吉林省通化县迎门岔一带白垩系下统火山碎屑岩稀有稀土矿找矿前景浅析

通化县迎门岔一带1∶20万水系沉积物测量,圈定出“通通-84-HS-10”号异常,异常区内出露的岩性主要为白垩系下统林子头组灰绿色、紫色流纹质凝灰岩、角砾凝灰岩、流纹质晶屑岩屑凝灰岩、灰紫色流纹岩、安山岩等火山碎屑岩。在1∶20万异常区内开展了1∶5万水系沉积物测量工作,圈出重点找矿前景区,并在该区内开展1∶1万土壤测量、高精磁测等工作,通过槽探工程验证,发现含铌钽矿化蚀变带,显示出该地区具有较好的稀有稀土矿找矿前景。     

Using multivariate statistical analysis of groundwater major cation and trace element concentrations to evaluate groundwater flow in a regional aquifer

Groundwater samples were collected from 11 springs in Ash Meadows National Wildlife Refuge in southern Nevada and seven springs from Death Valley National Park in eastern California. Concentrations of the major cations (Ca, Mg, Na and K) and 45 trace elements were determined in these groundwater samples. The resultant data were subjected to evaluation via the multivariate statistical technique principal components analysis (PCA), to investigate the chemical relationships between the Ash Meadows and Death Valley spring waters, to evaluate whether the results of the PCA support those of previous hydrogeological and isotopic studies and to determine if PCA can be used to help delineate potential groundwater flow patterns based on the chemical compositions of groundwaters. The results of the PCA indicated that groundwaters from the regional Paleozoic carbonate aquifers (all of the Ash Meadows springs and four springs from the Furnace Creek region of Death Valley) exhibited strong statistical associations, whereas other Death Valley groundwaters were chemically different. The results of the PCA support earlier studies, where potentiometric head levels, δ¹⁸O and δD, geological relationships and rare earth element data were used to evaluate groundwater flow, which suggest groundwater flows from Ash Meadows to the Furnace Creek springs in Death Valley. The PCA suggests that Furnace Creek groundwaters are moderately concentrated Ash Meadows groundwater, reflecting longer aquifer residence times for the Furnace Creek groundwaters. Moreover, PCA indicates that groundwater may flow from springs in the region surrounding Scotty's Castle in Death Valley National Park, to a spring discharging on the valley floor. The study indicates that PCA may provide rapid and relatively cost‐effective methods to assess possible groundwater flow regimes in systems that have not been previously investigated. Copyright © 1999 John Wiley & Sons, Ltd.     

南沙群岛海域沉积物稀土元素地球化学研究

应用电感耦合等离子质谱法测定了南沙群岛海域3个站位沉积物中的稀土元素(REE)和过渡金属元素的含量,讨论了沉积物中REE水平及深度分布的变化特征,以特征金属元素为指标对3个站位进行了沉积区划分,同时对REE与10种金属元素的相关性进行了研究。结果表明,3个站分别为近大陆架残留沉积区、大陆坡深海沉积区和碳酸盐沉积区,各站REE含量存在较大差别,但分布模式相似,均为轻稀土富集型和Eu负异常,每个站各层REE分布模式线几乎重合;3个站沉积物中REE都与Ti、Zr有很好的相关性,与其它金属元素不存在明显的相关性,表明3个站沉积物物源主要为陆源上地壳物质。结合测年资料,认为该海域3个站全新世以来沉积物物源变化很小,沉积环境稳定。     

NOBIAS PA1螯合树脂富集——ICP-MS定量测定近海水体中的稀土元素

稀土元素是海洋中一类极为重要的地球化学过程的示踪剂,但因其浓度多在pmol/kg数量级,分析测试一直是难点,为了使稀土元素在海洋研究中得到更广泛的应用,必须对海洋中低浓度的稀土元素进行准确测量。本研究建立了NOBIAS PA1螯合树脂富集—ICP-MS法,可以对近海的小体积水样中的稀土元素进行高准确度、高精密度分析。研究表明,调节样品溶液pH为4.59~4.69、清洗溶液为6 mL 0.05 mol/L NH_4AC、洗脱溶液为2 mL 1 mol/L HNO_3时,实验测试条件为最优。本方法对稀土元素的回收率在94%~106%,检出限范围为0.001~0.424 pmol/kg,分析精密度优于5%(n=5)。本研究所建立的方法,可用于河水、海水与河口盐度梯度区稀土元素的分析。     

离线固相萃取螯合富集分离-ICP-MS测定海水中的稀土元素

通过测定条件优化、方法比对等实验建立了一种固相萃取小柱离线螯合富集分离电感耦合等离子体质谱仪测定海水中稀土元素的方法。海水样品通过调节p H后,进入VAC ELUT SPS24 Agilent圆形固相萃取装置,其主要基体物质的去除率高于97%;萃取富集的优化条件是海水样品p H 4.0~7.0,海水进入萃取柱速率2 m L/min,硝酸洗脱液浓度为1 mol/L;方法对稀土元素的加标回收率为83%~108%,14种稀土元素的检出限为0.057~0.613 ng/L,RSD10%;该方法与氢氧化铁共沉淀法富集稀土元素比对测定结果一致,方法具有准确度与精密度高、操作简便快速等优点,可用于海水样品中稀土元素的定量精确测量。     

Implication of Apatite and Anhydrite for Formation of an Iron‐Oxide‐Apatite (IOA) Rare Earth Element Prospect,Benjamin River,Canada

The Benjamin River apatite prospect in northern New Brunswick, Canada, is hosted by the Late Silurian Dickie Brook plutonic complex, which is made up of intrusive units represented by monzogranite, diorite and gabbro. The IOA ores, composed mainly of apatite, augite, and magnetite at Benjamin River form pegmatitic pods and lenses in the host igneous rocks, the largest of which is 100 m long and 10–20 m wide in the diorite and gabbro units. In this study, 28 IOA ore and rock samples were collected from the diorite and gabbro units. Mineralogical observations show that the apatite–augite–magnetite ores are variable in the amounts of apatite, augite, and magnetite and are associated with minor amounts of epidote‐group minerals (allanite, REE‐rich epidote and epidte) and trace amounts of albite, titanite, ilmenite, titanomagnetite, pyrite, chlorite, calcite, and quartz. Apatite and augite grains contain small anhydrite inclusions. This suggests that the magma that crystallized apatite and augite had high oxygen fugacity. In back scattered electron (BSE) images, apatite grains in the ores have two zones of different appearance: (i) primary REE‐rich zone; and (ii) porous REE‐poor zone. The porous REE‐poor zones mainly appear in rims and/or inside of the apatite grains, in addition to the presence of apatite grains which totally consist of a porous REE‐poor apatite. This porous REE‐poor apatite is characterized by low REE (<0.84 wt%), Si (<0.28 wt%), and Cl (<0.17 wt%) contents. Epidote‐group minerals mainly occur in grain boundary between the porous REE‐poor apatite and augite. These indicate that REE leached from primary REE‐rich apatite crystallized as allanite and REE‐rich epidote. Magnetite in the ores often occurs as veinlets that cut apatite grains or as anhedral grains that replace a part of augite. These textures suggest that magnetite crystallized in the late stage. Pyrite veins occur in the ores, including a large amount of quartz and calcite veins. Pyrite veins mainly occur with quartz veins in augite. These textures indicate pyrite veins are the latest phase. Apatite–augite–magnetite ore, gabbro–quartz diorite and feldspar dike collected from the Benjamin River prospect contain dirty pure albite (Ab₉₈Or₂–Ab₁₀₀) under the microscope. The feldspar dikes mainly consist of dirty pure albite. Occurrences of the dirty pure albite suggest remarkable albitization (sodic alteration) of original plagioclase (An_25.3–An₆₀ in Pilote et al., 2012) associating with intrusion of monzogranite into gabbro and diorite. SO₄^2? bearing magma crystallized primary REE‐rich apatite, augite and anhydrite reacted with Fe in the sodic fluids, which result in oxidation of Fe²⁺ and release of S^2? into the sodic fluids. REE, Ca and Fe from primary REE‐rich apatite, augite and plagioclase altered by the sodic fluids were released into the fluids. Then Fe³⁺ in the sodic fluids precipitated as Fe oxides and epidote‐group minerals in apatite–augite–magnetite ores. Finally, residual S^2? in sodic fluids crystallized as latest pyrite veins. In conclusion, mineralization in Benjamin River IOA prospect are divided into four stages: (1) oxidized magmatic stage that crystallized apatite, augite and anhydrite; (2) sodic metasomatic stage accompanying alteration of magmatic minerals; (3) oxidized fluid stage (magnetite–epidote group minerals mineralization); and (4) reduced fluid stage (pyrite mineralization).     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).     

云南都龙超大型锡锌多金属矿床中闪锌矿微量及稀土元素地球化学特征

云南马关都龙锡锌多金属矿床位于滇东南老君山锡锌钨多金属成矿区南部,是我国三大锡石硫化物矿床之一,目前对其矿床成因认识存在较大分歧。本文采用ICP-MS对都龙矿床中闪锌矿微量元素及稀土元素组成进行分析,以探讨该矿床成矿作用,为甄别已有成因观点提供证据。结果表明,矿床中闪锌矿以富集Fe、Mn、In、Co、Sn和贫Cd、Ga、Ge、Ni等元素为特征,成矿温度属于中—高温,其微量元素组成与白牛厂矿床(与燕山晚期花岗岩有关的矽卡岩型矿床)中的闪锌矿非常相似,和远源矽卡岩型铅锌矿床(核桃坪和芦子园)中闪锌矿存在一定差异,明显有别于喷流沉积型铅锌矿床(云南澜沧老厂和广东大宝山)中闪锌矿。此外,该矿床闪锌矿稀土配分模式多为轻稀土元素富集中等的向右倾斜曲线,以LREE/HREE值高、Eu负异常明显和Ce异常不明显为特征,与矿区燕山晚期隐伏花岗岩稀土元素特征基本一致,成矿物质来源以矿区燕山晚期隐伏花岗岩为主。结合近期矿山开采和地质勘探所揭露的矿化和矽卡岩蚀变的垂向分带等矿床地质特征,认为云南马关都龙锡锌多金属矿床属于与燕山晚期花岗岩有关的矽卡岩型多金属矿床,其中层状矽卡岩的形成应为成矿流体顺层交代的结果,矿化类型和围岩蚀变的分带与隐伏岩体的距离有关。     

三溴偶氮胂分光光度法测定稀土元素的研究

在1.0 mol/L盐酸介质中,显色剂三溴偶氮胂与稀土元素能发生高灵敏度显色反应,形成稳定的蓝紫色络合物,表观摩尔吸光系数ε_La为1.69×10⁵ L·mol^-1·cm^-1.试剂和络合物的最大吸收波长分别位于525 nm和625 nm.确定了络合物的组成为1:3.在25 mL溶液中,稀土元素在0~17 μg范围内符合比尔定律.本方法受酸度及共存离子影响小,并且有准确、快速、简单的特点.对两个标样做了分析,精密度RSD分别为2.82%和2.57%,准确度RE分别为-2.34%和-5.82%.本方法可不经分离富集,直接用于稀土矿样分析,结果令人满意.     

Neoproterozoic calc‐alkaline peraluminous granitoids of the Deleihimmi pluton,Central Eastern Desert,Egypt: implications for transition from late‐ to post‐collisional tectonomagmatic evolution in the northern Arabian–Nubian Shield

The widely distributed late‐collisional calc‐alkaline granitoids in the northern Arabian–Nubian Shield (ANS) have a geodynamic interest as they represent significant addition of material into the ANS juvenile crust in a short time interval (∼630–590 Ma). The Deleihimmi granitoids in the Egyptian Central Eastern Desert are, therefore, particularly interesting since they form a multiphase pluton composed largely of late‐collisional biotite granitoids enclosing granodiorite microgranular enclaves and intruded by leuco‐ and muscovite granites. Geochemically, different granitoid phases share some features and distinctly vary in others. They display slightly peraluminous (ASI = 1–1.16), non‐alkaline (calc‐alkaline and highly fractionated calc‐alkaline), I‐type affinities. Both biotite granitoids and leucogranites show similar rare earth element (REE) patterns [(La/Lu)_N = 3.04–2.92 and 1.9–1.14; Eu/Eu* = 0.26–0.19 and 0.11–0.08, respectively) and related most likely by closed system crystal fractionation of a common parent. On the other hand, the late phase muscovite granites have distinctive geochemical features typical of rare‐metal granites. They are remarkably depleted in Sr and Ba (4–35 and 13–18 ppm, respectively), and enriched in Rb (381–473 ppm) and many rare metals. Moreover, their REE patterns show a tetrad effect (TE_1,3 = 1.13 and 1.29) and pronounced negative Eu anomalies (Eu/Eu* = 0.07 and 0.08), implying extensive open system fractionation via fluid–rock interaction during the magmatic stage. Origin of the calc‐alkaline granitoids by high degree of partial melting of mafic lower crust with subsequent crystal fractionation is advocated. The broad distribution of late‐collisional calc‐alkaline granitoids in the northern ANS is related most likely to large areal and intensive lithospheric delamination subsequent to slab break‐off and crustal/mantle thickening. Such delamination caused both crustal uplift and partial melting of the remaining mantle lithosphere in response to asthenospheric uprise. The melts produced underplate the lower crust to promote its melting. The presence of microgranular enclaves, resulting from mingling of mantle‐derived mafic magma with felsic crustal‐derived liquid, favours this process. The derivation of the late‐phase rare‐metal granites by open system fractionation via fluid interaction is almost related to the onset of extension above the rising asthenosphere that results in mantle degassing during the switch to post‐collisional stage. Consequently, the switch from late‐ to post‐collisional stage of crustal evolution in the northern ANS could be potentially significant not only geodynamically but also economically. Copyright © 2011 John Wiley & Sons, Ltd.