量表明伟晶岩熔体出溶的流体Cl含量较低;大部分磷灰石MnO含量为4.67%～8.71%,但2b号脉磷灰石MnO含量变化较大(1.23%～14.28%),这是由于2b号脉磷灰石具有分带结构,暗示其遭受后期热液作用,促使磷灰石溶解-再沉淀,导致MnO含量发生较大变化。LA-ICP-MS分析显示,贫矿伟晶岩脉磷灰石的稀土元素含量较低(180×10~(-6));相反,富矿伟晶岩脉磷灰石的稀土元素含量较高( 700×10~(-6)),并具有明显的四分组效应(TE_(1-3)平均值为1.7)。1号脉和3a号脉磷灰石均显示轻稀土元素富集,反映其形成过程中有含Cl热液的参与。3号脉磷灰石显示强烈Eu负异常和Ce正异常,而2b号脉磷灰石显示强烈Ce负异常和中等Eu负异常,这种Eu、Ce异常的差异可能与岩浆-热液阶段大量流体出溶密切相关。磷灰石的沉淀将导致热液中HF含量的降低,促使磷灰石周围铌钽矿结晶和Nb、Ta进入磷灰石中。可见,在伟晶岩形成过程中,磷灰石并非保持稳定,其分带结构和主微量成分变化记录了后期热液活动,暗示后期热液活动对伟晶岩的成矿具有重要作用。     

新疆阿尔泰协库斯特伟晶岩中锂的矿物学行为及其启示

协库斯特伟晶岩位于新疆阿尔泰可可托海镇，属于典型的Li-Cs-Ta(LCT)伟晶岩，发育大量锂的磷酸盐矿物和硅酸盐 矿物。文章利用电子探针和X射线衍射等分析手段，结合野外观察，系统研究了协库斯特伟晶岩中锂的矿物学行为，探讨 花岗质岩浆—热液过程中锂矿物的结晶演变与热液蚀变过程。研究表明：协库斯特伟晶岩中锂矿物结晶于两个阶段，花岗 质岩浆阶段，锂矿物主要有锂辉石、磷锂铝石与磷锰锂矿，而锂电气石、多硅锂云母、锂白云母等形成于岩浆—热液过渡 阶段至热液阶段。磷锰锂矿与羟磷锂铝石团块包体反映协库斯特伟晶岩中锂的磷酸盐熔体与硅酸盐熔体的不混溶机制。磷 锰锂矿逐渐蚀变形成黄白色—红色的结构相似的矿物相，揭示了磷锰锂矿的氧化过程以及锂的释放过程。早期锂辉石、磷 锰锂矿、磷锂铝石等锂矿物热液蚀变释放出Li进入热液，这种富Li热液作用形成了次生富锂矿物，显示了协库斯特伟晶岩 内部Li的地球化学循环过程。     

新疆阿尔泰协库斯特伟晶岩中锂的矿物学行为及其启示

协库斯特伟晶岩位于新疆阿尔泰可可托海镇,属于典型的Li-Cs-Ta(LCT)伟晶岩,发育大量锂的磷酸盐矿物和硅酸盐 矿物。文章利用电子探针和X射线衍射等分析手段,结合野外观察,系统研究了协库斯特伟晶岩中锂的矿物学行为,探讨 花岗质岩浆-热液过程中锂矿物的结晶演变与热液蚀变过程。研究表明：协库斯特伟晶岩中锂矿物结晶于两个阶段,花岗 质岩浆阶段,锂矿物主要有锂辉石、磷锂铝石与磷锰锂矿,而锂电气石、多硅锂云母、锂白云母等形成于岩浆-热液过渡 阶段至热液阶段。磷锰锂矿与羟磷锂铝石团块包体反映协库斯特伟晶岩中锂的磷酸盐熔体与硅酸盐熔体的不混溶机制。磷 锰锂矿逐渐蚀变形成黄白色-红色的结构相似的矿物相,揭示了磷锰锂矿的氧化过程以及锂的释放过程。早期锂辉石、磷 锰锂矿、磷锂铝石等锂矿物热液蚀变释放出Li进入热液,这种富Li热液作用形成了次生富锂矿物,显示了协库斯特伟晶岩 内部Li的地球化学循环过程。     

云母:花岗岩-伟晶岩稀有金属成矿作用的重要标志矿物

云母是花岗岩、伟晶岩中的重要造岩矿物,不仅是整个岩浆阶段的结晶产物,而且也是热液过程的参与者。作为层状硅酸盐矿物,层间或八面体位置上可容纳锂、铷铯、锡、铌钽等稀有金属。本文结合前人研究积累和作者近年来的研究成果,阐述了云母作为一个重要的稀有金属成矿标志矿物的矿物学特征。铁锂云母-锂云母是稀有金属成矿作用中重要的锂矿物,同时云母中锂含量可以反映花岗岩的分异程度。铷、铯可以置换云母层间钾,在高演化花岗岩、伟晶岩中可以形成铷、铯为主的云母(既可以是锂云母系列,也可以是黑云母系列)。黑云母是稀有金属花岗岩中一个特殊的矿物。准铝质含锡花岗岩中黑云母锡含量可达100×10~(-6),其锡含量可以指示其锡成矿能力。稀有金属花岗岩中,常见的是铌钽氧化物矿物。但是最近研究发现,黑云母中铌可以超常富集(超过1000×10~(-6)),成为稀有金属花岗岩中最重要、甚至唯一的铌矿物,形成一种以富铌黑云母为特色的新类型稀有金属花岗岩,并可能代表了一种新型的潜在铌资源。基于云母在花岗岩中的重要性和结构的特殊性,今后要利用微区成分和结构分析技术,加强对云母中稀有金属晶体化学的研究,以及进一步揭示云母对稀有金属成矿的特殊重要意义。     

湖南仁里矿田锂辉石白云母伟晶岩地质特征及其找矿意义

仁里矿田位于扬子陆块与华夏陆块交汇的江南隆起造山带中段、幕阜山岩体西南缘的舌状体区域。稀有金属伟晶岩矿化类型在空间上具分带性,矿田北东部为白云母伟晶岩,西南部为锂辉石白云母伟晶岩。本文对矿田内3条代表性的锂辉石白云母伟晶岩开展了地质和地球化学特征研究。测试结果为:SiO2含量为62.0%~78.0%(平均71.8%);Al2O3为14.8%~18.0%(平均16.1%),Al2O3/(K2O+Na2O+CaO)摩尔比(A/CNK=1.52~13.0)大于1.1,分异指数(DI)89.7~97.5,∑REE=2.07~14.8μg/g,LREE/HREE=6.90~15.9。研究表明:①仁里矿田伟晶岩为过铝质岩浆系统下高分异、富碱、富稀有金属、富铪锆型花岗质伟晶岩,锂铌钽等稀有金属矿化与磷灰石化关系密切。②锂辉石白云母伟晶岩具有良好的分带性,其结晶分异时间晚于白云母伟晶岩,我们推测伟晶岩岩浆的结晶、分异时间越长越有利于Li元素的富集;矿田稀有金属矿化组合呈现Be+Nb+Ta→Be+Nb+Ta+Li→Be+Li的演化规律。③仁里矿田锂矿资源丰富,主要集中在矿田西南部,有望在进一步增加矿田钽铌资源量的基础上,提交一处高品位的大型锂矿床;在锂矿找矿工作中,尤其注意伟晶岩中的贫Nb、Ta锂辉石白云母伟晶岩地段。     

Main types of rare-metal mineralization in Karelia

Rare-metal mineralization in Karelia is represented by V, Be, U deposits and In, Re, Nb, Ta, Li, Ce, La, and Y occurrences, which are combined into 17 types of magmatic, pegmatite, albitite–greisen, hydrothermal–metasomatic, sedimentary, and epigenetic groups. The main vanadium resources are localized in the Onega ore district. These are deposits of the Padma group (556 kt) and the Pudozhgorsky complex (1.5 Mt). The REE occurrences are primarily characterized by Ce–La specialization. The perspective of HREE is related to the Eletozero–Tiksheozero alkaline and Salmi anorthosite–rapakivi granite complexes. Rare-metal pegmatites bear complex mineralization with insignificant low-grade resources. The Lobash and Jalonvaara porphyry Cu–Mo deposits are potential sources of rhenium: Re contents in molybdenite are 20–70 and 50–246 ppm and hypothetical resources are 12 and 7.5 t, respectively. The high-grade (～100 ppm) and metallogenic potential of indium (～2400 t) make the deposits of the Pitkäranta ore district leading in the category of Russian ore objects most prospective for indium. Despite the diverse rare-metal mineralization known in Karelia, the current state of this kind of mineral commodities at the world market leaves real metallogenic perspective only for V, U, Re, In, and Nb.     

Ore geochemistry,zircon mineralogy,and genesis of the Sakharjok Y-Zr deposit,Kola Peninsula,Russia

The Sakharjok Y-Zr deposit in Kola Peninsula is related to the fissure alkaline intrusion of the same name. The intrusion ∼7 km in extent and 4–5 km² in area of its exposed part is composed of Neoarchean (2.68–2.61 Ma) alkali and nepheline syenites, which cut through the Archean alkali granite and gneissic granodiorite. Mineralization is localized in the nepheline syenite body as linear zones 200–1350 m in extent and 3–30 m in thickness, which strike conformably to primary magmatic banding and trachytoid texture of nepheline syenite. The ore is similar to the host rocks in petrography and chemistry and only differs from them in enrichment in zircon, britholite-(Y), and pyrochlore. Judging from geochemical attributes (high HSFE and some incompatible element contents (1000–5000 ppm Zr, 200–600 ppm Nb, 100–500 ppm Y, 0.1–0.3 wt % REE, 400–900 ppm Rb), REE pattern, Th/U, Y/Nb, and Yb/Ta ratios), nepheline syenite was derived from an enriched mantle source similar to that of contemporary OIB and was formed as an evolved product of long-term fractional crystallization of primary alkali basaltic melt. The ore concentrations are caused by unique composition of nepheline syenite magma (high Zr, Y, REE, Nb contents), which underwent subsequent intrachamber fractionation. Mineralogical features of zircon-the main ore mineral—demonstrate its long multistage crystallization. The inner zones of prismatic crystals with high ZrO₂/HfO₂ ratio (90, on average) grew during early magmatic stage at a temperature of 900–850°C. The inner zones of dipyramidal crystals with average ZrO₂/HfO₂ = 63 formed during late magmatic stage at a temperature of ∼500°C. The zircon pertaining to the postmagmatic hydrothermal stage is distinguished by the lowest ZrO₂/HfO₂ ratio (29, on average), porous fabric, abundant inclusions, and crystallization temperature below 500°C. The progressive decrease in ZrO₂/HfO₂ ratio was caused by evolution of melt and postmagmatic solution. The metamorphic zircon rims relics of earlier crystals and occurs as individual rhythmically zoned grains with an averaged ZrO₂/HfO₂ ratio (45, on average) similar to that of the bulk ore composition. The metamorphic zircon is depleted in uranium in comparison with magmatic zircon, owing to selective removal of U by aqueous metamorphic solutions. Zircon from the Sakharjok deposit is characterized by low concentrations of detrimental impurities, in particular, contains only 10–90 ppm U and 10–80 ppm Th, and thus can be used in various fields of application.     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

富锂氟含稀有矿化花岗质岩石的对比和成因思考

Li-F花岗质岩石以超酸性、过铝、富含H2O、F、B、P等挥发性组分和富含Li、Rb、Cs、Be、Ta、Nb、Sn、W等亲石稀有金属元素为主要特征，以黄玉－锂云母－钠长石花岗岩为典型代表。从该类岩石地质产状的多样性和可对比性、空间分布的规律性、矿物岩石的结构构造、硅酸盐－熔体包裹体特征以及实验岩石学的研究成果等方面，综合论证该类岩石主要是从经过分异演化而形成的残余熔浆中直接结晶而在的；充分的分离结晶作用，是产生这种残余熔浆的主要机制；岩体的空间分带特征和各带之间的渐变过渡关系，为分离结晶作用的途径和演化方向提供了重要信息；熔体中挥发性组分的大量存在，是分离结晶作用能充分进行的关键因素；亲石稀有金属元素在流／熔配分中倾向于进入熔体相，是残余熔体中逐步富集这些稀有金属元素的主要原因；岩浆－热液过渡阶段出溶的流体相与已晶出的共存固相之间的相互作用，造成了广泛的交代蚀变现象；残余熔浆在不同地质和物理化学环境中的侵位、结晶和演化，造成了Li-F花岗质岩石在产状、结构构造和矿物组合等方面的多样性。