Mineralogical control of rare earth elements in acid sulfate soils

Major, trace and rare earth element concentrations were measured in porewater, surface water and sediments at an acid sulfate soil site. The concentrations of La and Ce in porewater are up to 1-3 ppm. There is a strong correlation between REE concentration and acidity, except that the maximum concentrations were consistently found below the horizon of maximum acidity, associated with an increase in pH (to ca. 4) and change in mineralogy from jarosite-dominated to goethite-dominated mottles. Jarosite replacement by goethite is as expected with the rise in pH, which in turn is due to the occurrence of a fossil shell bed just below. The rare earth element patterns in the porewaters are enriched in the MREE with respect to Post-Archaean Australian Shale (PAAS). Measurements and calculations show that this is in accord with experiments on low-degree partial dissolution of jarosite, even when the jarosite itself is highly enriched in LREE. There is a clear fractionation in the patterns between the clay-rich soil matrix, which is slightly depleted in the LREE when normalized to PAAS (La/Yb_PAAS ∼0.5), and the secondary mineral phase jarosite, which is enriched in the LREE (La/Yb_PAAS = 15-50). The REE pattern in the porewater changes with the transition from jarosite- to goethite-rich mottles, becoming relatively more enriched in the LREE compared to the HREE, which is consistent with the incongruent dissolution of jarosite to form goethite and the release of greater amounts of jarosite REE to solution, including proportionately more of the jarosite-compatible LREE.Maximum surface water REE concentrations in acidic water were 100-200 ppb La and Ce. REE patterns in surface water were very similar to the porewater transition zone, enriched in the MREE, but asymmetric, relatively enriched in the LREE compared to the HREE.     

Petrology and geochemistry of prograde deserpentinized peridotites from Happo-O’ne, Japan: Evidence of element mobility during deserpentinization

The prograde deserpentinized peridotites from the talc zone in the Happo-O’ne complex, central Japan, show differences in their field relation and mineral assemblage with the high-P retrograde peridotites of the other part of the complex. They show a mineral assemblage, olivine + talc + antigorite ± prograde tremolite ± chlorite, formed by thermal metamorphism around the granitic intrusion at T, 500-650 °C and P < 7 kbar. The olivine has numerous opaque inclusions and high Fo (91.5-96.5) relative to the retrograde olivine, reflecting its formation by deserpentinization. The prograde tremolite, which is low in Al₂O₃ (<1.0 wt.%), Cr₂O₃ (<0.35 wt.%), and Na₂O (<0.6 wt.%) but high in Mg# (up to 0.98) and SiO₂ (up to 59.9 wt.%), is different in size, shape and chemistry from the retrograde tremolite. The prograde peridotites display a U-shaped REE pattern (0.02-0.5 times PM), similar to diopside-zone retrograde metaperidotites, possible protoliths. They are enriched in LILE (e.g., Cs, Pb, Sr, Rb) relative to HFSE (e.g., Ta, Hf, Zr, Nb), like their protoliths, because of their local re-equilibration with the fluid released during dehydration of the protoliths. They have high contents of REE and some trace elements (e.g., Cs, Th, U, Ta) relative to their protoliths because of an external-element addition from the granitic magma. In-situ analyses of peridotitic silicates confirmed that the prograde tremolite and talc display a spoon-shaped primitive mantle (PM)-normalized REE pattern (0.1-3 times PM) in which LREE are higher than HREE contents. The prograde tremolite is depleted in Al, Na, Cr, Sc, V, Ti, B, HREE and Li, but is enriched in Si, Cs, U, Th, HFSE (Hf, Zr, Nb, Ta), Rb and Ba relative to the retrograde tremolite; the immobile-element depletion in this tremolite is inherited from its source (antigorite + secondary diopside), whereas the depletion of mobile elements (e.g., Li, B, Na, Al) is ascribed to their mobility during the deserpentinization and/or the depleted character of the source of tremolite. The enrichment of HFSE and LILE in the prograde tremolite is related to an external addition of these elements from fluid/melt of the surrounding granitic magma and/or in situ equilibrium with LILE-bearing fluid released during dehydration of serpentinized retrograde metaperidotites and olivine-bearing serpentinites (protoliths). The prograde olivine is higher in REE and most trace-element contents than the retrograde one due to the external addition of these elements; it is enriched in B, Co and Ni, but depleted in Li that was liberated during deserpentinization by prograde metamorphism.     

“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因

赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔(ZK1、ZK2和ZK4)对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10^-6～835.8×10^-6之间,并富集轻稀土(LREE/HREE=2.28～10.78);钻孔ZK1中离子交换相稀土含量达1470×10^-6(9件样品均值),具有从轻稀土型向重稀土型过渡的配分特征(LREE/HREE=1.30～1.65),并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10^-6(8件样品均值),自上而下稀土配分类型从轻稀土型过渡至重稀土型(LREE/HREE=0.43～2.25),且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf...     

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya,Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu)_cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO₂, Al₂O₃, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.     

Flat rare earth element patterns as an indicator of cumulate processes in the Lesser Qinling carbonatites, China

The Lesser Qinling carbonatite dykes are mainly composed of calcites. They are characterized by unusually high heavy rare earth element concentrations (HREE; e.g. Yb > 30 ppm) and flat to weakly light rare earth element (LREE) enriched chondrite-normalized patterns (La/Yb_n = 1.0–5.5), which is in marked contrast with all other published carbonatite data. The trace element contents of calcite crystals were measured in situ by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Some crystals show reduced LREE from core to rim, whereas their HREE compositions are relatively constant. The total REE contents and chondrite-normalized REE patterns from the cores of carbonate crystals are similar to those of the whole rock. The carbon and oxygen isotopic compositions of calcites fall within the range of primary, mantle-derived carbonatites. The initial Sr isotopic compositions (0.70480–0.70557) of calcites are consistent with an EM1 source or mixing between HIMU and EM1 mantle sources. However these sources cannot produce carbonatite parental magmas with a flat or slightly LREE enrichment pattern by low degrees of partial melting. Analyses of carbonates from other carbonatites show that carbonates have nearly flat REE pattern if they crystallize from a LREE enriched carbonatite melt. This implies that when carbonates crystallize from a carbonatite melt the calcite/melt partition coefficients (D) for HREE are much greater than the D for the LREE. The nearly flat REE patterns of the Lesser Qinling carbonatites can be explained if they are carbonate cumulates that contain little trapped carbonatite melt. Strong enrichment of HREE in the carbonatites may require their derivation by small degrees of melting from a garnet-poor source.     

Composition of rare earth elements in settling particles collected in the highly productive North Pacific Ocean and Bering Sea: Implications for siliceous-matter dissolution kinetics and formation of two REE-enriched phases

Settling particles were sampled monthly for 1 year using an automated time-series sediment trap positioned at similar depths at two sites of high diatomaceous productivity in the North Pacific Ocean and Bering Sea. The particles were analyzed for rare earth elements (REEs) by inductively coupled plasma mass spectrometry (ICP-MS) with and without chemical treatment of the bulk samples to isolate siliceous fractions. The REE composition of the bulk samples is explained largely by the contribution of two distinct components: (i) carbonate with a higher REE concentration, a negative Ce anomaly and lighter REE (LREE) enrichment; (ii) opal with a lower REE concentration, a weaker negative Ce anomaly and heavier REE (HREE) enrichment.The siliceous fractions of settling particles are characterized by high Si/Al ratios (30-190), reflecting high diatom productivity at the studied sites. The La/Al ratio of the siliceous fraction is close to that of the upper crust, but the Lu/Al and Lu/La ratios are significantly higher than those of the upper crust or airborne particles, indicating the presence of excess HREEs in the siliceous fraction. Diatoms are believed to be important carriers of HREEs.The Ce anomaly, Eu anomaly, slope of the REE pattern, and ΣREE of the siliceous fraction vary exponentially with decreasing total mass flux. They can be well-reproduced according to the differential dissolution kinetics of elements in the order of Ce < lighter REEs (LREEs) < Eu = heavier REEs (HREEs) < Si from settling particles, where the dissolution rate is critically reduced through particle aggregation. This order is consistent with the vertical distribution of dissolved REEs and Si in oceans. The differential dissolution kinetics leads to HREE enrichment of the original diatoms and REE enrichment of dissolved diatoms. The Lu/Si ratio of the siliceous fraction of settling particles recovered from some of the highest diatom fluxes is identical to that of the two elements dissolved in deep seawater, providing further evidence for the dissolution of siliceous matter in deep water.     

REE Geochemical Study of the Permian—Triassic Marine Sedimentary Environment in Guizhou Province

This paper deals with the REE geochemical characteristics of Permian-Triassic marine carbonate rocks in Guizhou Province.It is found that there are two broad categories of strati-graphic units in the region studied in accordance with their ΣREE contents and REE distribu-tion patterns: one is characterized by LREE enrichment and slight Ce depletion,with the REE distribution patterns similar to those of North American shales,and the other featrures relative HREE enrichment and relatively remarkable Ce depletion,with the REE distribution patterns close to those of pelagic sediments.In terms of their different ΣREE contents,five types of stratigraphic units can be distinguished.Incorporation of detrital minerals,REE complexing ca-pability,oxidation-reduction conditions of the media are the main factors affecting the REE com-position and REE distribution patterns of marine carbonate rocks in the region studied.In the light of REE geochemical characteristics of carbonate rocks,coupled with sedimentary facies analysis,this paper discusses the characteristics of the Permian-Triassic marine sedimentary environment in Guizhou Province and its evolutional rules.     

Formation Process of Zircon Associated with REE‐Fluorocarbonate and Niobium Minerals in the Nechalacho REE Deposit,Thor Lake,Canada

The two drill holes, which penetrated sub‐horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high‐field‐strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type‐1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type‐2 zircon consists of a porous HREE‐rich core and LREE–Nb–F‐rich rim. Enrichment of F in the rim of type‐2 zircon suggests that F was related to the enrichment of HFSE. The core of type‐2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type‐3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type‐3 zircon has high REE, Nb and F contents. Type‐4 zircon consists of porous‐core and ‐rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type‐5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type‐4 and type‐5 zircon grains have low REE, Nb and F contents. Type‐1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type‐2 and type‐3 zircon grains mainly occur in the shallow units, while those of type‐4 and type‐5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type‐4 and type‐5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO₃, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type‐1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F‐rich hydrothermal zircon formed around HREE‐rich magmatic zircon (type‐2). (iii) type‐3 zircon crystallized through the F and CO₃‐rich hydrothermal alteration of type‐2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO₃‐rich hydrothermal fluid corroded type‐3, forming REE–Nb‐poor zircon (type‐4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb‐leached zircon (type‐4); (v) type‐5 zircon is formed by the more CO₃‐rich hydrothermal alteration of type‐4 zircon, suggested by the fact that type‐4 and type‐5 zircon grains are often included in ankerite. Type‐3 to type‐5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type‐2 zircon in the presence of F‐ and/or CO₃‐rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F‐rich hydrothermal stage caused the crystallization of REE–Nb‐rich zircon (type‐2 rim and type‐3), with abundant formation of phlogopite and fluorite; (ii) F‐ and CO₃‐rich hydrothermal stage led to the replacement of a part of REE–Nb–F‐rich zircon by REE fluorocarbonate; and (iii) CO₃‐rich hydrothermal stage resulted in crystallization of the REE–Nb–F‐poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F‐rich zircon in the hydrothermally altered units.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria (Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.     

Enriched and depleted arc basalts, with Mg-andesites and adakites: A potential paired arc-back-arc of the 2.6 Ga Hutti greenstone terrane, India

The ∼2.6 Ga Hutti greenstone belt is one of several Neoarchean greenstone terranes of the eastern Dharwar Craton. There are prevalent mafic volcanic flows with subordinate felsic volcanic units and siliciclastic sedimentary rocks. All lithologies show variable intensities of submarine hydrothermal alteration, polyphase deformation and greenschist to amphibolite grade metamorphism, yet pillow, cumulus, and other primary volcanic features are locally preserved. Well exposed interlayered metabasalts, Mg-andesites (MA), and felsic flows outcrop along an 11 km sector in the SE of the terrane. Based on combined petrographic and geochemical characteristics, two tholeiitic basalt populations have been identified within the metabasalts: (1) those with enriched LREE at 20-50 times chondrite, and (2) an depleted LREE population at 12-20 times chondrite. The former has fractionated LREE, where (La/Sm)_N = 1.2-1.7, but flat HREE, and negative anomalies at Nb, P, and Ti relative to neighbouring REE. The latter has lower absolute abundances of compatible and incompatible elements, mildly fractionated LREE, smaller anomalies at Nb, P, and Ti, with (Gd/Yb)_N = 1.1-1.6. Several samples have the “N-MORB” signature of LREE depletion coupled with positive Nb anomalies. On the Th/Yb vs. Nb/Yb discrimination diagram depleted basalts plot near the MORB field whereas enriched basalts overlap the backarc and arc fields, consistent with a paired arc-back-arc. Mg-andesites feature SiO₂ 57-61 wt.%, multielement pattens similar to enriched basalts, coupled with Cr, Co, Ni contents greater than “normal” andesites. Felsic volcanic rocks are characterized by low Y, high (La/Yb)_N, and Zr/Sm, but low Nb/Ta, with zero to positive Eu anomalies, thus conforming to most of the compositional criteria of Archean and Phanerozoic adakites. Similar associations of enriched and depleted arc basalts, with adakites, are known from Neoarchean greenstone terranes of the Superior Province. During intraoceanic subduction, slab dehydration-wedge melting generated arc basalts whereas slab melting-wedge hybridization, generated adakites and Mg-andesites.     

山东蒙阴科马提岩地球化学特征及其意义

山东蒙阴科马提岩具有典型的鬣刺结构，高镁低钛，铝不亏损，具有正的Rb、Ba、Sr、U异常，轻稀土元素亏损，重稀土元素平坦，稀土元素总量很低，高场强元素与稀土元素发生分异，Nb/Nb^＊〉1，与加拿大蒙罗镇科马提岩地球化学特征和同位素特征相似。研究表明，蒙阴科马提岩可能起源于长期亏损的地幔源区，岩浆不可能来源于以橄榄石、辉石和石榴石（或者majorite）为主要矿物相的地幔源区。最新Sm-Nd同位素研究显示，蒙阴科马提岩样品的εNd值为-0．4～＋3．6，新鲜样品一般为＋3．3，也证实了科马提岩来自长期亏损的地幔源区，并且地幔柱在上升过程中受到地壳混染程度很小，推测研究区科马提岩的喷出可能是新太古代大陆增生事件的重要组成部分。     

Compositional characteristics of wolframite in tin deposits,Dupangling, Guangxi

Statistical data on major, trace and rare-earth elements in wolframite from the quartz vein-and greisen-type tin deposits in the Dupangling orefield reveal: (1) The components in wolframite can be divided into two relatively independent groups: the WO₃-Nb-Ta-Sc-REE group, in which WO₃ is negatively correlated with the others and the FeO-MnO-Sn group, in which MnO is negatively correlated with the other two; (2) In general, REE fractionation is not significant, reflected mainly by the separation of Eu from other REE’s. LREE and HREE increase or decrease simultaneously, with HREE being more variable; (3) Nb, Ta, Sc, REE substitute for W, and Sn may enter into wolframite lattice accompanied by Fe-Mn substitution; (4) In contrast to wolframite in quartz veins, which is poor in REE, Nb, Ta and Sc and has highδ Eu values and LREE / HREE and Nb/Ta ratios, wolframite in greisen is rich in REE, Nb, Ta, Sc and has lowδ Eu values and LREE/HREE and Nb/Ta ratios; and (5) The contents and ratios of trace elements and REE partitioning parameters of wolframite can be used as guide for prospecting.     

浙江八面山萤石矿床稀土元素地球化学特征及成因探讨

对浙江八面山萤石矿床中不同类型萤石矿石和围岩样品的稀土元素的系统分析表明,细粒萤石矿石的ΣREE〈39×10-6,LREE为14.36×10-6～34.24×10-6,HREE0.96×10-6～2.04×10-6,Y〈3×10-6;巨晶萤石矿石中的ΣREE3.62×10-6～20.81×10-6,LREE2.71×10-6～17.67×10-6,HREE0.24×10-6～1.49×10-6;而围岩花岗岩的ΣREE460.29×10-6,LREE225.97×10-6,HREE91.32×10-6,Y＆gt;140×10-6;沉积岩中的ΣREE20.22×10-6、LREE16.11×10-6、HREE1.61×10-6。矿石与围岩中沉积岩的稀土总量、轻稀土、重稀土和Y的含量接近,与花岗岩的稀土总量、轻稀土、重稀土和Y元素含量相差悬殊。萤石矿石的稀土分布型式主要为轻稀土富集型,（La/Yb）N通常多数大于8,在8.07～17.26间,δEu值在0.45～1.30,δCe在0.89～1.14间,Ce、Eu基本不显异常。矿石与围岩的稀土地球化学研究显示,八面山萤石矿床为受地层、岩体与断裂共同控制＂三位一体＂的低温热液型矿床。     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

吉林勇新海西期花岗质岩石的同位素年代学及地球化学

吉林省龙井市勇新海西期花岗质岩石的锆石LA-ICPMS年龄为252.77±0.66 Ma,形成于晚二叠世.岩石地球化学表明,SiO₂含量在57.60%~76.50%之间（平均值为68.50%）,A/CNK小于1.1,Na₂O含量大于3.2%,K₂O/Na₂O普遍小于1,具有典型的Ⅰ型花岗岩特征.在（Na₂O+K₂O）-SiO₂岩石类型分类图中勇新岩体落在二长岩、石英二长岩、花岗闪长岩、花岗岩区.微量元素标准化具有大离子亲石元素Rb、Th、Ba富集,高强场元素Nb、Ta亏损的特点;在球粒陨石标准化配分中,相对富集轻稀土元素亏损重稀土元素,整体分配模式具有同碰撞花岗岩的特征.在R1-R2构造环境判别图上,样品点大部分也落在了同碰撞-碰撞抬升花岗岩区.通过构造环境的综合判断,勇新海西期花岗质岩石的形成时间代表了华北板块与佳木斯地块汇聚碰撞的时间.     

喜马拉雅造山带变泥质岩系及其地球化学特征

高喜马拉雅结晶岩系和北喜马拉雅穹隆都发育高角闪岩相-麻粒岩相变泥质岩,岩石组合以富铝质片麻岩类为主,伴生钾质花岗片麻岩、大理岩及基性麻粒岩等.元素地球化学特征表明,其原岩主要为较富铝的长石质砂岩和石英岩质砂岩及少量粘土岩,形成于大陆边缘浅海相沉积环境.这些变泥质岩具有相似的微量元素和稀土元素地球化学特征,表现为大离子亲石元素相对高场强元素较富集,轻稀土较重稀土富集,稀土总量较高,具有较显著的Eu负异常.在变质矿物组合、元素地球化学特征及锆石组成等特征上,它们与青藏高原北缘的康西瓦和阿尔金孔兹岩系相似,可能是来源于冈瓦纳大陆边缘的同一套岩石.     

REE Geochemistry and Mineralization Characteristics of the Zudong and Guanxi Granites,Jiangxi Province

Abstract The Zudong and Guanxi granites are original rocks of the ion adsorption-type HREE and LREE deposits in weathering crust of granites. The ∑REE ¹ ∑REE=REE+Y.
value and LREE ² LREE=∑(La-Eu) and HREE=∑(Gd-Lu)+Y.
/ HREE ratio of the Zudong granite are 264 ppm and 0.81-0.24 respectively, and the average Y/∑REE ratio is 35.8-54.5%. This is mainly due to magmatic crystallization and evolution and deuteric metasomatism (albitization, muscovitization and fluorite-doveritization). These alterations resulted in endogenic mineralizations of yttrium-group REE fluorine carbonates, silicates and arsenates. The Guanxi granite is characterized by LREE enrichment (the average LREE/HREE ratio is 2.43).