Origin of convex tetrads in rare earth element patterns of hydrothermally altered siliceous igneous rocks from the Zinnwald Sn-W deposit, Germany

The chondrite-normalized rare earth element (REE) patterns of whole rock samples from evolved granitic systems hosting rare metal deposits sometimes show a split into four consecutive curved segments, referred to as tetrads. In the present contribution, a rigorous statistical method is proposed that can be used to test whether geological significance should be attributed to tetrads that are only of limited size. The method involves a detailed evaluation of element and sample specific random and systematic errors that are constrained on the basis of independent repeated preparations and analyses of sample and reference materials. Application of the proposed method to samples from the granite-hosted Zinnwald Sn-W deposit, Germany, revealed that at least two tetrads in normalized whole rock REE patterns have to be analytically significant to rule out that fractional crystallization led to the unusual behavior of the REEs. Based on the analysis of altered albite granite and greisen samples from the endocontact of the Zinnwald granite massif, it is demonstrated that the lanthanide tetrad effect is responsible for the formation of the convex tetrads. Geological and petrological evidence suggests that the tetrads in the samples developed prior to greisenization and related cassiterite precipitation. In contrast to the endocontact samples, the rhyolitic wall rocks are typified by normalized REE patterns having tetrads that are variable in size and frequently close to the limit of analytical significance. The sizes of the tetrads apparently correlate with the intensity of albitization, but show no relation to subsequent alteration processes including greisenization and low-temperature argillization. This observation proves that curved segments in normalized whole rock REE patterns can be introduced during hydrothermal fluid-rock interaction.     

Tetrad effects in the rare earth element patterns of granitoid rocks as an indicator of fluoride-silicate liquid immiscibility in magmatic systems

This paper focuses on reasons for the appearance of tetrad effects in chondrite-normalized REE distribution patterns of granitoids (Li-F granites, peralklaine granites, ongonites, fluorine-rich rhyolites, and granitic pegmatites). The analysis of published data showed that the alteration of such rocks by high- and/or low-temperature metasomatic processes does not result in most cases in the appearance or enhancement of M-type tetrad effects in REE patterns. These processes are accompanied by the removal or addition of lanthanides, a W-type sag appears between Gd and Ho, and negative or positive Ce anomalies develop sometimes in REE patterns. The formation conditions of peculiar rocks enriched in Ca and F from the Ary Bulak ongonite massif (eastern Transbaikalia) and the character of REE distribution in these rocks and melt inclusion glasses were discussed. Based on the obtained data and the analysis of numerous publications, it was concluded that REE tetrad effects in rare-metal granitoids are caused by fluoride-silicate liquid immiscibility and extensive melt differentiation in the accumulation chambers of fluorine-rich magmas. A considerable increase in fluorine content in a homogeneous granitoid melt can cause its heterogenization (liquation) and formation of fluoride melts of various compositions. The redistribution of lanthanides between the immiscible liquid phases of granitoid magma will result in the formation of M-type tetrad effects in the silicate melts, because the REE patterns of fluoride melts exhibit pronounced W-type tetrad effects. The maximum M-type tetrad effect between La and Nd, which is observed in many rare-metal granitoids, is related to the character of REE partitioning between fluoride and silicate melts and F- and Cl-rich magmatic fluids. The low non-chondritic Y/Ho ratio (<15) of many rare-metal granitoids may be indicative of a contribution of fluoride melts to the differentiation of F-rich silicic magmas, from which these rocks were formed. The influence of high-temperature F-Cl-bearing fluids on melts and/or granitoid rocks results in an increase in Y/Ho ratio owing to the elevated solubility of Ho in such fluids.     

REE systematics of fluorides,calcite and siderite in peralkaline plutonic rocks from the Gardar Province,South Greenland

The Gardar failed-rift Province is world-famous for its (per-)alkaline plutonic rocks. Elevated contents of F in the mantle source and F-enrichment in the parental melts have been suggested to account for the peculiarities of the Gardar rocks (e.g. their rare mineralogy, extreme enrichment of HFSE elements, Be or REE in the Ilímaussaq agpaites, and the formation of the unique Ivigtut cryolite deposit). To constrain the formation and chemical evolution of F-bearing melts and fluids, fluorides (fluorite, cryolite, villiaumite, cryolithionite), calcite and siderite from the Ilímaussaq, Motzfeldt and Ivigtut complexes were analysed for their trace element content focusing on the rare earth elements and yttrium (REE).The various generations of fluorite occurring in the granitic Ivigtut, agpaitic Ilímaussaq and miaskitic to agpaitic Motzfeldt intrusions all share a negative Eu anomaly which is attributed to (earlier) feldspar fractionation in the parental alkali basaltic melts. This interpretation is supported by the abundance of anorthositic xenoliths in many Gardar plutonic rocks.The primary magmatic fluorites from Ilímaussaq and Motzfeldt display very similar REE patterns suggesting a formation from closely related parental melts under similar conditions. Hydrothermal fluorites from these intrusions were used to constrain the multiple effects responsible for the incorporation of trace elements into fluorides: temperature dependence, fluid migration/interaction and complexation resulting in REE fractionation. Generally, the REE patterns of Gardar fluorides reflect the evolution and migration of a F/CO₂-rich fluid leading to the formation of fluorite and fluorite/calcite veins. In certain units, this fluid inherited the REE patterns of altered host rocks. In addition, there is evidence of an even younger fluid of high REE abundance which resulted in highly variable REE concentrations (up to three orders of magnitude) within one sample of hydrothermal fluorite.The REE patterns of the granitic Ivigtut intrusion show flat to slightly heavy-REE-enriched patterns characterised by a strong tetrad effect. This effect is interpreted to record extensive fluid–rock interaction in highly fractionated, Si-rich systems.Interestingly, the fluorides appear to record different source REE patterns, as the spatially close Motzfeldt and Ilímaussaq intrusions show strong similarities and contrast with the Ivigtut intrusion located 100 km NE. These variations may be attributed to differences in the tectonic position of the intrusions or mantle heterogeneities.     

Trace and REE element geochemistry of fluorite and its relation to uranium mineralizations,Gabal Gattar Area,Northern Eastern Desert,Egypt

Uranium mineralizations occur and form in a broad range of geologic setting and age, including magmatic to surfacial conditions, and there are numerous controls on their transportation and deposition, such as redox, pH, ligand concentration, complexation, and temperature. These temporal and spatial variations have caused a range of ore deposit mineral assemblages. Consequently, understanding their conditions of formation is still in its infancy. This research reports rare earth elements (REE) and trace elements of fluorite associated with hexavalent uranium mineralizations and tests of genetic models for the deposits. These data contribute to a better understanding of the variables controlling fluorite formation and uranium ore composition through understanding the evolution of these ore-forming hydrothermal systems. Fluorite in Gabal Gattar granite occurs as disseminations and/or thin veinlets and encrustations filling some uranium mineralized fissures and fractures along the northern margin of host granite mass. In the U-poor samples, fluorite forms well-developed large crystals that are commonly zoned. The zones are represented by alternating colorless and violet zones, and the outer zones are frequently dark violet. In the U-rich samples, fluorite is usually anhedral, unzoned, and has a dark violet color. The results of analysis of REE and trace element contents of fluorites using laser ablation inductively coupled plasma mass spectrometry indicate that total REE in the anhedral unzoned fluorite are elevated compared to the well developed zoned fluorite, and also total REE in dark violet zones of zoned fluorite are elevated with respect to the colorless zones. The fluorites and host granite are generally characterized by strongly negative Eu anomalies and slightly negative or chondritic Ce anomalies. Accordingly, REE patterns of the fluorite and host granite are roughly alike, indicating that the source of REE and trace elements of hydrothermal fluids is the host granite leached by fluids. Y/Y*, Ce/Ce,* and Eu/Eu* patterns show that fluorite clearly records the compositional evolution of the hydrothermal solutions that have transferred trace and REE from host granite during the fluid–wall rocks interactions. The high uranium contents of fluorite in Gabal Gattar granite suggest that parent fluids bearing fluorine have interacted with host granite to leach uranium from the accessory minerals of granite and tetravalent uranium minerals in reduced or weakly oxidized zones.     

四川牦牛坪稀土矿床萤石Sr、Nd同位素对地幔成矿流体的指示意义

萤石是四川牦牛坪稀土矿床主要的脉石矿物之一，其形成贯穿了整个稀土成矿过程，因此同位素的研究对探讨萤石和稀土成矿流体的来源具有重要的价值。矿区6件萤石样品的Sr、Nd同位素组成没有明显差异，结合围岩（碳酸岩－正长岩，花岗岩）同位素组成特征研究表明，不同颜色、来自不同矿石类型、具有不同REE类型的萤石为同源产物，稀土成矿流体来源于富集地幔，与区内碳酸岩－正长岩岩浆活动密切相关。     

Genesis and formation conditions of deposits in the unique Strel’tsovka Molybdenum-Uranium ore field: New mineralogical,geochemical, and physicochemical evidence

The ambiguity of genetic interpretations of uranium ore formation at Mo-U deposits of the Strel’tsovka ore field led us to perform additional geochemical, mineralogical, and thermobarogeochemical studies. As a result, it has been established that closely related U and F were progressively gained in the Late Mesozoic volcanic rocks from the older basic volcanics (170 Ma) to the younger silicic igneous rocks (140 Ma). The Early Cretaceous postmagmatic hydrothermal epoch (140–125 Ma) is subdivided into preore, uranium ore, and first and second postore stages. The primary brannerite-pitchblende ore was formed in association with fluorite. At the first postore stage, this assemblage was replaced by a U-Si metagel, which was previously identified as coffinite. The metagel shows a wide compositional variation; its fine structure has been studied. The preore metasomatic alteration and related veined mineralization were formed under the effect of sodium (bicarbonate)-chloride solution at a temperature of 250–200°C. The uranium ore formation began with albitization and hematitization of rocks affected by supercritical fluid at 530–500°C; brannerite and pitchblende precipitated at 350–300°C. The chondrite-normalized REE patterns of pitchblende hosted in trachybasalt, trachydacite, and granite demonstrate a pronounced Sm-Nd discontinuity and a statistically significant tetrad effect of W type. These attributes were not established in REE patterns of rhyolites derived from the upper crustal magma chamber. This circumstance and a chronological gap of 5 Ma between silicic volcanism and ore formation do not allow us to suggest that uranium was derived from this magma chamber. According to the proposed model, the evolved silicic Li-F magma was a source of uranium. U⁴⁺, together with REE, was fractionated into the fluid phase as complex fluoride compounds. The uranium mineralization was deposited at a temperature barrier. It is suggested that hydromica alteration and the formation of molybdenum mineralization were genetically unrelated to the uranium ore formation.     

REE Geochemistry of Fluorite from the Maoniuping REE Deposit, Sichuan Province, China： Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit,Sichuan Province,China.Fluorite with different colors occurs not only within various orebodies,but also in wallrocks of the orefield.Based on REE geochemistry,fluorite in the orefield can be classified as the LREE-rich,LREE-flat and LREE-depleted types.The three types of fluorite formed at different stages from the same hydrothermal fluid source,with the LREE-rich fluorite forming at the relatively early stage,the LREE-flat fluorite in the middle,and the LREE-depleted fluorite at the latest stage.Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color.The mineralization of the Maoniuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.     

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。     

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.     

义县萤石矿床稀土元素地球化学特征及其指示意义

为了研究辽西义县萤石矿床的成矿机理及成矿流体来源,文章对矿区萤石稀土元素进行了分析。结果表明:2种类型的萤石为同源不同阶段的产物,从成矿早期至晚期,LREE逐渐减少,Ce负异常由弱变强,Eu则均显明显的正异常;矿床成矿流体主要来源于中侏罗世髫髻山旋回岩浆热液;成矿过程为岩浆热液与围岩(主要为白云质灰岩和灰岩)的相互作用,并有天水的混入;成矿环境相对氧化。     

川西呷村超大黑矿型矿床成矿流体烯土元素组成

本文用ＩＣＰ－ＭＳ首次测定了呷村银多金属黑矿型矿床矿石流体包裹体中的稀土元素含量,研究表明,主成矿期流体稀土元素配分模式均为轻稀土富集,Ｅｕ具明显正异常,通过初步对比,本区主成矿期流体与东太平洋脊、大西洋脊等现代高温酸性地热系统热液具有相似的稀土模式,反映了它们物化条件的相似性;但前者∑ＰＥＥ高于后者,且两者Ｅｕ／Ｅｕ＾＊值不同,经过分析,本区成矿流体Ｅｕ正异常主要为Ｔ、ｐＨ、ｆｏ２控制,另外,围     

The Laal-Kan fluorite deposit,Zanjan Province,NW Iran: constraints on REE geochemistry and fluid inclusions

The Laal-Kan fluorite deposit (west of Zanjan city, NW Iran) mainly occurred as some open-space filling and vein/veinlet in the schist of the Paleozoic age. Mineralogically, calcite, fluorite types (white, smoky, and violet), and quartz are the principal constituents accompanied by a number of minor accessory minerals such as hemimorphite, hematite, barite, and clays. Based on chemical analyses, fluorites of various colors were found to have low rare earth element (REE) concentrations (4.16–25.67 ppm). The chondrite-normalized REE patterns indicated that early fluorites were enriched in LREE, relative to HREE, whereas late fluorites were enriched in HREE relative to LREE. This study, therefore, indicated that fugacity of oxygen likely played a significant role in the occurrence of positive Ce and negative anomaly in the late fluorite. Furthermore, the Gd behavior of the fluorite samples could be attributed to the Gd-F complex in ore-forming fluids. On the other hand, low pH hydrothermal fluids under alkaline conditions were probably the main mechanism responsible for the deposition of the early fluorites in this district. Fluorite-hosted fluid inclusion analyses also indicated that fluorite-forming fluids consisted of NaCl, MgCl₂, CaCl₂, and LiCl with a narrow T_H (118–151 °C) and high salinities (18.96–23.47 wt.% NaCl equiv.). Further, the diagram of Tb/La-Tb/Ca ratios revealed that fluorites were predominantly deposited in the hydrothermal environment and the late stage fluorites could be considered as the product of the secondary mineralization of the early fluorites due to the interaction of the fluid with the early fluorites.     

Behaviour of rare earth elements in geothermal systems of New Zealand

Rare earth element (REE) patterns of hydrothermally altered rhyolite from geothermal systems located in the Taupo Volcanic Zone in the North Island of New Zealand provide evidence of REE mobility. REE trends of unaltered rhyolites are characterised by moderate LREE enrichment ((La/Lu)_cn = 3.84 to 5.62) and pronounced negative Eu anomalies. In contrast, REE patterns of hydrothermally altered rhyolites commonly exhibit different signatures and may be placed into four chemically and petrographically distinct categories. Rocks with clay + quartz + feldspar + calcite (±zeolites, epidote, sphene, chlorite, opaque minerals) assemblages typically display patterns subparallel to fresh rock, whereas, samples which contain quartz + chlorite, or quartz + clay + zeolite assemblages have flat patterns without Eu anomalies, and highly silicified samples are characterised by depleted, bowed REE trends. These patterns may be produced by interaction with alkaline or acid fluids. A fourth group of very intensely altered samples, affected by interaction with acid fluids, exhibits unusual REE trends with highly enriched HREE and depleted LREE, or depleted HREE.These results indicate that some of the REE released by the breakdown of primary phases during alteration are transported away in the fluid. In addition, the degree of depletion is positively correlated with alteration intensity and the fluid/rock ratio. The similarity of REE patterns resulting from alteration by alkaline and acid fluids suggests that the shape of the REE trends is controlled principally by fluid/rock ratios and secondarily by mineralogy. The REE are retained in rocks with a diverse alteration mineralogy, whereas in samples with only one dominant alteration phase (e.g. quartz) it is more probable that not all REE liberated during alteration can be accommodated in the altered rock. Eu commonly behaves differently from the other REE, possibly due to the dominance of Eu²⁺.     

Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier,central Australia

Tourmaline rocks of previously unclear genesis and spatially associated with W- (Cu)-bearing calc-silicate rocks occur in Palaeoproterozoic supracrustal and felsic intrusive rocks in the Bonya Hills in the eastern Arunta Inlier, central Australia. Tourmalinisation of metapelitic host rocks postdates the peak of regional low-pressure metamorphism (M₁/D₁, ~500 °C, ~0.2 GPa), and occurred synkinematically between the two main deformation events D₁ and D₂, coeval with emplacement of Late Strangways (~1.73 Ga) tourmaline-bearing leucogranites and pegmatites. Tourmaline is classified as schorl to dravite in tourmaline–quartz rocks and surrounding tourmaline-rich alteration zones, and as Fe-rich schorl to foitite in the leucogranites. Boron metasomatism resulted in systematic depletion of K, Li, Rb, Cs, Mn and enrichment of B, and in some samples of Na and Ca, in the tourmaline rocks compared to unaltered metasedimentary host rocks. Whole-rock REE concentrations and patterns of unaltered schist, tourmalinised schist and tourmaline–quartz veins—the latter were the zones of influx of the boron-rich hydrothermal fluid—are comparable to those of post-Archaean shales. Thus, the whole-rock REE patterns of these rocks are mostly controlled by the metapelitic precursor. In contrast, REE concentrations of leucogranitic rocks are low (10 times chondritic), and their flat REE patterns with pronounced negative Eu anomalies are typical for fractionated granitic melts coexisting with a fluid phase. REE patterns for tourmalines separated from metapelite-hosted tourmaline–quartz veins and tourmaline-bearing granites are very different from one another but each tourmaline pattern mirrors the REE distribution of its immediate host rock. Tourmalines occurring in tourmaline–quartz veins within tourmalinised metasediments have LREE-enriched (La_N/Yb_N=6.3–55), shale-like patterns with higher REE (54–108 ppm). In contrast, those formed in evolved leucogranites exhibit flat REE patterns (La_N/Yb_N=1.0–5.6) with pronounced negative Eu anomalies and are lower in REE (5.6–30 ppm). We therefore conclude that REE concentrations and patterns of tourmaline from the different tourmaline rocks studied are controlled by the host rock and not by the hydrothermal fluid causing boron metasomatism. From the similarity of the REE pattern of separated tourmaline with the host rock, we further conclude that incorporation of REEs in tourmaline is not intrinsically controlled (i.e. by crystal chemical factors). Tourmaline does not preferentially fractionate specific REEs or groups of REEs during crystallisation from evolved boron- and fluid-rich granitic melts or during alteration of clastic metasediments by boron-rich magmatic-hydrothermal fluids.Editorial responsibility: J. Hoefs     

湘南界牌岭锡多金属矿床萤石LA-ICP-MS微量元素地球化学特征及意义

湘南界牌岭矿床不仅是南岭地区发育的一个晚白垩世超大型锡多金属矿床,同时也是该区乃至中国重要的萤石产地,锡多金属矿及萤石的找矿勘查均具有重要前景.通过野外地质调查与岩石学研究,文章识别出多种类型的锡多金属与萤石矿化,并针对不同类型萤石开展原位LA-ICP-MS微量元素分析,研究表明:①矿体分为锡多金属矿体与萤石矿体2类,...     

REE controls in ultramafic hosted MOR hydrothermal systems: An experimental study at elevated temperature and pressure

A hydrothermal experiment involving peridotite and a coexisting aqueous fluid was conducted to assess the role of dissolved Cl⁻ and redox on REE mobility at 400°C, 500 bars. Data show that the onset of reducing conditions enhances the stability of soluble Eu⁺² species. Moreover, Eu⁺² forms strong aqueous complexes with dissolved Cl⁻ at virtually all redox conditions. Thus, high Cl⁻ concentrations and reducing conditions can combine to reinforce Eu mobility. Except for La, trivalent REE are not greatly affected by fluid speciation under the chemical and physical condition considered, suggesting control by secondary mineral-fluid partitioning. LREE enrichment and positive Eu anomalies observed in fluids from the experiment are remarkably similar to patterns of REE mobility in vent fluids issuing from basalt- and peridotite-hosted hydrothermal systems. This suggests that the chondrite normalized REE patterns are influenced greatly by fluid speciation effects and secondary mineral formation processes. Accordingly, caution must be exercised when using REE in hydrothermal vent fluids to infer REE sources in subseafloor reaction zones from which the fluids are derived. Although vent fluid patterns having LREE enrichment and positive Eu anomalies are typically interpreted to suggest plagioclase recrystallization reactions, this need not always be the case.     

塔里木盆地奥陶系萤石成因及其油气地质意义

塔里木盆地塔中45井上奥陶统发现以萤石层为储层的特殊类型油气藏。为了明确塔里木盆地奥陶系萤石成因及热液溶蚀储层形成时期,本文通过电子自旋共振测年、稀土元素、微量元素、激光拉曼、包裹体氢氧同位素、硫同位素等多种分析手段,对塔中45井区及巴楚-柯坪露头区奥陶系内萤石发育段进行了热液成矿、热液溶蚀与油气成藏关系的综合研究。目前,多数学者认为萤石形成于晚二叠世的岩浆期后热液,并相应存在一期海西期的热液溶蚀,此次研究表明,塔中45井区及巴楚-柯坪露头区的萤石成矿流体可能为低温大气淡水循环热液。塔中45井区断裂溶扩带充填萤石形成于晚燕山-喜马拉雅期,与海西期岩浆期后热液无必然联系;巴楚-柯坪露头区风化壳溶洞充填萤石形成于海西期,萤石成矿期与海西期火山活动热事件影响期匹配关系良好。由此推断,塔中45井区萤石成矿热液溶蚀作用发生于晚燕山-喜马拉雅期。     

Mineralogy of high-field-strength elements (Y,Nb, REE) in the world-class Vergenoeg fluorite deposit,South Africa

The Vergenoeg fluorite deposit in the Bushveld Complex in South Africa is hosted by a volcanic pipe-like body. The distribution characteristics, composition and formation conditions of high-field-strength element (HFSE)-rich minerals in different lithological units of the deposit were investigated by optical and cathodoluminescence microscopy, scanning electron microscopy, X-ray fluorescence, inductively-coupled plasma mass-spectrometry and electron-probe microanalysis. The Vergenoeg host rocks comprise a diverse silica-undersaturated assemblage of fayalite–magnetite–fluorite with variably subordinate apatite and mineral phases enriched in rare-earth elements (REEs). The Sm–Nd isotope systematics of the fluorite from the various lithological units of the pipe support the model that the HFSE budget of the Vergenoeg pipe was likely derived from a Lebowa-type granitic magma. Isotopically, there is no evidence for other REE sources. Formation of the pipe, including development of the fluorite mineralization, occurred within the same time frame as the emplacement of other magmatic rock units of the Bushveld Complex (Sm–Nd isochron age for fluorite separates: 2040 ± 46 Ma). Hydrothermal alteration is manifested in strongly disturbed Rb–Sr isotope systematics of the Vergenoeg deposit, but did not affect its HFSE and REE budget. Whole-rock chondrite-normalized REE + Y distribution patterns of two types were observed: (i) flat patterns characteristic of magnetite–fluorite unit, gossan, metallurgical-grade fluorite (“metspar”) plugs and siderite lenses, and (ii) U-shaped patterns showing enrichment towards the heaviest REE (Tm–Lu) observed in the fayalite-rich units. Common HFSE minerals are complex Nb-rich oxides (samarskite, fergusonite), REE phosphates and fluorocarbonates. Additionally, fluocerite and REE silicates, whose identification requires further work, were found. Most of the HFSE-rich minerals are spatially associated with Fe-rich phases (e.g., pyrite, magnetite, greenalite and hematite). To a smaller extent, they are found finely disseminated or healing micro-fractures in fluorite. The whole-rock REE + Y distribution patterns of the individual lithological units are mainly controlled by the distribution of Yb-rich and Y-rich xenotime in these rocks. The common occurrence of bastnäsite-(Ce) in the gossan, “metspar” plugs and especially in the rhyolitic carapace at the pipe–wall-rock contact, controls the REE + Y distribution patterns of these rocks. HFSE minerals in the Vergenoeg pipe rocks have formed in several stages. Samarskite and coarse fluorapatite belong to the primary mineral assemblage. Fergusonite and Yb-rich xenotime formed during high- to moderate-temperature hydrothermal activity. Significant remobilization of the HFSE from the early-crystallized minerals (breakdown of fluorapatite and possibly allanite with release of REE + Y) and subsequent partial redistribution of these elements into near surface rocks are inferred. The late-stage assemblages are characterized by the presence of fine-grained REE fluorocarbonates, monazite-(Ce), monazite-(La) and xenotime-(Y).     

Highly evolved juvenile granites with tetrad REE patterns: the Woduhe and Baerzhe granites from the Great Xing'an Mountains in NE China

In NE China, voluminous granitoids were emplaced in late Paleozoic and Mesozoic times. We report here Sr–Nd–O isotopic and elemental abundance data for two highly evolved granitic plutons, Woduhe and Baerzhe, from the Great Xing'an Mountains. They show a rather “juvenile” Sr–Nd isotopic signature and a spectacular tetrad effect in their REE distribution patterns as well as non-CHARAC (charge-and-radius-controlled) trace element behavior. The emplacement ages are constrained at 130±4 Ma for the Woduhe and 122±5 Ma for the Baerzhe granites by Rb–Sr and Sm–Nd isotope analyses. Both granites are also characterized by low but imprecise initial ⁸⁷Sr/⁸⁶Sr ratios of about 0.703. The Nd–Sr isotope data argue for their generation by melting of dominantly juvenile mantle component with subordinate recycled ancient crust. This is largely compatible with the general scenario for much of the Phanerozoic granitoids emplaced in the Central Asian Orogenic Belt. The parental magmas for both the Woduhe and Baerzhe granites have undergone extensive magmatic differentiation, during which intense interaction of the residual melts with aqueous hydrothermal fluids (probably rich in F and Cl) resulted in the non-CHARAC trace element behavior and the tetrad effect of REE distribution. Both the Woduhe and Baerzhe granites show the characteristic trace element patterns of rare-metal granites, but their absolute abundances differ by as much as two orders of magnitude. The oxygen isotope compositions of the two granites have been severely disturbed. Significant ¹⁸O depletion in feldspar, but not so much in quartz, suggests that the hydrothermal alteration took place in a temperature condition of 300–500 °C. This subsolidus hydrothermal alteration is decoupled from the late-stage magma–fluid interaction at higher temperatures. Despite the two distinct and intense events of “water–rock” interaction, the Rb–Sr and Sm–Nd geochronological systems seem to have maintained closed, hence, suggesting that the two events occurred shortly after the plutonic emplacements.     

The lanthanide tetrad effect and its correlation with K/Rb,Eu/Eu1, Sr/Eu,Y/Ho,and Zr/Hf of evolving peraluminous granite suites

Lanthanide tetrad effects are often observed in REE patterns of more highly evolved Variscan peraluminous granites of mid-eastern Germany (Central Erzgebirge, Western Erzgebirge, Fichtelgebirge, and Northern Oberpfalz). The degree of the tetrad effect (TE_1,3) is estimated and plotted vs. K/Rb, Sr/Eu, Eu/Eu1, Y/Ho, and Zr/Hf. The diagrams reveal that the tetrad effect develops parallel to granite evolution, and significant tetrad effects are strictly confined to highly differentiated samples. Mineral fractionation as a cause for the tetrad effect is not supported by a calculated Rayleigh fractionation, which also could not explain the fractionation trends of Sr/Eu and Eu/Eu1. The strong decrease of Eu concentrations in highly evolved rocks suggests that Eu fractionates between the residual melt and a coexisting aqueous high-temperature fluid. Mineral fractionation as a reason for the tetrad effect is even more unlikely as REE patterns of accessory minerals display similar tetrad effects as the respective host rocks. The accessory minerals inherit the REE signature of the melt and do not contribute to the bulk-rock tetrad effect via mineral fractionation. These results point in summary to significant changes of element fractionation behavior in highly evolved granitic melts: ionic radius and charge, which commonly control the element distribution between mineral and melt, are no longer the exclusive control. The tetrad effect and the highly fractionated trace element ratios of Y/Ho and Zr/Hf indicate a trace element behavior that is similar to that in aqueous systems in which chemical complexation is of significant influence. This distinct trace element behavior and the common features of magmatic-hydrothermal alteration suggest the increasing importance of an aqueous-like fluid system during the final stages of granite crystallization. The positive correlation of TE_1,3 with bulk-rock fluorine contents hints at the importance of REE fluorine complexation in generating the tetrad effect. As the evolution of a REE pattern with tetrad effect (M-type) implies the removal of a respective mirroring REE pattern (W-type), the tetrad effect identifies open system conditions during granite crystallization.