钠长花岗岩—H2O—HF体系中流体／熔体间氟的分配实验研究

在ｐ＝１００Ｍｐａ,在７７０℃≤ｔ≤８００℃和ＷＦ＝２％－６％条件下进行了钠长花岗岩－Ｈ２Ｏ－ＨＦ体系液相线附近线体／熔体间氟的分配实验。对淬火玻璃的主要元素和氟含量进行了电子探针测定。用质量平衡法计算了流体中的氟含量,所获得的氟的流体／熔体分配系数ＤＦ均不盱１．０随体系氟含量的增加ＤＦ有所增大,表明在花岗岩岩浆一热液体系,氟优先进入熔体相,含氟花岗岗岩结晶晚期流体释放阶段残余熔体仍保保持富氟特征     

华南富锂氟含稀有金属花岗岩的成冈分析

雪球结构的产出特征、钠长石电子探针分析及其它间接证据都说明,雪球结构是在岩浆结晶过程中形成的。雪球结构形成与否主要与岩浆熔体中Ｎａ２Ｏ／Ｋ２Ｏ比值和Ｆ、Ｈ２Ｏ含量有关。较大的Ｎａ２Ｏ／Ｋ２Ｏ比值（〉１）例钠长石首先从熔体中晶出;较高的Ｆ含量使岩浆固相线温度大大降低,有利于岩浆分异演化并形成接近端员组分的钠长石和钾长石同的Ｈ２Ｏ含量有利于石英以较快的速度生长并逐渐包裹钠长石形成雪球结构。自形的α－石英斑晶、接近各自端员组分的甲和工石和钠长石等说明该类花岗岩形成温度较低,众多的地质、地球化学依据都证明了,华南富锂氟含稀有金属花岗岩是从过铝富氟富钠的残余熔体中直接结晶而成的。     

黑鳞云母花岗质岩浆的结晶分异及钠长花岗质岩浆的形成

以含F、过铝质、K_2O>Na_2O为特征的浅色黑鳞云母花岗岩为初始物,在P=150MPa,T=850～650℃和H_2O不饱和条件下进行熔化-结晶分异实验,结果表明:首先晶出的是石英和富钾碱性长石;随结晶温度下降和结晶相含量的增加,残余熔体中挥发份F及Na_2O、Al_2O_3含量逐渐增加,SiO_2、K_2O、CaO含量减少,显示含F浅色花岗质熔体具有向贫硅富钠的富氟钠长花岗质熔体组成演化的趋势;700℃开始,残余熔体具有天然富氟钠长花岗岩的组成特征:富Na_2O(Na_2O>K_2O)、Al_2O_3(>16％)和F(>1.5％)。上述残余熔体组成的演化特征与自然界从含氟黑鳞云母花岗岩到富氟钠长花岗岩的组成变化规律是一致的,充分证明了在本文的实验条件下,含氟黑鳞云母花岗岩能够经结晶分异演化出富氟钠长花岗岩熔体。     

纳长石花岗岩中雪球结构形成机理的研究

在某些富锂、氟含稀有金属花岗岩的石英和钾长石斑晶中常见（半）雪球结构。雪球结构的产出特征、雪球体中钠长石的电子探针分析结果以及其他间接证据都说明,雪球结构是在岩浆结晶分异过程中形成的。对矿物结晶顺序、石英和纳长石的生长速率以及固相线温度的研究表明,富锂、氟、钠的花岗质残余岩浆完全具备形成雪球结构的条件．岩浆熔体中较高的Ｎａ２Ｏ／Ｋ２Ｏ比值和Ｆ、Ｈ２Ｏ含量在雪球结构的形成过程中起着重要的作用：Ｆ的高     

俯冲带复杂的壳幔相互作用

俯冲带除俯冲板片脱水形成的富大离子亲石元素流体、交代地幔楔形成的岛弧钙碱性玄武岩安山岩-英安岩-流纹岩及相应侵入岩组合外，还存在由俯冲扳片熔融形成的埃达克质熔体交代地慢楔形成的埃达克岩-富铌玄武岩-富镁安山岩组合，从而构成了俯冲带的流体交代与熔体交代两大类壳慢相互作用体系及相应的岩石组合。熔体交代作用的显著特点是Mg、高场强元素Nb、Ti、P等含量增加，Nd／Sr值增高，而Si、K、Na及La／Yb降低。洋壳板片或洋脊俯冲、玄武质岩浆底侵使地壳增厚，或板片断离、撕裂等作用均可产生埃达克质熔体并随之产生熔体交代作用。流体和熔体与地幔橄揽岩的相互作用构成了俯冲带复杂的地球化学体系。     

攀西地区新街层状岩体粒间不混熔作用:来自斜长石环带结构的记录

位于攀西地区的新街层状岩体赋含大量钒钛磁铁矿,是峨眉山大火成岩省的一部分。岩体下部带和中部带以单斜辉石岩为主,并伴生浸染状钒钛磁铁矿矿化;上部带以辉长岩为主,赋存厚层的钒钛磁铁矿矿体。之前研究认为厚层的钒钛磁铁矿矿体的形成与粒间不混熔的富Fe熔体有关,但对富Fe熔体的演化过程缺乏细致研究。本文通过对新街岩体上部带的富矿辉长岩层和上覆浅色辉长岩中斜长石环带结构和成分的研究,揭示了富Fe熔体的演化过程。在浅色辉长岩中保存的岩浆不混熔的直接证据表现为矿物粒间共轭的富Si交生体和富钛铁矿交生体代表的非反应结构。本次研究发现,与粒间富Si交生体接触的斜长石边部的FeO和TiO_2含量随斜长石牌号(An)值的降低而降低,而与粒间富钛铁矿交生体接触的斜长石边部的FeO和TiO_2含量随An值的降低而升高,说明斜长石的边部成分变化记录了粒间共轭的富Si和富Fe熔体的成分特征。在富矿辉长岩中,斜长石可分为初生和新生两种,初生斜长石的An值介于57~62,FeO含量为0.34%~0.50%,TiO_2含量为0.06%~0.13%,新生斜长石具有相对较高的An值(61~81)和FeO、TiO_2含量,二者的内部和边部还发育增生斜长石,其An值(~50)相对较低;在初生斜长石边部可见不连续的新生斜长石环带和增生斜长石边,造成其内部成分显著不均一,并发育复杂的环带结构。本文认为,初生斜长石是岩浆正常分离结晶作用的产物。在粒间熔体发生不混熔后,不混熔的富Fe熔体逐渐向岩浆房下方迁移并结晶出了一些相对高An值的新生斜长石,或沿一些初生斜长石边部生长形成不连续的高An环带。当富Fe熔体演化至晚期,由于矿物生长空间受限,仅在初生和新生斜长石局部形成了相对低An值的增生边、或沿颗粒裂隙进入斜长石内部形成增生斜长石核。     

金在花岗质熔体中溶解度的初步实验研究

以合成花岗岩、水、不同浓度的盐酸溶液、氢氟酸溶液作为反应初始物,在850℃,100 MPa,接近于NNO的条件下开展了金在不同花岗质熔体中溶解度的实验研究,实验固液相产物中的金含量使用石墨炉原子吸收法测定。实验结果显示,金在花岗质熔体中的溶解度变化范围为1.87～156.62μg/g,流体相中金的溶解度为0.31～6.92μg/g;金在熔体相中的溶解度较其在共存液相中的高。花岗质熔体相中金的溶解度明显受熔体化学组成的影响,过碱性富钠花岗质熔体中金的溶解度明显高些;金在花岗质熔体中的溶解度随着熔体中Na2O/K2O摩尔比增大而增大;在氟氯共存岩浆体系中,氟含量变化对金在熔体相中的溶解度影响不明显,而液相中氯含量增大有利于提高金在流体相中的含量。     

富氟花岗岩体系岩浆流体内稀土元素演化规律的实验研究

高温高压实验结果表明，随着富氟过铝花岗质岩浆分离结晶作用的进行，在与熔体相共存的流体相中，REE浓度呈有规律地变化：当温度从750℃下降至接近固相线（570℃）时，流体相中REE浓度逐渐降低，这一规律与REE在稀有金属花岗岩体上部岩相带中REE含量贫化的地质事实相一致。在富氟过铝质花岗岩体系中，REE易于分散进入某些造岩矿物（如黑云母等）和副矿物（如萤石和锡石等）中，从而不利于REE形成热液矿床。     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

钠长石花岗岩中雪球结构形成机理的研究

在某些富锂、氟含稀有金属花岗岩的石英和钾长石斑晶中常见 (半 )雪球结构。雪球结构的产出特征、雪球体中钠长石的电子探针分析结果以及其他间接证据都说明 ,雪球结构是在岩浆结晶分异过程中形成的。对矿物结晶顺序、石英和钠长石的生长速率以及固相线温度的研究表明 ,富锂、氟、钠的花岗质残余岩浆完全具备形成雪球结构的条件。岩浆熔体中较高的Na2 O/K2 O比值和F、H2 O含量在雪球结构的形成过程中起着重要的作用 :F的高含量使岩浆固相线温度降低 ,岩浆得以充分分异演化 ,形成接近端员组分的钾长石和钠长石 ;Na2 O/K2 O比值较大使钠长石首先结晶 ;较高的F和H2 O含量使岩浆粘度降低 ,石英的生长速率相对加快并逐渐包裹钠长石形成雪球结构。     

富F熔体-溶液体系流体地球化学及其成矿效应--研究现状及存在问题

高度演化花岗岩类多为富F的熔体溶液体系 ,具有鲜明的、不同于其他体系的地球化学行为。富F岩浆固相线和液相线的降低和岩浆寿命的延长 ,使残余熔体与热水热液的性状差异减小 ,模糊了岩浆与热液之间的界线。最近对于富F、B和P伟晶岩中熔融包裹体的研究获得了新的进展。在约 70 0～ 5 0 0℃的温度和 1 0 0 0× 1 0 5Pa的压力下 ,在伟晶岩石英中发现两种不同类型的熔体包裹体 ,一种是富硅酸盐、贫水的熔体包裹体 ,另一种是贫硅酸盐、富水的熔体包裹体。两种熔体在硅酸盐 (+F +B +P) 水体系的溶离线边界上同时被圈闭。这表明 ,在地壳浅部侵位的侵入体 ,当温度≥ 70 0℃时 ,水在富F、B和P的熔体中可以无限混溶 ;而一旦温度降低 ,就会分离为两种共存的熔体并伴随强烈的元素分异作用。在溶离线的富水一侧形成与正常硅酸盐熔体有很大不同的高度富挥发份的熔体 ,这种致密、高粘度、高扩散性以及高活动性的超富水 (hyper aqueousmelt)熔体 ,可以与水溶液流体相类比。这为岩浆热液过渡性流体的假说提供了新的有利的证据。此外 ,在这种具有超富水和熔体特征的过渡性流体中 ,微迹元素可能具有特殊的地球化学行为 ,如在许多晚期花岗岩包括淡色花岗岩和伟晶岩中稀土元素配分模式所显示的四分组效应等。富F熔体溶液体?     

Partitioning of F between aqueous fluids and albite granite melt and its petrogenetic and metallogenetic significance

The fluid/melt partitioning experiments on fluorine were carried out in the system albite-H₂O-HF atP = 100 MPa, 770°C ≤T≤800°C: and wt = 2% −6% conditions. The concentrations of fluorine in quenched glasses (melt) were determined by electron microprobe and those of fluorine in the coexisting aqueous fluid were calculated by the method of mass balance. The result shows that the fluorine was concentrated in granitic melt relative to the coexisting fluid. The partition coefficient D_F(wt _F ^F1 /wt _F ^Mt ) ranges from 0.35 to 0.89. It increases with increasing fluorine content in the system. This means that there is not just one single value of partition coefficient for fluorine in the granitic melt-fluid system. The partitioning behavior of fluorine in this system depends critically on fluorine and proton (H⁺) concentrations. Our data suggest that F-rich granitic melts exist in nature and that fluorine may not be an important complexing agent of metal elements in F-bearing fluids. The project was financially supported by both the National Natural Science Foundation of China (No. 49603048) and the State Key Laboratory of Mineral Deposit Research, Nanjing University.     

Geochemical evolution of halogen-enriched granite magmas and mineralizing fluids of the Zinnwald tin-tungsten mining district,Erzgebirge, Germany

We remelted and analyzed crystallized silicate melt inclusions in quartz from a porphyritic albite-zinnwaldite microgranite dike to determine the composition of highly evolved, shallowly intruded, Li- and F-rich granitic magma and to investigate the role of crystal fractionation and aqueous fluid exsolution in causing the extreme extent of magma differentiation. This dike is intimately associated with tin- and tungsten-mineralized granites of Zinnwald, Erzgebirge, Germany. Prior research on Zinnwald granite geochemistry was limited by the effects of strong and pervasive greisenization and alkali-feldspar metasomatism of the rocks. These melt inclusions, however, provide important new constraints on magmatic and mineralizing processes in Zinnwald magmas.The mildly peraluminous granitic melt inclusions are strongly depleted in CAFEMIC constituents (e.g., CaO, FeO, MgO, TiO₂), highly enriched in lithophile trace elements, and highly but variably enriched in F and Cl. The melt inclusions contain up to several thousand ppm Cl and nearly 3 wt% F, on average; several inclusions contain more than 5 wt% F. The melt inclusions are geochemically similar to the corresponding whole-rock sample, except that the former contain much more F and less CaO, FeO, Zr, Nb, Sr, and Ba. The Sr and Ba abundances are very low implying the melt inclusions represent magma that was more evolved than that represented by the bulk rock. Relationships involving melt constituents reflect increasing lithophile-element and halogen abundances in residual melt with progressive magma differentiation. Modeling demonstrates that differentiation was dominated by crystal fractionation involving quartz and feldspar and significant quantities of topaz and F-rich zinnwaldite. The computed abundances of the latter phases greatly exceed their abundances in the rocks, suggesting that the residual melt was separated physically from phenocrysts during magma movement and evolution.Interactions of aqueous fluids with silicate melt were also critical to magma evolution. To better understand the role of halogen-charged, aqueous fluids in magmatic differentiation and in subsequent mineralization and metasomatism of the Zinnwald granites, Cl-partitioning experiments were conducted with a F-enriched silicate melt and aqueous fluids at 2,000 bar (200 MPa). The results of the experimentally determined partition coefficients for Cl and F, the compositions of fluid inclusions in quartz and other phenocrysts, and associated geochemical modeling point to an important role of magmatic-hydrothermal fluids in influencing magma geochemistry and evolution. The exsolution of halogen-charged fluids from the Li- and F-enriched Zinnwald granitic magma modified the Cl, alkali, and F contents of the residual melt, and may have also sequestered Li, Sn, and W from the melt. Many of these fluids contained strongly elevated F concentrations that were equivalent to or greater than their Cl abundances. The exsolution of F-, Cl-, Li-, ± W- and Sn-bearing hydrothermal fluids from Zinnwald granite magmas was important in effecting the greisenizing and alkali-feldspathizing metasomatism of the granites and the concomitant mineralization.Editorial Handling: B. Lehmann     

富F熔体-溶液流体体系的地球化学性状及成矿效应研究进展

F既是重要的岩浆挥发分,又是重要的助熔剂和矿化剂,同时也是克拉克值较大的元素之一,并且在(铝)硅酸盐熔体中高度可溶。本文从F的常见工业矿物和主要赋存形式、分配行为的多样性、对其它元素分配行为的影响、矿化作用(即亲氟元素在热液体系中的氟化物络合形式、存在环境和沉淀机制等)、萤石和冰晶石的溶解及沉淀机制以及富F岩浆一热液体系的成矿专属性及特征6个方面探讨了F的地球化学成矿作用。结论认为:F必须有能力大量进入与花岗质或伟晶岩质熔体共存的含水流体相中才具有进一步的成矿学意义,云英岩化、钠长石化、含黄玉—萤石石英脉、具有较高F/CaO比值的残余熔体以及F在高度演化花岗质岩浆中的过饱和等因素均可能导致含矿富F热液的出溶;但总体上,富F岩浆—热液体系具有成矿专属性的原因之一仍在于:F首先通过对熔体物理化学性质的影响间接支配着高场强亲氟元素如W、Sn、Nb、Ta、REE、U等的热液成矿效应。     

Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks

Some F-rich granitic rocks show anomalous, nonchondritic ratios of Y/Ho, extreme negative Eu anomalies, and unusual, discontinuous, segmented chondrite-normalised plots of rare earth elements (REE). The effects of F-rich fluids have been proposed as one of the explanations for the geochemical anomalies in the evolved granitic systems, as the stability of nonsilicate complexes of individual rare earths may affect the fluid-melt element partitioning. The lanthanide tetrad effect, related to different configurations of 4f-electron subshells of the lanthanide elements, is one of the factors affecting such complexing behaviour. We present the first experimental demonstration of the decoupling of Y and Ho, and the tetrad effect in the partitioning of rare earths between immiscible silicate and fluoride melts. Two types of experiments were performed: dry runs at atmospheric pressure in a high-temperature centrifuge at 1100 to 1200°C, and experiments with the addition of H₂O at 700 to 800°C and 100 MPa in rapid-quench cold-seal pressure vessels. Run products were analysed by electron microprobe (major components), solution-based inductively coupled plasma mass spectrometry (ICP-MS) (REE in the centrifuged runs), and laser ablation ICP-MS (REE and Li in the products of rapid-quench runs). All the dry centrifuge runs were performed at super-liquidus, two-phase conditions. In the experiments with water-bearing mixtures, minor amounts of aqueous vapour were present in addition to the melts. We found that lanthanides and Y concentrated strongly in the fluoride liquids, with two-melt partition coefficients reaching values as high as 100-220 in water-bearing compositions. In all the experimental samples, two-melt partition coefficients of lanthanides show subtle periodicity consistent with the tetrad effect, and the partition coefficient of Y is greater than that of Ho. One of the mixtures also produced abundant fluorite (CaF₂) and cryolite (Na₃AlF₆) crystals, which enabled us to study fluorite-melt and cryolite-melt REE partitioning. REE concentrations in fluorite are high and comparable to those in the fluoride melt. However, fluorite-melt partition coefficients appear to depend mostly on ionic radii and show neither significant tetrad anomalies, nor differences in Y and Ho partitioning. In contrast, REE concentrations in cryolite are low (∼5-10 times lower than in the silicate melt), and cryolite-melt REE partitioning shows very strong tetrad and Y-Ho anomalies. Our results imply that Y-Ho and lanthanide tetrad anomalies are likely to be caused mainly by aluminofluoride complexes, and the tetrad REE patterns in natural igneous rocks can result from fractionation of F-rich magmatic fluids.     

Nb-Ta-Ti-W-Sn-oxide minerals as indicators of a peraluminous P- and F-rich granitic system evolution: Podlesí, Czech Republic

Summary The strongly peraluminous, P- and F-rich granitic system at Podlesí in the Krušné Hory Mountains, Czech Republic, resembles the zonation of rare element pegmatites in its magmatic evolution (biotite → protolithionite → zinnwaldite granites). All granite types contain disseminated Nb-Ta-Ti-W-Sn minerals that crystallized in the following succession: rutile + cassiterite (in biotite granite), rutile + cassiterite → ferrocolumbite (in protolithionite granite) and ferrocolumbite → ixiolite → ferberite (in zinnwaldite granite). Textural features of Nb-Ta-Ti-W minerals indicate a pre-dominantly magmatic origin with only minor post-magmatic replacement phenomena. HFSE remained in the residual melt during the fractionation of the biotite granite. An effective separation of Nb + Ta into the melt and Sn into fluid took place during subsequent fractionation of the protolithionite granite, and the tin-bearing fluid escaped into the exocontact. To the contrast, W contents are similar in both protolithionite and zinnwaldite granites. Although the system was F-rich, only limited Mn-Fe and Ta-Nb fractionation appeared. Enrichment of Mn and Ta was suppressed due to foregoing crystallization of Mn-rich apatite and relatively low Li content, respectively. The content of W in columbite increases during fractionation and enrichment in P and F in the melt. Ixiolite (up to 1 apfu W) instead of columbite crystallized from the most fluxes-enriched portions of the melt (unidirectional solidification textures, late breccia).     

Origin of biotite-apatite-rich enclaves, Achala batholith, Argentina

The Achala batholith of Argentina contains very unusual layered enclaves containing up to 30% apatite and 50% biotite in some layers. This modal mineralogy produces bulk-rock compositions that cannot represent liquids, having as little as 29% SiO₂ and up to 8% P₂O₅. Nor can the enclaves represent metasedimentary xenoliths because: (1) none of the Precambrian wall rocks has these compositions; (2) none of the metasedimentary xenoliths present within the batholith shows any degree of transition to the mica-apatite-rich enclaves; (3) the compositions and textures in the enclaves are inconsistent with metasediments; (4) a geochronological study of zircon from an enclave gives an age of 368 ± 2 Ma, the exact age of zircons in the granitic host rocks. For these reasons, we conclude that the enclaves are neither xenoliths of Precambrian wall rocks nor restite of a Precambrian source. The identical age of the enclave and the host granites, coupled with textural, mineralogical, and bulk-rock characteristics of the enclaves, indicates that the enclaves are magmatic segregations, i.e., cumulates. The F-rich nature of the stubby-shaped apatites and biotites indicates a high F content of the magma parental to the enclaves. We infer that the viscosity of the melt was lowered sufficiently to allow cumulates to form in spite of the granitic composition of the melt. Received: 12 December 1996 / Accepted: 11 August 1997     

新疆喀拉萨依含锡花岗岩体地质特征及成岩成矿机制

通过对大量实际资料的分析认为,喀拉萨依含锡花岗岩体形成于造山期后阶段,年龄300Ma左右,岩体中出露的肉红色和灰白色黑云母钾长花岗岩由强分异岩浆先后侵入形成,二者具同源演化关系;原始岩浆为上地壳变碎屑质沉积岩部分熔融形成的黑云母二长花岗质岩浆;发育于岩体边部的云英岩型锡矿化同岩浆期后富含氟的高温气液流体作用有关。     

Topaz–albite granites and rare-metal mineralization in the Limu District, Guangxi Province, southeast China

The topaz-albite granites of the Limu district are ultra-acidic, peraluminous, Li-F-Na-rich and Sn-Ta-Nb-mineralized. A distinct vertical zonation is developed in the granite stocks. There is an upward, systematic transition from leucocratic microcline-albite granite, through albite-microcline granite, topaz-albite granite, pegmatite stockscheider and layered pegmatite-aplite dikes, to K-feldspar-quartz veins and lepidolite-fluorite stringers in the country rocks. Snow-ball textures, homogeneous distribution of rock-forming and accessory minerals, disseminated mineralization, and melt inclusions in quartz, topaz, and albite are typical features indicative of their crystallization from the late stage Li-F-Na-rich and Sn-Ta-Nb-bearing residual granitic melts at a higher intrusion level. A comparison with rare-metal-bearing pegmatite, ongonite, topaz rhyolite and obsidian glass from other regions shows the worldwide existence of these specialized residual melts. Their emplacement and crystallization in a variety of geological environments result in the formation of a series of chemically similar rocks with different petrographic textures and mineral associations. The topaz-albite granites and associated mineralization in the Limu district provide a good example of highly evolved magmatic fractionation in the F-rich granite system and fluid/melt partitioning behavior of rare-metal elements during magmatic-hydrothermal evolution.