溶剂浸渍滤纸的制备及其在X射线荧光光谱分析中的应用研究之三地质样…

报道了Ｐ５０７－ＰＭＢＰ溶剂浸渍滤纸（ＳＩＦＰ）的制备及其吸附性质，提出含微量Ｚｒ，Ｈｆ岩矿样品经碱熔分解后强了离子交换树脂静态吸附分离大量干扰元素，再用Ｐ５０７－ＰＭＢＰＳＩＦＰ富集Ｚｒ与Ｈｆ，然后用ＸＲＦ光谱直接测定ＳＩＦＰ上Ｚｒ、Ｈｆ的方法，考察了阳离子交换树脂分离干扰元素的条件，以及在残留干扰元素存在下Ｐ５０７－ＰＭＢＰ ＳＩＦＰ对Ｚｒ，Ｈｆ的富集情况等，对分析误差的来源，样品分析的精密度     

同位素稀释－感耦等离子体质谱法测定钐铕钆的研究

文章研究了地质样品中稀土元素Ｓｍ、Ｅｕ、Ｇｄ的同位素稀释－感耦等离子体质谱的测定方法。验证了同位素稀释法不受基体的影响，实验了利用Ｐ５０７树脂分离干扰元素Ｂａ、Ｌａ和Ｐｒ的条件。Ｓｍ、Ｅｕ、Ｇｄ的检出限（ｎｇ／ｇ）分别为１５、２．７１、１２；对标样ＧＳＤ－１０平行测定１０次，各元素的相对标准偏差均＜２．５％；标样测定结果与推荐值相符。     

P507负载泡塑反相色层富集岩石中的稀土元素

研究了Ｐ５０７负载泡塑萃取柱色谱分离富集稀土元素的条件，并与Ｐ５０７萃淋树脂柱进行了对比；拟定了Ｐ５０７负载泡塑反相色属富集岩石中稀土元素的方法。在ｐＨ２．５介质中ＲＥＥ上柱率９８％，用５０ｍｌ２．５ｍｏｌ／ＬＨＮＯ３作洗脱液，ＲＥＥ总回收率达９６．１％，干扰测定的Ｔｈ，Ｕ，Ｔｉ，Ｚｒ，Ｈｆ等均被除法。方法用于标样分析验证，结果与推荐值相符。     

1，5－二（2－羟基－5－磺基苯基）－3－氰基甲■分光光度法测定煤矸石中微量镓

常温下在ｐＨ４的ＨＡｃ－ＮａＡｃ缓冲体系中，Ｇａ与１，５－二（２－羟基－５－磺基苯基）－３－氰基甲　（ＤＳＰＣＦ）形成稳定的蓝色配合物。该配合物在波长６３０ｎｍ处有最大吸收，其表观摩尔吸光系数为３．８×１０￣４Ｌ·ｍｏｌ￣－１·ｃｍ￣－１，配合比为ｎ（Ｇａ）：ｎ（ＤＳＰＣＦ）＝１：２，显色反应在２０ｍｉｎ内完成，稳定时间至少２４ｈ，Ｇａ量在０～１．８ｍｇ／Ｌ时遵守比尔定律。采用ＴＢＰ萃淋树脂分离干扰元素后可实现煤矸石中Ｇａ的测定。     

同位素稀释—感耦等离子体质谱法测定钐铕钆的研究

文章研究了地质样品中稀土元素Ｓｍ，Ｅｕ，Ｇｄ的同位素稀释－感耦等离子体质谱的测定方法。验证了同位素稀释法不受基体的影响，实验了利用Ｐ５０７树脂分离干扰元素Ｂａ，Ｌａ和Ｐｒ的条件。Ｓｍ，Ｅｕ，Ｇｄ的检出限（ｎｇ／ｇ）分别为１５、２．７１、１２；对样样ＧＳＤ－１０平行测定１０次，各元素的相对标准偏差均＜２．５％；标样测定结果与推荐值相符。     

色层分离－端视电感耦合等离子体发射光谱法测定高纯氧化铕中稀土杂质元素

对Ｐ５０７萃淋树脂分离稀土元素的条件进行了实验，拟定了以Ｐ５０７萃淋树脂为固定相，ＨＣｌ为流动相分离４Ｎ级荧光材料Ｅｕ＿２Ｏ＿３中１４种稀土杂质元素的流程，使被测杂质与基体Ｅｕ＿２Ｏ＿３达到了较好的分离；再用阳离子交换树脂分离被测液中非稀土杂质元素。选择了端视ＩＣＰ－ＡＥＳ测量稀土杂质元素的最佳条件。称样量５０ｍｇ时各杂质组分的测定下限（ｕｇ／ｇ）为：ＣｅＯ＿２、Ｐｒ＿６Ｏ＿（１１）、Ｎｄ＿２Ｏ＿３、Ｓｍ＿２Ｏ＿３、Ｔｂ＿４Ｏ＿７、Ｈｏ＿２Ｏ＿３、Ｅｒ＿２Ｏ＿３，Ｔｍ＿２Ｏ＿３、Ｌｕ＿２Ｏ＿３０．４，Ｌａ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３、０．２，Ｄｙ＿２Ｏ＿３、Ｙ＿２Ｏ＿３０．０４，Ｙｂ＿２Ｏ＿３０．０２。６次取样分析，各杂质组分加入量为１０ｕｇ／ｇ（ＣｅＯ＿２为２ｕｇ／ｇ），加入回收率在８４％～１１２％；ＲＳＤ＜１３％。方法可用于纯度在９９．９９％～９９．９９９５％Ｅｕ＿２Ｏ＿３中１４种稀土杂质元素的测定。     

用ICP－MS准确测定岩石样品中的40余种微量元素

本文建立了一种用ＨＦ＋ＨＮＯ３，密封溶解样品、以ＵＳＧＳ标准岩石样品ＢＣＲ－１作参考标准、外加质量监控样品测定岩石样品中微量元素的ＩＣＰ－ＭＳ分析方法。该方法具有简单、准确、测定元素多的特点。用该方法对ＵＳＧＳ和ＡＧＳＯ的标准岩石样品中４０余种微量元素进行测定，结果表明，除个别元素的分析结果与推荐值偏差接近或略大于１０％外，绝大多数元素的分析结果与推荐值偏差在５％以内。     

色层分离—端视电感耦合等离子体发射光谱法测定高纯氧化铕中稀土…

对Ｐ５０７萃淋树脂分离稀土元素的条件进行了实验，拟定了Ｐ５０７萃淋树脂为固定相，ＨＣＬ为流动相分离４Ｎ级荧光材料Ｅｕ２Ｏ３中１４种稀土杂质元素的流程，使被测杂质与基体Ｅｕ２Ｏ３达到了较好的分离；再用阳离子交换树脂分离被测液中非稀土杂质元素，选择了端视ＩＣＰ－ＡＥＳ测量稀土杂质元素的最佳条件，称样量５０ｍｇ时各杂质组分的测定下限为：ＣｅＯ２，Ｐｒ６Ｏ１１，Ｎｄ３Ｏ３，Ｓｍ２Ｏ３，Ｔｂ４Ｏ７，Ｈｏ２Ｏ     

用ICP—MS准确测定岩石样品中的40余种微量元素

本文建立了一种用ＨＦ＋ＨＮＯ３密封溶解样品，以ＵＳＧＳ标准岩石样品ＢＣＲ－１作参考标准，外加质量监控样品测定岩石样品中微量元素的ＩＣＰ－ＭＳ分析方法。该方法具有简单，准确，测定元素多的特点。用该方法对ＵＳＧＳ和ＡＧＳＯ的标准岩石样品中４０余种微量元素进行测定，结果表明，除个别元素的分析结果与推荐值偏差接近或略大于１０％外，绝大多数元素的分析结果与推荐值偏差在５％以内。     

1,5—二（2—羟基—5—磺基苯基）—3—氰基甲Zan分光光度法测定煤矸石中微量镓

常温下ＰＨ４的ＨＡｃ－ＮａＡｃ缓冲体系中，Ｇａ与１，５－二（２－羟基－５－磺基苯基）－３－氰基甲Ｚａｎ（ＤＳＰＣＦ）形成稳定的蓝色配合物。采用ＴＢＰ萃淋树脂分离干扰元素后可实现煤矸石中Ｇａ的测定。     

XO螯合形成纤维分离富集微量锆铪性能的研究

本文采用先螯合后吸着的方法,研究了XO螯合形成纤维分离富集微量锆铪的性能。试验研究表明,该纤维能富集浓度低至0.04ppm的锆铪,并且能与大量基体元素相分离;当锆铪总量约为0.41ppm时,采用本方法九次测定的标准偏差为0.21,变异系数为1.05％;回收率可达99.24％。该方法具有操作简便、交换速率快、干扰少、富集能力强、成本低等特点,适用于成分较复杂样品中微量锆铪的分离和富集。     

Geochemistry and Fractionation of Zr and Hf in the Magmatic System of the Kugda Massif (Polar Siberia)

The patterns of the distribution and fractionation of strategic metals (Zr, Hf) in the Kugda intrusion (Polar Siberia) have been studied. The contents of these elements significantly exceed their concentrations in other rocks (Zr, 246 ppm; Hf, 7.4 ppm). A significant increase in Zr and Hf from early rocks (olivinite and melilite rocks) to later differentiation products, syenites with up to 570 ppm of Zr and 16 ppm of Hf, has been revealed. During the evolution of the Kuga magmatic system, notable fractionation of Zr and Hf occurred. The Zr/Hf ratios in the dyke rock, similar in composition to the primary Kugda Massif magma, and the early intrusions are fairly close to that of chondrite (Zr/Hf = 37 [1]), while in the latest phases this ratio increases by almost 5-fold.     

Sorption of Zr~(4+) and Hf~(4+) onto Hydrous Ferric Oxide and Their Fractionation Behaviors:An experimental Study

1 Introduction Coherent element pairs (Y3+-Ho3+, Zr4+-Hf4+, Nb5+-Ta5+ and Sr2+-Eu2+) have the same valences and very similar ionic radii. They are seldom fractionated during silicate mineral/melt interaction systems because the partitioning of these element pairs between melts and minerals is tightly controlled by charge valence and crystal structure (lattice site size) or ionic radius. The concentration ratios of these pairs in igneous rocks are close to the chondritic values (Y/Ho=28, Zr…     

峨眉山二滩高钛玄武岩Zr/Hf分异的指示意义

对峨眉山二滩高钛玄武岩高场强元素的研究表明,Zr/Hf比值出现了明显分异,可分为高Zr/Hf组和低Zr/Hf组两组玄武岩。Zr/Hf比值的分异与岩浆结晶分异作用无关,而是由部分熔融和地幔源区的不同所导致,暗示高Zr/Hf组和低Zr/Hf组玄武岩分别具有不同的部分熔融条件和不同的地幔物质组分。     

Zirconium and hafnium fractionation in differentiation of alkali carbonatite magmatic systems

Zirconium and hafnium are valuable strategic metals which are in high demand in industry. The Zr and Hf contents are elevated in the final products of magmatic differentiation of alkali carbonatite rocks in the Polar Siberia region (Guli Complex) and Ukraine (Chernigov Massif). Early pyroxene fractionation led to an increase in the Zr/Hf ratio in the evolution of the ultramafic–alkali magmatic system due to a higher distribution coefficient of Hf in pyroxene with respect to Zr. The Rayleigh equation was used to calculate a quantitative model of variation in the Zr/Hf ratio in the development of the Guli magmatic system. Alkali carbonatite rocks originated from rare element-rich mantle reservoirs, in particular, the metasomatized mantle. Carbonated mantle xenoliths are characterized by a high Zr/Hf ratio due to clinopyroxene development during metasomatic replacement of orthopyroxene by carbonate fluid melt.     

Geochemistry of fractionation of coherent elements (Zr and Hf) during the profound differentiation of peralkaline magmatic systems: A case study of the Lovozero Complex

The paper presents pioneering data on Hf distribution in peralkaline rocks, ores, and rock-forming and accessory minerals of the Lovozero Complex. Variations in the Zr/Hf ratio are determined in all rocks of the Lovozero alkaline massif. This ratio is proved to increase in the course of evolution of alkaline magma because of fractionation of alkaline pyroxene. The Hf distribution coefficient is evaluated for alkali-rich pyroxene, whose crystallization controls Zr and Hf fractionation during the differentiation of alkaline magma. These data and the equation of equilibrium and fractional crystallization are utilized in a model suggested for Zr and Hf fractionation in the course of evolution of the Lovozero intrusion.     

The Zr/Hf ratio as a fractionation indicator of rare-metal granites

The Zr-Hf geochemical indicator, i.e., the Zr/Hf ratio (in wt %) in granitic rocks is proposed to be used as the most reliable indicator of the fractionation and ore potential of rare-metal granites. It was empirically determined that the fractional crystallization of granitic magma according to the scheme granodiorite → biotite granite → leucogranite → Li-F granite is associated with a decrease in the Zr/Hf ratio of the granites. The reason for this is the stronger affinity of Hf than Zr to granitic melt. This was confirmed by experiments on Zr and Hf distribution between granitic melt and crystals of Hf-bearing zircon (T = 800°C, P= 1 kbar). The application of the Zr/Hf indicator was tested at three classic territories of rare-metal granites: eastern Transbaikalia, central Kazakhstan, and the Erzgebirge in the Czech Republic and Germany. The reference Kukul’bei complex of rare-metal granites in eastern Transbaikalia (J₃) is characterized by a uniquely high degree of fractionation of the parental granitic melt, with the granites and their vein derivatives forming three intrusive phases. The biotite granites of phase 1 are barren, the leucogranites of phase 2 are accompanied by greisen Sn-W mineral deposits (Spokoininskoe and others), and the final dome-shaped stocks of amazonite Li-F granites of phase 3 host (in their upper parts) Ta deposits of the “apogranite” type: Orlovka, Etyka, and Achikan. The Kukul’bei Complex includes also dikes of ongonites, elvanes, amazonite granites, and miarolitic pegmatites. All granitic rocks of the complex are roughly coeval and have an age of 142±0.6 Ma. The Zr/Hf ratio of the rocks systematically decreases from intrusive phase 1 (40–25) to phases 2 (20–30) and 3 (10–2). Compared to other granite series, the granites of the Kukul’bei Complex are enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but are depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From earlier to later intrusive phases, the rocks become progressively more strongly enriched or depleted in these elements, and their Zr/Hf ratio systematically decreases from 40 to 2. This ratio serves as a reliable indicator of genetic links, degree of fractionation, and rare-metal potential of granites. Greisen Sn, W, Mo, and Be deposits are expected to accompany granites with Zr/Hf < 25, whereas granites related to Ta deposits should have Zr/Hf < 5.     

火山岩风化过程中难熔元素的活动性研究——以广西凭祥英安岩风化剖面为例

对广西凭祥叫弄英安岩风化剖面中6个难熔元素的活动性进行了研究。结果表明，Ti,Nb和Ta 3种元素在整个风化成土过程中基本上保持了它们的不活动性。Zr,Hf和Th在风化的初期阶段基本上保持不活动，而在风化中期表现出一定的富集，风化高级阶段则有明显的富集。Th的富集可能与风化壳表层（已剥蚀）淋溶出来的Th向下迁移过程中被氧化铁吸附和形成磷酸盐矿物有关，而Zr的富集则可能与淋溶出来的Zr与SiO2或磷酸盐结合形成某种硅酸盐矿物和磷酸盐矿物有关，具体富集原因还需作进一步的研究。     

延边开山屯花岗闪长岩-石英闪长岩体年代学、地球化学特征及对古太平洋板块俯冲作用时限的制约

近年来古太平洋构造域的构造演化备受学者关注。本文报道的延边开山屯地区花岗闪长岩-石英闪长岩体LAICP-MS U-Pb年龄表明其形成时间为早侏罗世早期(198±1Ma),所采样品可根据Zr/Hf值分为高Zr/Hf值组花岗闪长岩和低Zr/Hf值组石英闪长岩。高Zr/Hf值组花岗闪长岩起源深度浅,富集Rb、Th、U、K等大离子亲石元素(LILEs),贫Nb、Ta、Ti等高场强元素(HFSEs),具壳源岩浆的特点。低Zr/Hf值组为壳源岩浆与来自深部的亏损地幔岩浆混合而成,岩石亏损Nb、Ta、Zr、Hf、Ti等高场强元素,具有典型的弧型岩浆地球化学特征。岩体中存在细粒闪长质包体,镜下可见针柱状磷灰石。开山屯岩体属钙碱性系列岩石,结合前人资料,认为其与该地区同时代火成岩组成北-东向分布的早侏罗世活动大陆边缘型火成岩带,而位于该带西侧的小兴安岭-张广才岭地区存在同时代弧后拉张带,两者构成典型的大陆弧与弧后拉张带模型,共同揭示了早侏罗世早期古太平洋板块对东北地区的俯冲作用。     

Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: evidence from Y/Ho,Zr/Hf,and lanthanide tetrad effect

 The parameters which control the behaviour of isovalent trace elements in magmatic and aqueous systems have been investigated by studying the distribution of yttrium, rare-earth elements (REEs), zirconium, and hafnium. If a geochemical system is characterized by CHArge-and-RAdius-Controlled (CHARAC) trace element behaviour, elements of similar charge and radius, such as the Y-Ho and Zr-Hf twin pairs, should display extremely coherent behaviour, and retain their respective chondritic ratio. Moreover, normalized patterns of REE(III) should be smooth functions of ionic radius and atomic number. Basic to intermediate igneous rocks show Y/Ho and Zr/Hf ratios which are close to the chondritic ratios, indicating CHARAC behaviour of these elements in pure silicate melts. In contrast, aqueous solutions and their precipitates show non-chondritic Y/Ho and Zr/Hf ratios. An important process that causes trace element fractionation in aqueous media is chemical complexation. The complexation behaviour of a trace element, however, does not exclusively depend on its ionic charge and radius, but is additionally controlled by its electron configuration and by the type of complexing ligand, since the latter two determine the character of the chemical bonding (covalent vs electrostatic) in the various complexes. Hence, in contrast to pure melt systems, aqueous systems are characterized by non-CHARAC trace element behaviour, and electron structure must be considered as an important additional parameter. Unlike other magmatic rocks, highly evolved magmas rich in components such as H₂O, Li, B, F, P, and/or Cl often show non-chondritic Y/Ho and Zr/Hf ratios, and “irregular” REE patterns which are sub-divided into four concave-upward segments referred to as “tetrads”. The combination of non-chondritic Y/Ho and Zr/Hf ratios and lanthanide tetrad effect, which cannot be adequately modelled with current mineral/melt partition coefficients which are smooth functions of ionic radius, reveals that non-CHARAC trace element behaviour prevails in highly evolved magmatic systems. The behaviour of high field strength elements in this environment is distinctly different from that in basic to intermediate magmas (i.e. pure silicate melts), but closely resembles trace element behaviour in aqueous media. “Anomalous” behaviour of Y and REEs, and of Zr and Hf, which are hosted by different minerals, and the fact that these minerals show “anomalous” trace element distributions only if they crystallized from highly evolved magmas, indicate that non-CHARAC behaviour is a reflection of specific physicochemical properties of the magma. This supports models which suggest that high-silica magmatic systems which are rich in H₂O, Li, B, F, P, and/or Cl, are transitional between pure silicate melts and hydrothermal fluids. In such a transitional system non-CHARAC behaviour of high field strength elements may be due to chemical complexation with a wide variety of ligands such as non-bridging oxygen, F, B, P, etc., leading to absolute and relative mineral/melt or mineral/aqueous-fluid partition coefficients that are extremely sensitive to the composition and structure of this magma. Hence, any petrogenetic modelling of such magmatic rocks, which utilizes partition coefficients that have not been determined for the specific igneous suite under investigation, may be questionable. But Y/Ho and Zr/Hf ratios provide information on whether or not the evolution of felsic igneous rocks can be quantitatively modelled: samples showing non-chondritic Y/Ho and Zr/Hf ratios or even the lanthanide tetrad effect should not be considered for modelling. However, the most important result of this study is that Y/Ho and Zr/Hf ratios may be used to verify whether Y, REEs, Zr, and Hf in rocks or minerals have been deposited from or modified by silicate melts or aqueous fluids. Received: 4 September 1995 / Accepted: 30 October 1995