An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.     

Prograde metamorphic sequence of REE minerals in pelitic rocks of the Central Alps: implications for allanite–monazite–xenotime phase relations from 250 to 610 °C

The distribution of REE minerals in metasedimentary rocks was investigated to gain insight into the stability of allanite, monazite and xenotime in metapelites. Samples were collected in the central Swiss Alps, along a well‐established metamorphic field gradient that record conditions from very low grade metamorphism (250 °C) to the lower amphibolite facies (～600 °C). In the Alpine metapelites investigated, mass balance calculations show that LREE are mainly transferred between monazite and allanite during the course of prograde metamorphism. At very low grade metamorphism, detrital monazite grains (mostly Variscan in age) have two distinct populations in terms of LREE and MREE compositions. Newly formed monazite crystallized during low‐grade metamorphism (<440 °C); these are enriched in La, but depleted in Th and Y, compared with inherited grains. Upon the appearance of chloritoid (～440–450 °C, thermometry based on chlorite–choritoid and carbonaceous material), monazite is consumed, and MREE and LREE are taken up preferentially in two distinct zones of allanite distinguishable by EMPA and X‐ray mapping. Prior to garnet growth, allanite acquires two growth zones of clinozoisite: a first one rich in HREE + Y and a second one containing low REE contents. Following garnet growth, close to the chloritoid–out zone boundary (～556–580 °C, based on phase equilibrium calculations), allanite and its rims are partially to totally replaced by monazite and xenotime, both associated with plagioclase (± biotite ± staurolite ± kyanite ± quartz). In these samples, epidote relics are located in the matrix or as inclusions in garnet, and these preserve their characteristic chemical and textural growth zoning, indicating that they did not experience re‐equilibration following their prograde formation. Hence, the partial breakdown of allanite to monazite offers the attractive possibility to obtain in situ ages, representing two distinct crystallization stages. In addition, the complex REE + Y and Th zoning pattern of allanite and monazite are essential monitors of crystallization conditions at relatively low metamorphic grade.     

Monazite–xenotime miscibility gap thermometry. I. An empirical calibration

Rare earth element (REE) and yttrium concentrations of coexisting monazite and xenotime were determined from a suite of seven metapelites from the Variscan fold belt in NE Bavaria, Germany. The metapelites include a continuous prograde, mainly low-P (3–5 kbar) metamorphic profile from greenschist (c. 400 °C) to lower granulite facies conditions (c. 700 °C). The LREE (La–Sm) are incorporated preferentially in monoclinic monazite (REO₉ polyhedron), whereas the HREE plus Y are concentrated in tetragonal xenotime (REO₈ polyhedron). The major element concentrations of both phases in all rocks are very similar and do not depend on metamorphic grade. Monazite consists mainly of La, Ce and Nd (La_0.20–0.23, Ce_0.41–0.45, Nd_0.15–0.18)PO₄, all other elements are below 6 mol%. Likewise, xenotime consists mainly of YPO₄ with some Dy and Gd solid solutions (Y_0.76–0.80, Dy_0.05–0.07, Gd_0.04–0.06). In contrast, the minor HREE concentrations in monazite increase strongly with increasing metamorphic grade: Y, Dy and Gd increase by a factor of 3–5 from greenschist to granulite facies rocks. Monazite crystals often show zonation with cores low in HREE and rims high in HREE that is interpreted as growth zonation attained during prograde metamorphism. Similarly, Sm and Nd in xenotimes increase by a factor of 3–4 with increasing metamorphic grade. Prograde zonation in single crystals of xenotime was not observed. The X_HREE+Y in monazite and X_LREE in xenotime of the seven rocks define two limbs along the strongly asymmetric miscibility gap from c. 400 °C to 700 °C. The empirical calibration of the monazite miscibility gap limb coexisting with xenotime is appropriate for geothermometry. Due to its contents of U and Th, monazite has often been used for U–Pb age determination. The combination of our empirical thermometer on prograde zoned monazite along with possible age determination of zoned single crystals may provide information about prograde branches of temperature–time paths.     

Residence of REE, Y, Th and U in Granites and Crustal Protoliths; Implications for the Chemistry of Crustal Melts

A systematic study with laser ablation—ICP-MS, scanningelectron microscopy and electron microprobe revealed that 70–95wt% of REE (except Eu), Y, Th and U in granite rocks and crustalprotoliths reside within REEYThU-rich accessories whose nature,composition and associations change with the rock aluminosity.The accessory assemblage of peraluminous granites, migmatitesand high-grade rocks is composed of monazite, xenotime (in low-Cavarieties), apatite, zircon, Thorthosilicate, uraninite andbetafite-pyrochlore. Metaluminous granites have allanite, sphene,apatite, zircon, monazite and Thorthosilicaie. Peralkaline graniteshave aeschinite, fergusonite, samarskite, bastnaesite, fluocerite,allanite, sphene, zircon, monazite, xenotime and Th-orthosilicate.Granulite-grade garnets are enriched in Nd and Sm by no lessthan one order of magnitude with respect to amphibolite-gradegarnets. Granulitegrade feldspars are also enriched in LREEwith respect to amphibolite-grade feldspars. Accessories causenon-Henrian behaviour of REE, Y, Th and U during melt—solidpartitioning. Because elevated fractions of monazite, xenotimeand zircon in common migmatites are included within major minerals,their behaviour during anatexis is controlled by that of theirhost. Settling curves calculated for a convecting magma showthat accessories are too small to settle appreciably, beingseparated from the melt as inclusions within larger minerals.Biotite has the greatest tendency to include accessories, therebyindirectly controlling the geochemistry of REE, Y, Th and U.We conclude that REE, Y, Th and U are unsuitable for petrogeneticalmodelling of granitoids through equilibrium-based trace-elementfractionation equations. KEY WORDS: accessory minerals; geochemical modelling; granitoids; REE, Y, Th, U     

Dating metamorphic reactions and fluid flow: application to exhumation of high-P granulites in a crustal-scale shear zone, western Canadian Shield

The Legs Lake shear zone is a crustal‐scale thrust fault system in the western Canadian Shield that juxtaposes high‐pressure (1.0+ GPa) granulite facies rocks against shallow crustal (< 0.5 GPa) amphibolite facies rocks. Hangingwall decompression is characterized by breakdown of the peak assemblage Grt + Sil + Kfs + Pl + Qtz into the assemblage Grt + Crd + Bt ± Sil + Pl + Qtz. Similar felsic granulite occurs throughout the region, but retrograde cordierite is restricted to the immediate hangingwall of the shear zone. Textural observations, petrological analysis using P–T/P–M_H2O phase diagram sections, and in situ electron microprobe monazite geochronology suggest that decompression from peak conditions of 1.1 GPa, c. 800 °C involved several distinct stages under first dry and then hydrated conditions. Retrograde re‐equilibration occurred at 0.5–0.4 GPa, 550–650 °C. Morphology, X‐ray maps, and microprobe dates indicate several distinct monazite generations. Populations 1 and 2 are relatively high yttrium (Y) monazite that grew at 2.55–2.50 Ga and correspond to an early granulite facies event. Population 3 represents episodic growth of low Y monazite between 2.50 and 2.15 Ga whose general significance is still unclear. Population 4 reflects low Y monazite growth at 1.9 Ga, which corresponds to the youngest period of high‐pressure metamorphism. Finally, population 5 is restricted to the hydrous retrograded granulite and represents high Y monazite growth at 1.85 Ga that is linked directly to the synkinematic garnet‐consuming hydration reaction (KFMASH): Grt + Kfs + H₂O = Bt + Sil + Qtz. Two samples yield weighted mean microprobe dates for this population of 1853 ± 15 and 1851 ± 9 Ma, respectively. Subsequent xenotime growth correlates with the reaction: Grt + Sil + Qtz + H₂O = Crd. We suggest that the shear zone acted as a channel for fluid produced by dehydration of metasediments in the underthrust domain.     

High-Grade Fluid Metasomatism on both a Local and a Regional Scale: the Seward Peninsula, Alaska, and the Val Strona di Omegna, Ivrea-Verbano Zone, Northern Italy. Part II: Phosphate Mineral Chemistry

This study explores the origin and geochemical evolution ofapatite, monazite, and xenotime along two metamorphic traverses.The first, from the Kigluaik Mountains, Seward Peninsula, Alaska,consists of a localized (85 cm) orthopyroxene–clinopyroxene-bearingdehydration zone. The second consists of orthopyroxene ±clinopyroxene-bearing granulite facies metabasite layers interlayeredwith metapelites over a 3–4 km traverse, along the ValStrona, Ivrea–Verbano Zone, Northern Italy (IVZ). In bothdehydration zones small Th- and U-poor inclusions of monaziteand/or xenotime occur in the apatite. These inclusions are metasomaticallyinduced and nucleated within the apatite via the coupled substitutionsNa⁺ + (Y + REE)³⁺ = 2 Ca²⁺ and Si⁴⁺ + (Y + REE)³⁺ = P⁵⁺ + Ca²⁺.These are not present in apatite from the original amphibolitefacies gneiss. Apatite, in both dehydration zones, also showsa relative increase in both F and Cl compared with apatite fromthe amphibolite facies zone. Granulite facies metabasites inthe IVZ also contain isolated monazite grains, which range fromuniform to complexly zoned in Th the (13–30·1 mol% ThSiO₄). These are the product of breakdown and subsequentmobilization of the lanthanides and actinides from monazite-(Ce)in the metapelite layers into the metabasite layers at the startof granulite facies metamorphism. KEY WORDS: apatite; monazite; xenotime; KCl–NaCl brines; metasomatism; phosphate minerals; charnockite–enderbite; granulite facies metamorphism     

新疆拜城波孜果尔碱性岩中副矿物的特征

在野外地质调查的基础上,结合室内显微镜观察及电子探针分析测试,对新疆拜城波孜果尔碱性岩中的副矿物的矿物学特征和化学成分进行了研究.发现这些副矿物常以共生组合的形式产在碱性岩中,主要分布在石英二长闪长岩和石英二长岩中.烧绿石中U、Th和REE替代Ca、Na.独居石富含LREE,Th和LREE相互替代;根据独居石中w(La+ Ce) ＞40％和La/Nd比值在1.6～4.5,推断独居石为热液成因.磷钇矿中富含REE,且以HREE为主;w(Th)＞w(U).锆石中Zr/Hf比值在60％以上,符合碱性岩特征;其Th/U比值为0.6,属于岩浆锆石.星叶石中w(Rb2O)、w(Cs2O)较高.萤石中Y、Ce替代Ca.锆石中的钍石w(U)明显高于磁铁矿中钍石w(U).在石英二长岩中,烧绿石的w(CaO)、w(TiO2)、w(ZrO2)、w(U3O8),磷钇矿的w(Y2O3),星叶石的w(TiO2),萤石的w(Ca),氟碳铈镧矿的w(CaO)较丰富;而在石英二长闪长岩中,烧绿石的w(Ce2O3),磷钇矿的REE含量,星叶石的w(Nb2O5)、w(Rb2O),萤石w(Ce)、w(Y)和氟碳铈镧矿的w(La2O3)较高.     

应用电子探针-扫描电镜研究陕西华阳川铀稀有多金属矿床稀土矿物特征

陕西华阳川铀稀有多金属矿床伴生大量的稀土资源,其矿石类型独特、组分复杂,系统的稀土矿物学工作将揭示矿石主要稀土矿物类型、稀土元素赋存状态,进而对矿床开发中稀土元素综合利用及选冶技术提供重要参考.本文在岩相学基础上,利用电子探针、扫描电镜对陕西华阳川铀稀有多金属矿床矿石中的稀土独立矿物与含稀土矿物进行系统研究,在矿石中发...     

Experimental metasomatism of monazite and xenotime: mineral stability, REE mobility and fluid composition

In this study a Th-bearing monazite from a Brazil beach sand, a low Th monazite from a Malawi carbonatite, and a xenotime from a pegmatite in northern Pakistan were experimentally metasomatised in a series of common metamorphic and igneous fluids at 600°C/500 MPa and 900°C/1000 MPa. Fluids included H₂O, NaCl, and KCl brines, CaF₂?+?H₂O, 1m and 2m HCl, 1m and 2m H₂SO₄, 1m NaOH, and Na₂Si₂O₅?+?H₂O. The monazite show a variety of responses to the fluids ranging from no reaction (KCl?+?H₂O) to small compositional changes and partial replacement of the monazite grain rim by Th-enriched monazite in the NaOH and (Na₂Si₂O₅?+?H₂O) experiments respectively. The other acid and brine fluids induced varying degrees of partial dissolution in the monazite and xenotime, but no compositional alteration. Partial replacement of monazite grain rims by Th-enriched monazite occurred only in the alkaline fluids as the result of a coupled dissolution-reprecipitation process.     

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。     

Whole-rock, Phosphate, and Silicate Compositional Trends across an Amphibolite- to Granulite-facies Transition, Tamil Nadu, India

Chemical trends from north (amphibolite facies) to south (granulitefacies) along a 95 km traverse in Tamil Nadu, Southern India,include: whole-rock depletion of Rb, Cs, Th and U, enrichmentin Ti and F, and depletion in Fe and Mn in biotite and amphibole;increases in Al and decreases in Mn in orthopyroxene; enrichmentof fluorapatite in F. K-feldspar blebs are widespread alongquartz–plagioclase grain boundaries, and could indicateeither partial melting or metasomatism. In the northernmostportion of the traverse the principal rare earth element (REE)-bearingminerals are allanite and titanite. South of a clinopyroxeneisograd, monazite grains independent of fluorapatite are themajor REE- and Th-bearing phase. Further south independent monaziteis rare but Th-free monazite inclusions are common in fluorapatite.During prograde metamorphism, independent monazite was replacedby REE-rich fluorapatite in which the monazite inclusions laterformed. The loss of independent monazite was accompanied bya loss of whole-rock Th and possibly a small depletion in lightREE. Most mineralogical features along the traverse can be accountedfor by progressive dehydration and oxidation reactions. Trace-elementdepletion is best explained by the action of an externally derivedlow H₂O activity brine migrating from a source at greater depth,possibly preceded or accompanied by partial melting. KEY WORDS: granulite facies; charnockite; metasomatism; Archean; Tamil Nadu, India; fluorapatite; monazite; allanite; titanite; biotite     

Synchysite-(Y)–synchysite-(Ce) solid solutions from Markersbach, Erzgebirge, Germany: REE and Th mobility during high-T alteration of highly fractionated aluminous A-type granites

Summary The Ca,REE-fluorocarbonate synchysite, which forms anhedral grains hosted in albite, was identified in the Markersbach pluton (Erzgebirge, Germany) composed of F-rich, highly fractionated and autometasomatically altered granites. These granites were emplaced in a post-collisional setting and are of aluminous A-type affinity. The grains were identified by electron microprobe analysis as intermediate members of the probably complete solid-solution series between synchysite-(Y) and synchysite-(Ce). The rareearth elements likely were liberated upon complete destruction of magmatic monazite and xenotime during interaction with a F-CO₂-Ca-bearing, late-magmatic fluid at relatively high temperatures. The geochemical patterns of different granite samples from Markersbach indicate that the REE and Th were not trapped immediately at the site of their release but mobilized over distances of at least decimeters. During transport of the elements in the fluid, presumably as fluoride (HREE) and chloride (LREE) complexes, no significant fractionation took place among the REE. Received May 8, 2000; revised version accepted November 21, 2000     

Behavior of accessory phases and redistribution of Zr,REE, Y,Th, and U during metamorphism and partial melting of metapelites in the lower crust: an example from the Kinzigite Formation of Ivrea-Verbano,NW Italy

This study is aimed at understanding the behavior of monazite, xenotime, apatite and zircon, and the redistribution of Zr, REE, Y, Th, and U among melt, rock-forming and accessory phases in a prograde metamorphic sequence, the Kinzigite Formation of Ivrea-Verbano, NW Italy, that may represent a section from the middle to lower continental crust. Metamorphism ranges from middle amphibolite to granulite facies and metapelites show evidence of intense partial melting and melt extraction. The appearance of melt controls the grain size, fraction of inclusions and redistribution of REE, Y, Th, and U among accessories and major minerals. The textural evolution of zircon and monazite follows, in general, the model of Watson et al. (1989). Apatite is extracted from the system dissolved into partial melts. Xenotime is consumed in garnet-forming reactions and is the first source for the elevated Y and HREE contents of garnet. Once xenotime is exhausted, monazite, apatite, zircon, K-feldspar, and plagioclase are progressively depleted in Y, HREE, and MREE as the modal abundance of garnet increases. Monazite is severely affected by two retrograde reactions, which may have consequences for U-Pb dating of this mineral. Granulite-grade metapelites (stronalites) are significantly richer in Ti, Al, Fe, Mg, Sc, V, Cr, Zn, Y, and HREE, and poorer in Li, Na, K, Rb, Cs, Tl, U, and P, but have roughly the same average concentration of Cu, Sr, Pb, Zr, Ba, LREE, and Th as amphibolite-grade metapelites (kinzigites). The kinzigite-stronalite transition is marked by the sudden change of Th/U from 5–6 to 14–15, the progressive increase of Nb/Ta, and the decoupling of Ho from Y. Leucosomes were saturated in zircon, apatite, and (except at the lowest degree of partial melting) monazite. Their REE patterns, especially the magnitude of the Eu anomaly, depend on the relative proportion of feldspars and monazite incorporated into the melt. The presence of monazite in the source causes an excellent correlation of LREE and Th, with nearly constant Nd/Th ≈ 2.5–3. The U depletion and increase in Th/U characteristic of granulite facies only happens in monazite-bearing rocks. It is attributed to enhancement of the U partitioning in the melt due to elevated Cl activity followed by the release of a Cl-rich F-poor aqueous fluid at the end of the crystallization of leucosomes. Halide activity in partial melts was buffered by monazite and apatite. Since the U (and K) depletion does not substantially affect the heat-production of metapelites, and mafic granulites maintain similar Th/U and abundance of U and Th as their unmetamorphosed equivalents, it seems that geochemical changes associated to granulitization have only a minor influence on heat-production in the lower crust.     

Tectonothermal events in the Olympic IOCG Province constrained by apatite and REE-phosphate geochronology

The Olympic iron oxide–copper–gold province in South Australia contains numerous deposits and prospects, including the Olympic Dam Cu–U–Au–Ag deposit and the Acropolis prospect. The Acropolis prospect comprises massive, coarse-grained magnetite–apatite veins partly replaced by a hematite-stable assemblage. The apatite grains in the veins contain zones with abundant inclusions of other minerals (including monazite and xenotime) and low trace-element concentrations relative to the inclusion-free zones. The inclusion-rich apatite zones are interpreted to be formed from the recrystallisation of the inclusion-free apatite and remobilisation of U, Th and rare earth element (REE) from apatite into monazite and xenotime. Apatite, monazite and xenotime are all established U–Th–Pb geochronometers and offer the potential to constrain the alteration history of the Acropolis prospect. The LA-ICPMS U–Pb age of inclusion-free apatite is within error of the age of the host volcanic units (ca 1.59 Ga). Inclusion-rich apatite yields both near-concordant analyses that are within error of the inclusion-free apatite as well as highly disturbed (discordant) analyses. The most concordant analyses of monazite (Th–Pb) inclusions and xenotime (U–Pb) inclusions and rim grains indicate an alteration event occurred at ca 1.37 Ga and possibly also at ca 500 Ma. The disparity in age of the inclusion-rich apatite and the REE-phosphate inclusions (and rim grains) is suggested to be owing to the apatite being initially recrystallised at ca 1.59 Ga and modified again by a later event that also formed (or coarsened) most of the inclusions. Partial resetting of the majority of the monazite inclusions as well as the presence of significant amounts of common Pb has complicated the interpretation of the monazite results. In contrast, xenotime is a more robust geochronometer in this setting. The ages of the two post-1.59 Ga events that appear to have affected the Acropolis prospect do not correspond to any events known to have occurred in the Gawler Craton. The earlier (ca 1.37 Ga) age instead corresponds best with metamorphic–magmatic–hydrothermal activity in Laurentia, consistent with the proximity of Laurentia and the Gawler Craton inferred from palaeogeographic reconstructions. The later (ca 500 Ma) event corresponds to the Delamerian Orogeny and has been shown by prior studies to have also affected the Olympic Dam deposit.     

Tveitite-(Y) and REE-enriched fluorite from amazonite pegmatites of the Western Keivy,Kola Peninsula,Russia: Genetic crystal chemistry of natural Ca,REE-fluorides

Tveitite-(Y) as pods up to 10 cm across has been found at Mt. Rovgora, the Western Keivy, Kola Peninsula, Russia, in an albite-quartz-amazonite pegmatite vein related to alkaline granite. Tveitite-(Y) grains (up to 4 cm) are parallel microintergrowths of two isostructural varieties, Ca_9.5Na_1.7Y_5.2Ln_2.0F_42.6 and Ca_11.4Na_1.9Y_4.4Ln_1.4F_42.0. The idealized structural formula (Z = 3) is (Y, Na)₆(Ca, LREE)₆(Ca, Na, HREE)₆(Ca, Na)F₄₂; the simplified formula is (Ca, REE, Na)₁₃(Y, Na)₆F₄₂; space group R \(\bar 3\) a = 17.020, c = 9.679 Å. [Lanthanoides are abbreviated in this paper as Ln, whereas Ln + Y as REE]. Nine fluorite samples containing from 0 to 18 mol % (REE)F₃ were examined by electron microprobe, X-ray powder diffraction, and IR spectroscopy. The crystal structure of natural yttrofluorite has been determined for the first time (R _aniso = 1.47 %): Fm3m, a = 5.493 Å; the structural formula is (Ca_0.82Y_0.12Ln_0.06)F_2.15. Earlier published and new data show that yttrofluorite containing (REE)F₃ > 20 mol % and REE-enriched fluorite with LREE > Y (HREE) are metastable under room conditions. In nature, tveitite-(Y) is a product of solid-state transformation of metastable yttrofluorite with (REE)F₃ > 20 mol %. Inferred protophases could have been exsolved into tveitite-(Y) variable in composition or tveitite-(Y) + yttrofluorite stable under normal conditions. The formation of tveitite-(Y) requires the erichment of a protophase not only in Y but also in LREE and HREE as stabilizing admixtures regularly distributed by different types of Ca-dominant structural sites. Tveitite-(Y) and yttrofluorite are geochemical indicators of a medium that is not only enriched in Y, Ln, and F, but also depleted in Na, Ca, CO₂ and P.     

Uranium-rich accessory minerals in the peraluminous and perphosphorous Belvís de Monroy pluton (Iberian Variscan belt)

The strongly peraluminous, perphosphorous (<0.85 wt% P₂O₅) and low-Ca granites from the Belvís de Monroy pluton contain the most U-rich monazite-(Ce) and xenotime known in igneous rocks. Along with these accessory minerals, P-rich zircon occurs, reaching uncommon compositions particularly in the more fractionated units of this zoned pluton. Monazite displays a wide compositional variation of UO₂ (<23.13 wt%) and ThO₂ (<19.58 wt%), positively correlated with Ca, Si, P, Y and REE. Xenotime shows a high UO₂ content (2.37–13.34 wt%) with parallel increases of LREE, Ca and Si. Zircon contains comparatively much lower UO₂ (<1.53 wt%) but high P₂O₅ (<14.91 wt%), Al₂O₃ (<6.96 wt%), FeO (<2.93 wt%) and CaO (<2.24 wt%) contents. The main mechanism of incorporating large U and Th amounts in studied monazite and U in xenotime is the cheralite-type [(Th,U)⁴⁺ + Ca²⁺ = 2(Y,REE)³⁺] substitution. Zircon requires several coupled mechanisms to charge balance the P substitution, resulting in non-stoichiometric compositions with low analytical totals. Compositional variations in the studied accessory phases indicate that the substitution mechanisms during crystal growth depend on the availability of non-formula elements. The strong P-rich character of the studied granites increases monazite crystallization, triggering a progressive impoverishment in Th and LREE in the residual melts, and consequently increasing extraordinarily the U content in monazite and xenotime. This is in marked contrast to other peraluminous (I-type or P-poor S-type) granite series. The P-rich and low-Ca peraluminous melt inhibits uraninite crystallization, so contributing to the U availability for monazite and xenotime.     

Petrography and mineral chemistry of Alkaline-Carbonatite Complex in Singhbhum Crustal Province,Purulia region,Eastern India

The variant rock types of an Alkaline-Carbonatite Complex (ACC) comprising alkali pyroxenite, nepheline syenite, phoscorite, carbonatite, syenitic fenite and glimmerite along with REE and Nb-mineralization are found at different centres along WNW-ESE trending South Purulia Shear Zone (SPSZ) in parts of Singhbhum Crustal Province. The ACC occurs as intrusions within the Mesoproterozoic Singhbhum Group of rocks. Alkali pyroxenite comprises of aegirine augite, magnesiotaramite, magnesiokatophorite as major constituents. Pyrochlore and eucolite are ubiquitous in nepheline syenite. Phoscorite contains fluorapatite, dahllite, collophane, magnetite, hematite, goethite, phlogopite, calcite, sphene, monazite, pyrochlore, chlorite and quartz. Coarse fluorapatite shows overgrowth of secondary apatite (dahllite). Secondary apatite is derived from primary fluorapatite by solution and reprecipitation. The primary fluorapatite released REE to crystallize monazite grains girdling around primary apatite. Carbonatite is composed dominantly of Srcalcite along with dolomite, tetraferriphlogopite, phlogopitic biotite, aegirine augite, richterite, fluorapatite, altered magnetite, sphene and monazite. The minerals comprising of the carbonatite indicate middle stage of carbonatite development. Fenite is mineralogically syenite. Glimmerite contains 50–60% tetraferriphlogopite. An alkali trend in the evolution of amphiboles (magnesiotaramite-magnesiokatophorite-richterite) and chinopyroxenes (aegirine augite, aegirine) during the crystallization of the suite of rocks is noted. Monazite is the source of REE in phoscorite and carbonatite. Fluorapatite has low contents of REE, PbO, ThO₂ and UO₂. Pyrochlore reflects Nb-mineralization in nepheline syenite and it is enriched in Na₂O, CaO, TiO₂, PbO and UO₂. Pyrochlore containing UO₂ (6.605%) and PbO (0.914%) in nepheline syenite has been chemically dated at 948 ± 24 Ma by EPMA.     

江西雅山富氟高磷花岗岩中的磷酸盐矿物及其成因意义

江西雅山黄玉锂云母花岗岩属典型的华南[富氟高磷花岗岩（P2O5＝0．15％－0．55％），表现为富氟（F＝1．07％－2．04％），强过铝性（A／NKC＝1．26－1．60），具有很高的Li,Rb,Cs,Be,Nb,Ta含量和很低的Y、REE含量.磷锂铝石是雅山黄玉锂云母花岗岩中的主要磷酸盐矿物，其产出与否同体的Li,Rb,Cs含量密切相关；磷锂铝石和长石矿物都是雅山黄玉锂云母花岗岩中磷的主要贮体，并且相互之间呈互补关系，当出现磷锂铝石时，磷锂铝石为全岩磷的主要贡献者，当无磷锂铝石晶出时，长石矿物为全岩磷的主要贡献者，体系的强过铝性以及很低的REE，Y，Ca含量使得磷灰石，独居石，磷钇矿都难以达到饱和结晶，磷灰石为少量出现，并且大部分为晚期形成；独居石和磷钇矿都为极少出现，反映出雅山岩体演化过程中具有独居石，磷钇矿等稀土磷酸盐矿物的结晶分离，铍磷酸盐矿物－羟磷铍钙石的出现反映了雅山黄玉锂云母花岗岩存在岩浆期后的含Be,Ca热液流体的作用。     

Formation conditions and rare-earth mineralization of Riphean carbonaceous shales of the Upper Nyatygran Subformation,Russian Far East

Graphitic and graphite varieties are distinguished in the carbonaceous shales of the Riphean Upper Nyatygran Subformation in the Melgin fragment of the Turan block, eastern Bureya Massif. The protolith of the graphitic shales had a terrigenous source related to island-arc volcanism. Pelagic sedimentation played a great role in the formation of the protolith of the graphite shale. These rocks were juxtaposed during the formation of an accretionary wedge on an active continental margin. The carbonaceous shales are characterized by high (>600 ppm) REE + Y contents, especially in the zones of brecciation and hydrothermal reworking. Detrial monazite enriched in LREE and MREE is the main carrier of REE mineralization in the graphitic shales. The main REE carrier in the graphite shales is REE phosphate (xenotime) formed during lithogenesis of sediments. Preliminary experimental treatment of the graphite shales of the Upper Nyatygran Subformation by ammonium hydrofluoride shows their potential for economic extraction of REE and Y.