Oxidation potential and the composition of metamorphic fluid as a solution to the inverse problem of convex programming

Using the Selektor-C software program package, oxidation potential and the composition of metamorphogenic fluid were determined for mineral assemblages from nine samples of granulite-grade metamorphic rocks by solving the inverse problems of convex programming. The calculated and real mineral assemblages are in good agreement with respect to the composition and association of minerals, which is compelling evidence for the attainment of chemical equilibrium (minimum of Gibbs free energy) under given P-T conditions. Based on the dual solution of the inverse problem, a new approach was proposed for the estimation of the oxidation potential of fluid and mineral assemblages, which can be used to determine oxygen potential for almost any mineral association, independent of the presence of magnetite, ilmenite, or graphite. It was found that magnetite-free mineral associations are characterized by highly reducing conditions corresponding to oxygen potentials close to the CCO buffer. The external metamorphic fluid that was present during granulite-facies metamorphism was probably formed in the graphite stability field. The results of calculations for the model aqueous electrolyte solution-mineral assemblage suggest high SiO₂ solubility in the metamorphogenic fluid. Therefore, the process of granulite metamorphism may be a potent geochemical factor of the redistribution and transportation of silica from lower to upper crustal levels.     

Equilibration and disequilibration between monazite and garnet: indication from phase‐composition and quantitative texture analysis

The integration of information which can be gained from accessory [i.e. age (t)] and rock‐forming minerals [i.e. temperature (T) and pressure (P)] requires a more profound understanding of the equilibration kinetics during metamorphic processes. This paper presents an approach comparing conventional P–T estimate from equilibrated assemblages of rock‐forming minerals with temperature data derived from yttrium‐garnet‐monazite (YGM) and yttrium‐garnet‐xenotime (YGX) geothermometry. Such a comparison provides an initial indication on differences between equilibration of major and trace elements. Regarding this purpose, two migmatites, two polycyclic and one monocyclic gneiss from the Central Alps (Switzerland, northern Italy) were investigated. While the polycyclic samples exhibit trace‐element equilibration between monazite and garnet grains assigned to the same metamorphic event, there are relics of monazite and garnet obviously surviving independent of their textural position. These observations suggest that surface processes dominate transport processes during equilibration of those samples. The monocyclic gneiss, on the contrary, displays rare isolated monazite with equilibration of all elements, despite comparably large transport distances. With a nearly linear crystal‐size distribution of the garnet grain population, growth kinetics, related to the major elements, were likely surface‐controlled in this sample. In contrast to these completely equilibrated examples, the migmatites indicate disequilibrium between garnet and monazite with a change in REE patterns on garnet transects. The cause for this disequilibrium may be related to a potential disequilibrium initiated by a changing bulk chemistry during melt segregation. While migmatite environments are expected to support high transport rates (i.e. high temperatures and melt presence), the evolution of equilibration in migmatites is additionaly related to change in chemistry. As a key finding, surface‐controlled equilibration kinetics seem to dominate transport‐controlled processes in the investigated samples. This may be decisive information towards the understanding of age data derived from monazite.     

北京十三陵地区前寒武纪岩石中稀土矿物的发现及对同位素测年的意义

华北中、新元古代地层的年龄数据很混乱(表1),本文建议将北京十三陵地区新发现的稀土矿物用SHRIMP方法测年,有助于问题的解决。北京十三陵地区保存了新太古代五台群和新—中元古代较完整的地层,电子耦合等离子体分析(即原子收光谱分析)(ICP)的定量分析数据表明,在这些地层中,岩石中所含钾和稀土元素含量都比北美页岩(NASC)、欧洲页岩(ES)和澳大利亚后太古宙页岩(PAAS)高出很多,经电子扫描+能谱仪+波谱仪(SEM+EDS+WDS)分析证明,在岩石中包含独居石(碎屑的和自生-成岩的)和磷钇矿(自生-成岩的),并首次发现钍石-独居石环带状混合矿物(变质的)以及显微脉状稀土硅酸盐矿物(地下流体形成的)等稀土矿物。利用激光拉曼光谱鉴定发现稀土矿物的分布状态包括:1在太古宙五台群的片麻岩中,云母、石英和长石之间有非自形晶独居石,而且在石英单晶里还有独居石的自形晶包裹体;并发现独居石和钍石-独居石环带状混合矿物,这些稀土矿物都是变质成因的;2在新太古代五台群片麻岩的准平原化风化面上,沉积的元古宙常沟组的底砾岩中发现了碎屑的独居石,这些独居石的同位素年龄对于元古宇的底界定年意义重大;3在常州沟组下部压扁-透镜状层理的粉砂岩中,普遍发现碎屑锆石的外缘生长出自生-成岩磷钇矿,磷钇矿的同位素定年对于常州沟组的地层年代有代表性意义;4串岭沟组的粉砂岩中发现了无形晶状自生-成岩独居石和磷钇矿,并且较多出现在显微缝合线内外,可作为SHRIMP测年的对象;5大红峪组粉砂岩中除了发现碎屑独居石外还发现脉状硅-铝稀土矿物,可能与后元古宙热液活动有关。事实上这些自生-成岩的稀土矿物的形成,都是源自太古宙富含稀土元素的变质岩石,其形成机理也与地下流体活动有关。笔者认为北京十三陵以及至华北地区,前寒武系富稀土元素形成的自生-成岩的稀土矿物,有助于用SHRIMP方法对前寒武纪地层的同位素测年研究。     

Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part I: Crystallization of zircon and REE-phosphates over three million years—a geochemical and U–Pb geochronological study

Zircon, monazite and xenotime crystallized over a temperature interval of several hundred degrees at the magmatic to hydrothermal transition of the Sn and W mineralized Mole Granite. Magmatic zircon and monazite, thought to have crystallized from hydrous silicate melt, were dated by conventional U–Pb techniques at an age of 247.6 ± 0.4 and 247.7 ± 0.5 Ma, respectively. Xenotime occurring in hydrothermal quartz is found to be significantly younger at 246.2 ± 0.5 Ma and is interpreted to represent hydrothermal growth. From associated fluid inclusions it is concluded that it precipitated from a hydrothermal brine ≤ 600 °C, which is below the accepted closure temperature for U–Pb in this mineral. These data are compatible with a two-stage crystallization process: precipitation of zircon and monazite as magmatic liquidus phases in deep crustal magma followed by complete crystallization and intimately associated Sn–W mineralization after intrusion of the shallow, sill-like body of the Mole Granite. Later hydrothermal formation of monazite in a biotite–fluorite–topaz reaction rim around a mineralized vein was dated at 244.4 ± 1.4 Ma, which distinctly postdates the Mole Granite and is possibly related to a younger hidden intrusion and its hydrothermal fluid system.

Obtaining precise age data for magmatic and hydrothermal minerals of the Mole Granite is hampered by uncertainties introduced by different corrections required for multiple highly radiogenic minerals crystallising from evolved hydrous granites, including ²³⁰Th disequilibrium due to Th/U fractionation during monazite and possibly xenotime crystallization, variable Th/U ratios of the fluids from which xenotime was precipitating, elevated contents of common lead, and post-crystallization lead loss in zircon, enhanced by the fluid-saturated environment. The data imply that monazite can also survive as a liquidus phase in protracted magmatic systems over periods of 10⁶ years. The outlined model is in agreement with prominent chemical core-rim variation of the zircon.     

诸广南部产铀花岗岩长江岩体中的绿泥石和铀源矿物研究

长江岩体是诸广南部地区重要的产铀花岗岩体之一,此次研究运用电子探针和扫描电镜对长江岩体新鲜花岗岩和 蚀变花岗岩中的绿泥石和有关含铀矿物进行了精细对比,揭示花岗岩中铀的活化与成矿前期或早期致使花岗岩发生绿泥 石化的还原性热液蚀变作用关系密切,黑云母等的绿泥石化蚀变,使其中包裹的一些含铀副矿物也发生蚀变,导致原来 以类质同象形式存在于副矿物中的惰性铀转变成活性铀,并在绿泥石附近沉淀成铀石等铀含量高且在成矿期低度氧化性 热液作用下容易释放铀的矿物。长江岩体中的副矿物有锆石、磷灰石、褐帘石、铀石-钍石、晶质铀矿、独居石等,其 中,晶质铀矿、铀石、铀钍石中铀含量高且铀容易释放,是长江岩体的主要铀源矿物;独居石中铀含量较高,当其周围 矿物绿泥石化时,独居石蚀变形成直氟碳钙铈矿并释放铀,因而也是长江岩体的潜在铀源矿物;锆石中铀含量虽高,但 因其结构稳定,铀难以释放,因此它不是长江岩体中重要的铀源矿物;磷灰石、褐帘石中铀含量均低于检测限,作为铀 源矿物的可能性很小。     

Hydrothermal alteration of monazite in the Precambrian crystalline basement of the Athabasca Basin (Saskatchewan, Canada): implications for the formation of unconformity-related uranium deposits

Microanalytical studies of basement rocks below the Athabasca sandstone basin indicate that monazite is the dominant uranium-bearing mineral in the study area. Drill core samples of hydrothermally altered basement show that monazite is commonly altered to a Th–silicate phase, and uranium has been significantly mobilized. On average, 75% of the uranium bound to monazite is leached out during monazite alteration. In contrast, no substantial mobilization of uranium from detrital minerals (e.g. zircon) has yet been observed in the Athabasca sandstones. It is suggested that hydrothermal alteration of granitic rocks (especially potassic pegmatoids and potassic orthogneisses) of the sub-Athabasca basement, represents the most important uranium source for the unconformity-type deposits. Received: 3 December 1999 / Accepted: 24 May 2000     

Monazite chemistry: evidence for a prehistoric journey

The chemistry of monazite from the black sand deposits of northern Sinai beach suggests that pegmatites and granites of the Eastern Desert of Egypt are the most likely source rocks. The floods associated with the pluvial periods prevailed in Egypt during the Pleistocene were able to erode the source rocks and liberate heavy minerals including monazite. The mineral grains were moved through several wadis and tributaries to the River Nile. At the confluence sites, these heavy minerals were mixed with the Ethiopian and central African heavy mineral assemblages. The grains continued to move together downriver until being deposited in their current locations.     

电子探针技术研究粤北龙华山岩体中独居石蚀变晕圈的结构与成分特征

独居石是华南产铀花岗岩中常见的含铀副矿物.龙华山岩体是粤北诸广山复式岩体中一个重要的产铀花岗岩,该岩体的独居石具有蚀变晕圈现象.但是,该岩体中独居石蚀变晕圈的结构和成分特征以及对铀成矿的指示意义尚未开展研究.本文利用电子探针(EPMA)对龙华山岩体的独居石蚀变晕圈开展结构和成分研究.测试结果表明:独居石蚀变晕圈是从内到...     

The trace element compositions of S-type granites: evidence for disequilibrium melting and accessory phase entrainment in the source

Within individual plutons, the trace element concentrations in S-type granites generally increase with maficity (total iron and magnesium content and expressed as atomic Fe + Mg in this study); the degree of variability in trace element concentration also expands markedly with the same parameter. The strongly peraluminous, high-level S-type granites of the Peninsular Pluton (Cape Granite Suite, South Africa) are the product of biotite incongruent melting of a metasedimentary source near the base of the crust. Leucogranites within the suite represent close to pure melts from the anatectic source and more mafic varieties represent mixtures of melt and peritectic garnet and ilmenite. Trace elements such as Rb, Ba, Sr and Eu, that are concentrated in reactant minerals in the melting process, show considerable scatter within the granites. This is interpreted to reflect compositional variation in the source. In contrast, elements such as LREE, Zr and Hf, which are concentrated within refractory accessory phases (zircon and monazite), show well-defined negative correlations with increasing SiO₂ and increase linearly with increasing maficity. This is interpreted to reflect coupled co-entrainment of accessory minerals and peritectic phases to the melt: leucocratic rocks cannot have evolved from the more mafic compositions in the suite by a process of fractional crystallisation because in this case they would have inherited the zircon-saturated character of this hypothetical earlier magma. Trace element behaviour of granites from the Peninsular Pluton has been modelled via both equilibrium and disequilibrium trace element melting. In the disequilibrium case, melts are modelled as leaving the source with variable proportions of entrained peritectic phases and accessory minerals, but before the melt has dissolved any accessory minerals. Thus, the trace element signature of the melt is largely inherited from the reactants in the melting reaction, with no contribution from zircon and monazite dissolution. In the equilibrium case, melt leaves the source with entrained crystals, after reaching zircon and monazite saturation. A significant proportion of the rocks of the Peninsular Pluton have trace element concentrations below those predicted by zircon and monazite saturation. In the case of the most leucocratic rocks all compositions are zircon undersaturated; whilst the majority of the most mafic compositions are zircon oversaturated. However, in both cases, zircon is commonly xenocrystic. Thus, the leucocratic rocks represent close to pure melts, which escaped their sources rapidly enough that some very closely match the trace element disequilibrium melting model applied in this study. Zircon dissolution rates allow the residency time for the melt in the source to be conservatively estimated at less than 500 years.     

Bastnaesite from Kanigiri granite, Prakasam district, Andhra Pradesh

For the first time we report bastnaesite and hydroxyl bastnaesite (lanthanum cerium fluoro-carbonate) from the Kanigiri granite. The host granitoids are of A-type and vary in composition from quartz syenites to peralkaline granites. Rare metal and rare earth-bearing minerals identified by X-ray diffraction (XRD) studies in Kanigiri granite are bastnaesite and hydroxyl bastnaesite, besides columbite-tantalite, monazite, fergusonite, thorite and euxenite. Petromineralogical studies have also revealed the presence of bastnaesite. The presence of bastnaesite in Kanigiri granite suggests that the host felsic rocks may also form a potential source for light rare earth mineral, bastnaesite, apart from the already known rare-metal minerals.     

长白山天池火山的岩石矿物学特征——对结晶分异过程和岩浆混合作用的启示

本文对天池火山玄武岩盾,粗面质-碱流质层状锥体以及顶部的粗面质-碱流质碎屑岩类及熔岩的岩石矿物成分做了系统分析,发现在玄武岩类中的主要矿物组合为斜长石、富钙辉石以及富镁橄榄石,而粗面岩-碱流岩类的主要矿物组合为碱性长石、富铁的辉石及橄榄石,并开始出现石英、独居石以及大量的铁钛氧化物,符合结晶分异的演化趋势。同时在玄武岩类及粗面-碱流岩类中均存在不平衡矿物,再结合矿物环带的成分变化、矿物的熔蚀现象及不同特征的岩石条带等,认为天池火山在黑石沟玄武岩、第一、三造锥阶段粗面岩以及千年大喷发的浮岩中均存在岩浆混合作用。根据岩石学及年代学等特征,认为不同时期的玄武质岩浆来自同一地幔源区,经不同程度的结晶分异作用形成,前造锥阶段及造锥阶段的岩石由不同阶段的玄武岩演化而来,全新世的碱流岩类则由造锥阶段粗面岩类演化而来。     

江西崇义铁木里碱长花岗岩中铌和稀土元素的富集机制

华南是我国重要的战略性矿产资源基地,以花岗岩相关的稀有和稀土金属成矿作用而举世瞩目。其中,铌的成矿作用一般与过铝质高分异花岗岩有关,稀土元素则随岩浆演化程度增强而富集程度降低,而江西铁木里含黑云母碱长花岗岩体同时富集铌和稀土元素,矿化组合极具特色。本文在详细的矿物岩相学研究基础上,利用电子探针、飞秒激光电感耦合等离子质谱对铌和稀土矿物进行了矿物地球化学分析,借此对铁木里碱长花岗岩中铌和稀土元素的富集机制进行探讨。铁木里岩体由肉红色含黑云母碱长花岗岩(r-G)和灰白色含黑云母碱长花岗岩(g-G)组成,发育暗色包体。r-G中的铌矿物主要为岩浆期形成的铌铁金红石,稀土矿物包括岩浆期形成的硅钛铈矿、独居石、磷灰石和热液期形成的独居石和氟碳(钙)铈矿。g-G中的铌矿物包括岩浆期形成的铌铁金红石和热液期形成的铌铁金红石、易解石、铌铁矿,稀土矿物包括岩浆期磷灰石和热液期磷灰石、独居石、氟碳(钙)铈矿。暗色包体为岩浆混合成因,内含磷灰石、独居石和零星的硅钛铈矿、金红石。矿物组合特征显示,铁木里碱长花岗岩中的铌和稀土元素经过了岩浆和热液两个时期的富集。应用金红石、磷灰石、绿泥石等矿物成分特征约束了岩浆-...     

独居石成因矿物学特征及其对U-Th-Pb年龄解释的制约

独居石U-Pb定年在岩浆活动、变质作用和沉积作用等方面发挥着日益重要的作用,但是由于独居石成因复杂,因此从成因矿物学角度对不同成因独居石的特征进行总结将有助于解释独居石年代学数据.总结了不同成因独居石的矿物共生关系和组构特征、外部形貌-内部结构、化学元素特征,依托Th、U、Y、Ca、Pb、REE含量及其比值关系进行化学...     

Monazite U-Pb dating of staurolite grade metamorphism in pelitic schists

A study of the occurrence of and relations between rare-earth element (REE) minerals in pelitic schists indicates that monazite forms at or near the P and T of the staurolite isograd. Samples at staurolite grade from the Silurian Perry Mountain Formation in the Rumford quadrangle of Maine yield monazite in sufficient quantities to permit accurate dating of the metamorphic events forming the monazites. The bulk chemistry of the metapelites, as seen in the major element abundances and REE patterns, does not vary significantly across the study area. Thus the appearance and disappearance of REE phases is assumed to reflect changes in metamorphic grade. In a sample from the biotite zone, scanning electron microscope and microprobe studies show allanite and monazite intimately associated on a 10 m scale. The texture suggest that metastable detrital monazite breaks down, distributing its REE components to allanite. From samples below staurolite grade in which monazite is not present, our observations suggest that REEs are partitioned into allanite. At or near the staurolite isograd monazite forms as a metamorphic mineral, initiating its role as a geochronometer. Garnet-biotite geothermometry on samples at this grade from this and other studies places constraints on the minimum temperature necessary to form monazite: 525° C±25°C at 3.1±0.25 kbar. A total of 15 separates from nine schist samples ranging up to sillimanite grade have been dated. Each date is remarkably concordant, even though petrologic and textural studies by previous workers have shown that the rocks in the area have been affected by at least three metamorphic episodes. Calculations indicate insignificant Th disequilibrium in these monazites. The conditions associated with the metamorphic events suggest that monazite remains closed to lead loss provided that subsequent metamorphisms are at or below sillimanite grade. Two distinct metamorphic events are resolved, one at around 400 Ma and one at about 370 Ma. The latter was due to thermal effects of a nearby pluton that yields concordant monazite ages of 363 Ma. This work suggests that in addition to dating plutonism and high-grade metamorphism, monazite should be viewed as a reliable geochronometer for moderate metamorphism of pelitic schists.     

Interaction of rhyolite melts with monazite,xenotime, and zircon surfaces

The interfacial contact region between a rhyolite melt and the accessory minerals monazite, xenotime, and zircon is investigated using molecular dynamics simulations. On all surfaces, major structural rearrangement extends about 1 nm into the melt from the interface. As evidenced by the structural perturbations in the ion distribution profiles, the affinity of the melt for the surface increases in going from monazite to xenotime to zircon. Alkali ions are enriched in the melt in contact with an inert wall, as well as at the mineral surfaces. Melt in contact with zircon has a particularly strong level of aluminum enrichment. In xenotime, the enrichment of aluminum is less than that in zircon, but still notable. In monazite, the aluminum enrichment in the contact layer is much less. It is expected that the relative surface energies of these accessory minerals will be a strong function of the aluminum content of the melt and that nucleation of zircon, in particular, would be easier for melts with higher aluminum concentration. The crystal growth rate for zircon is expected to be slower at a higher aluminum concentration because of the effectiveness of aluminum in solvating the zircon surface. The variable interfacial concentration profiles across the series of accessory minerals will likely affect the kinetics of trace element incorporation, as the trace elements must compete with the major elements for surface sites on the growing accessory minerals.     

胶南榴辉岩矿物氧同位素平衡及其Sm-Nd年代学制约

对苏鲁地体中的胶南榴辉岩进行了矿物氧同位素分析，并与同一手标本矿物的Sm-Nd内部等时线定年和Nd-Sr同位素分布进行了对比。研究表明，石榴子石与绿辉石之间的氧同位素平衡与否能够对矿物Sm-Nd同位素体系的平衡状况和内部等时线定年结果的有效性给予直接制约。合理的石榴子石＋绿辉石Sm-Nd内部等时线年龄产于两矿物之间达到并在峰变质条件下保持氧同位素平衡的样品中，而两矿物之间处于氧同位素不平衡的样品不能给出正确的Sm-Nd内部等时线年龄。同一矿物在手标本尺度出现显著的O-Nd-Sr同位素不均一性，据此对这些元素在石榴子石和绿辉石中的扩散速率顺序进行了估计，不仅得到了与实验扩散系数相吻合的结果，而且由此估计出在峰变质条件下达到矿物内部同位素均一化所需要的时间应大于10Ma。     

扫描电镜能谱法测定独居石中铈、镧、钍等元素的含量

粒度细小的独居石、锆石等矿物在变质岩中含量少,利用岩石薄片偏反光显微镜鉴定技术一般不易确认,X射线粉晶衍射分析通常也检测不出此类微量矿物.利用电镜能谱分析技术能够检测出矿物主要组成元素,并能给出所测元素的浓度值.运用Casino程序和Quanta程序,据元素的浓度值可以计算出矿物中各元素的质量分数（%）.本次研究利用扫描电镜能谱仪检测了6个样品中微量矿物,结果表明：6个样品中主要元素组成为O、Ce、Nd、La、Al、P、Ca、Si、Ag、Th,与独居石矿物化学组成一致,可以判定所检测的6个样品为独居石.     

Oxygen isotope equilibrium between eclogite minerals and its constraints on mineral Sm-Nd chronometer

Sm-Nd and oxygen isotope analyses were carried out for mineral separates of ultrahigh pressure eclogites from the Sulu terrane in eastern China. The results show a direct correspondence in equilibrium or disequilibrium state between the oxygen and Sm-Nd isotope systems of eclogite minerals. The omphacite-garnet pairs of oxygen isotope equilibrium at eclogite-facies conditions yield meaningful Triassic Sm-Nd isochron ages, whereas those of oxygen isotope disequilibrium give non-Triassic ages of geological meaninglessness. This can be reasonably interpreted by the fact that the rates of oxygen diffusion in garnet and pyroxene are lower than, or close to, those of Nd diffusion, and thus attainment of isotopic equilibrium in the omphacite-garnet O system suggests achievement of Nd isotope equilibrium in the same mineral pairs. The presence or absence of fluid in the eclogite protoliths is a major rate-controlling factor for isotopic equilibration during high-grade metamorphism. It appears that the state of oxygen isotope equilibrium between cogenetic minerals can provide a critical test for the validity of the Sm-Nd mineral chronometer. In addition, the exact timing of the ultrahigh pressure metamorphism in the Dabie-Sulu terranes is constrained at Early Triassic rather than Late Triassic.     

New evidence of the Late Palaeozoic age of the quartzite-schist frame of the Ilmenogorsk complex (Southern Urals)

In the Ilmenogorsk metamorphic complex, Southern Urals, the Archean gneissic core and Riphean-Vendian quartzite-schist framing are traditionally distinguished. The age of the latter is not reliably determined. There were speculations about its possible Paleozoic age. Those are partially confirmed by isotopic data. The quartzite in the upper part of the section of schist strata detrital mineral grains were found, and they are similar to accessory minerals of the Kisegach Massif granitoids occurring among quartzite. The granitoids demonstrated to form phases of various age. It is assumed that the oldest of them (predating folding) could be intruded synchronously with sedimentation and serve as porvenance for the quartzite. The most informative of these minerals is monazite. Microprobe analyses results on monazite from quartzite and granite are given. Their REE distribution is demonstrated to be similar. This confirms the possibility of the granitoid erosion at the time of quartz sandstone deposition. Since the K-Ar age of granitoids Kisegach Massif is 252 ± 8 Ma, it was concluded that the Kyshtym quartzite-schist unit of Ilmeny has about the same age.     

变质矿床的成因分类

本文溯本求源,讨论了变质成矿作用学说的建立、变质作用及变质成矿作用研究的几个历史阶段和现状,对以往的变质矿床分类做了分析,论证了本分类的理论前提,在该分类中划分出前变质、流变质(peo-)①和正变质矿床。