小体积萃取-石墨炉原子吸收法测定高纯硝酸钡中纳克级重金属元素

本文研究了石墨炉原子吸收光谱法测定高纯硝酸钡中超痕量重金属元素的分析技术。提出在大量钡基体存在时,采用小体积萃取体系APDC-MIBK同时萃取纳克级的Fe、Cu、Co和Ni。该法具有灵敏度高、无干扰、操作方便和减少沾污等特点。方法检出限为:Fe 7.2ng/g、Cu 12.8ng/g、Co 4.4ng/g和Ni 6.7ng/g。应用于红外光纤原料硝酸钡、硝酸铝中痕量重金属的测定,效果良好。     

关于成矿系列的结构

成矿系列是一个自然系统,它由若干矿床成因类型组成。各矿床类型间的时空结构关系表现为各类型间的“共生性”、“过渡性”和“重叠性”;其物质结构关系表现为“互补性”.本文按系统论观点,分析了上述结构,提出长江中下游铁铜成矿系列的新模式,并指出研究成矿系列的结构对预测矿产的重要意义.     

西天山伊宁-新源-巴仑台地区铁矿找矿远景综述

文章利用地质、物探资料对新疆西天山地区铁矿成矿情况进行了分析,并指出可供进一步开展工作的成矿远景区.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Electronic absorption spectra of Fe2+ ions in oxygen-based rock-forming minerals at temperatures between 297 and 600 K

 Polarized electronic single crystal spectra of natural Fe²⁺ ion-bearing oxygen-based minerals, in which ferrous ions enter octahedral sites of different symmetry and distortion (olivine, cordierite, ortho- and clinopyroxene, amphibole), eightfold sites in garnet (almandine) and clinopyroxene (M2), and tetrahedral sites in spinel, were studied at temperatures from 300 to ca. 600 K. In the minerals studied, the spin-allowed bands of Fe²⁺ display rather variable temperature behaviour. In most cases, due to the thermal expansion of the Fe²⁺-bearing polyhedra, bands shift to lower energies upon increasing temperature, though there are some exceptions to this rule: in cases of other than sixfold octahedral or close to octahedral coordination, in almandine and spinel the bands shift to higher energies, which can be explained by an increase in distortions of the Fe²⁺-bearing polyhedra. Splitting of the excited ⁵ E _g-level of Fe²⁺ ions usually, but not always, increases with temperature, reflecting thermally induced increase in distortion of the Fe²⁺-bearing sites in the minerals studied. Integral intensities of the bands in question do not always obey the general rule, according to which intensity should increase with temperature, when the 3d ^N-centred site is centrosymmetric, or should remain unchanged when the 3d ^N site lacks an inversion centre. The experimental results show that the response of the characteristics of absorption bands such as width, intensity and energy caused by dd transitions of Fe²⁺ in oxygen-based minerals to increasing temperature is not always uniform and is at variance with expectation. This temperature dependence cannot be used directly to solve band assignment problems, as earlier proposed in the literature. Received: 22 December 1999 / Accepted: 30 October 2000     

富钴结壳生长过程中铁锰氧化物矿物组合的变化

富钴结壳的矿物学研究是一个难点，本文运用电子探针微区分析结合X射线衍射和矿相显微镜观察的综合方法对富钴结壳中的铁锰氧化物矿物组合及其组分变化进行了研究，研究发现，富钴结壳是从与胶状粘土类混合共沉积开始生长的，结壳内部的韵律层和柱状构造也是始于粘土层终于粘土层的；铁锰团粒的核心一般是较纯的水羟凶国矿小核心，可能是在生物媒介作用下在水体中形成后沉降叠积的，FM、FPE海山结壳的中层存在一较纯水羟锰矿层，但该层中Co含量FM15比FPE06低得多，可能反映了FM15在该层形成时Co通量较低，而该层在FN12中不存在，反映了区域环境的较大差异，在FN12火焰状构造亚带存在Mn氧化物和Fe氧化物的极度分异现象，可能反映了结壳形成环境的重大变化。     

X射线荧光光谱法测定叶腊石中的铝铁钾钠

采用同一矿区已知成分含量的叶腊石配制标样系列，克服了粉末法测定叶腊石中Ａｌ２Ｏ３，Ｆｅ２Ｏ３，Ｋ２Ｏ，Ｎａ２Ｏ的矿物和粒度效应。分析结果准确度满足出口材料的检测要求。     

Intracrystalline fractionation of Fe in synthetic (Fe, Mg, Zn) - bearing staurolite: a Mössbauer spectroscopic study

⁵⁷Fe-Mössbauer spectra of eleven Fe-Mg-bearing staurolite samples, synthesized at 5, 20 and 25 kbar and 680°C, ranging in composition from x_Fe?=1.00 to x_Fe?=0.15, and of two Zn-Fe-bearing staurolite samples, synthesized at 20 kbar and 700°C with x_Fe?=0.10 and x_Fe?=0.32 were collected at room temperature. The spectra reveal that about 80% of Fe_tot (in case of Fe-Mg-bearing staurolite) and about 70% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the three subsites Fe1, Fe2 and Fe3 of the tetrahedral T2-site. The refinement of the spectra results in almost identical values for the isomer shift (IS) (±1.0 mm/s) but significantly different values for the quadropole splitting (QS) for the three subsites which is in accordance with the different distortions of these sites. About 8% of Fe_tot (in case of Fe-Mg-bearing staurolite) and 13% of Fe_tot (in case of Fe-Zn-bearing staurolite) are located as Fe²⁺ at the octahedral M4 site, while the remainder percents of Fe_tot indistinguishably occur as Fe²⁺ at the octahedral M1 and M2 sites of the kyanite-like part of the structure. Within the whole Fe-Mg-staurolite solid solution series the Mössbauer parameters QS of the sites M4 and (M1, M2) vary systematically with composition whereas IS remains constant. There is a high negative correlation of the total Mg-content with Fe-occupation of all the Fe-bearing sites indicating a continuous substitution of Fe²⁺ by Mg on all these sites. Synthetic Fe-staurolites show no increasing occupation of the octahedral sites by two-valent cations with pressure, as was assumed by several authors.     

宁芜盆地凹山和东山铁矿床流体包裹体和氢氧同位素研究

本文对宁芜地区凹山和东山铁矿床中的磷灰石流体包襄体进行了较为系统的测温研究,并测定了不同时期形成的磁铁矿、阳起石和石英的 H、O 同位素组成。凹山和东山铁矿磷灰石含有丰富的流体包裹体,原生气液包裹体包括早期细长管状、针状包裹体(类型Ⅱ)和晚期不规则状包襄体(类型Ⅰ);早期包裹体又可分为单一液相包裹体(类型Ⅱ-a)、气液两相(富气相)包襄体(类型Ⅱ-b)、气液两相(富液相)包裹体(类型Ⅱ-c)和气相、液相及固相多相包裹体(类型Ⅱ-d)四种亚类。包襄体中至少含有五种不同的子矿物。磷灰石包裹体记录了多个峰值温度,从600℃～800℃到～410℃和～270℃,分别对应于磷灰石(磁铁矿 透辉石)、阳起石和石英的形成。流体的盐度随温度的降低而逐渐减小,从高达～80%NaCl equiv。到<20%NaCl equiv。磷灰石形成时流体处于不均匀的状态,流体包裹体为非均一捕获。H、O 同位素研究显示成矿流体早期为演化的初始岩浆(水),在高温下形成了铁矿石;此后,成矿流体有可能与蒸发盆地卤水或大气降水发生混合;晚期则可能有较显著的大气降水加入。