透闪石质玉中黄玉与糖玉致色成因差异研究

采用常规宝石学仪器并结合电子探针、电子顺磁共振谱及紫外-可见光谱等测试方法,对软玉中不同深浅的黄玉与糖玉样品进行了系统分析,以探讨其致色原因及其差异。分析结果表明,黄玉的致色原因主要为O^2-→Fe³⁺的电荷转移跃迁及Fe³⁺的⁶A₁→⁴T₂（D）跃迁,糖玉则主要由Fe³⁺的⁶A₁→⁴E （D）、⁶A₁→⁴T₂（D）谱项跃迁与Mn³⁺的Jahn-Teller效应致色。黄玉中O^2-→Fe³⁺的电荷转移跃迁导致可见光区的412~500 nm处吸收,是形成与控制黄玉颜色的重要因素;而糖玉因含有Mn³⁺致使黄绿色光被吸收而显示出黄绿色的补色。此外,Fe²⁺—Fe³⁺的荷移与Fe²⁺（⁵T₂）+Fe³⁺（⁶A₁）→Fe²⁺（⁵E）+Fe³⁺（⁶A₁）跃迁也对糖玉和黄玉的致色具有贡献。     

绿柱石中铁离子的晶格占位及致色作用

绿柱石族宝石颜色丰富,一直是市场上重要的宝石品种。几十年来,国内外学者对不同颜色绿柱石的致色机理及改色工艺开展了广泛的研究。铁离子作为重要的致色过渡金属离子之一,其价态调控是绿柱石改色工艺的关键,所以铁离子的价态、晶格占位和对应的致色作用也一直是绿柱石研究的焦点。铁离子被认为可能存在于绿柱石中的铝氧八面体Al³⁺格位、硅氧四面体Si⁴⁺格位、铍氧四面体Be²⁺格位、结构通道2a或2b位和晶格间隙6g位等位置,是蓝、绿或黄等颜色绿柱石的主要致色元素。本文通过对绿柱石的晶体结构、铁离子的核外电子排布和晶格占位等方面文献资料的梳理及综合分析,认为Fe²⁺和Fe³⁺分别对蓝色和黄色绿柱石的呈色起着主导作用。当Fe²⁺和Fe³⁺处于晶格中不同位置时致色作用的具体差异,仍有待于进一步研究。     

锡铁山石晶体结构中Fe3+的两种亚晶位

对产于青海锡铁山铅锌矿氧化带中的锡铁山石进行了５７Ｆｅ穆斯堡尔谱的研究，在晶体结构分析的基础上进行了谱峰的重新解释，发现由于配位Ｃｌ－离子无序占位引起Ｆｅ３＋离子所占配位八面体的畸变，形成了Ｆｅ３＋的两种亚晶位，并根据结构数据指定了这两种亚晶位各自形成的四极双峰。     

小秦岭金硐岔金矿床九号石英脉中自然铁的发现及研究

自然铁产于含金石英脉中,其外壳为磁铁矿。多数自然铁外壳被闪锌矿包裹,个别闪锌矿又被包裹在自然铁外壳中.按表面形态自然铁可分为两种类型:园滑状;不规则的港湾状.锯齿状。据穆斯堡尔谱峰面积法,外壳磁铁矿Fe~(+++)/Fe~(++)比值为1.4～1.7.电镜成分面扫描表明,随外壳厚度增加,氧浓度增高而硫浓度降低。不规则状自然铁外壳磁铁矿可能由黄铁矿氧化而来。     

东疆红山Cu-Au矿床氧化带硫酸盐矿物穆斯堡尔谱特征及其意义

穆斯堡尔谱对确定铁离子占位、核外环境及氧化态方面有着独特的优势。在红山铜金矿床氧化带硫酸盐矿物的XRD、TA、湿法化学分析和红外光谱测试的基础上,测定了板铁矾、针绿矾等8种硫酸盐矿物的室温57Fe穆斯堡尔谱,并根据常温下硫酸盐矿物穆斯堡尔谱参数和其晶体结构中Fe3+和Fe2+的占据位置对其谱峰进行了指派。结果表明本矿床氧化带硫酸盐矿物的穆斯堡尔谱的同质异能位移较小、四级矩分裂值分布范围较大、无磁超精细分裂等特征,且硫酸盐矿物结构中存在着共价键。通过与青海锡铁山铅锌矿氧化带硫酸盐矿物的穆斯堡尔谱相比较,两者在近地表风化及氧化过程中所处的物理化学条件基本相同,酸性和氧化性的环境为硫酸盐矿物的产生和保存提供了良好条件,但红山矿床更为干旱少雨,导致两者硫酸盐的穆斯堡尔谱参数略有不同。     

天然磁铁矿中铁的占位分布和类质同象替代的穆斯堡尔研究

磁铁矿是一种重要的常见矿物。人们用穆斯堡尔方法对磁铁矿已经做了一些研究。在室温下,磁铁矿的穆斯堡尔谱由两套六线谱组成。通常它们被分别指派给A位上的Fe~(3 )和B位上的Fe~(2 )与Fe~(3 )。等曾对这种指派提出不同看法,讨论了几种可能的指派方法。大多数天然磁铁矿的情况比组份简单的、正分的磁铁矿要复杂得多。它们常     

华南某矿区磁铁矿的谱学研究

从~（57）Fe和~（119）Sn无反冲共振吸收谱分析,配合x射线衍射分析等方法,获知华南某铁矿-多金属矿区,两种铁矿石中磁铁矿的组份。从穆斯堡尔谱峰面积法,推算出非正分的磁铁矿晶体结构式,并由此算出其中Fe~（2+）和Fe~（3+）的含量比。综合矿石产状及铁的氧化态分析,获得不同铁矿石的成因信息。     

表生环境下闪锌矿氧化反应模拟实验

采用混合流反应器装置,进行了表生环境条件下闪锌矿氧化动力学模拟实验研究,选择Fe³⁺和O₂为氧化剂,实验条件为:温度20～55℃,pH=1.0～7.8、氧化剂Fe³⁺浓度1.0×10^-5～1.0×10^-2 mol/L,氧气流量0.5 L/min。实验结果表明,在Fe³⁺为氧化剂时,闪锌矿氧化速率随着Fe³⁺浓度的增加、温度升高、pH值降低而增加,且氧化过程中Zn和Cd的释放速率大致相同,其反应的活化能分别为Ea(Zn) 41.75 kJ/mol或Ea(Cd) 42.51 kJ/mol,表明闪锌矿氧化速率主要受矿物表面反应控制;而以氧气作为氧化剂时,随着pH值的变化闪锌矿的氧化机理发生变化,在pH值小于5.95范围内,闪锌矿氧化速率随着pH值的增加而降低,进入碱性范围后,随着pH值增加,闪锌矿氧化速率反而增加。对实验数据进行双对数处理并建立了闪锌矿的氧化速率公式。     

磁铁矿的穆斯堡尔谱研究

我们对大冶、马坑、大顶、黄沙坪、鞍山五个矿区的七个铁矿石样品中的磁铁矿作了室温~(57)Fe和~(119)Sn穆斯堡尔谱测定,并根据穆斯堡尔数据和化学分析推算出磁铁矿的非理想配比的分子结构式. 初步研究表明,不同的成矿条件和Zn、Mg等二价阳离子的类质同像替代的多少,明显地影响晶胞参数和穆斯堡尔参数.文中讨论了它们的变化规律性.     

多硅白云母中Fe2+的高压有序效应

21个多硅白云母来自4个低温高压变质带。用电子探针、X射线粉末衍射及穆斯堡尔谱测定其化学成分、b0值及Fe²⁺占位。建立Fe²⁺(M1)/Fe²⁺(M2)对b0值相关图,发现Fe²⁺在八面体晶位有序化并解释其有序机理。     

Partitioning of Ni2+, Co2+, Fe2+, Mn2+ and Mg2+ between olivine and silicate melts: compositional dependence of partition coefficient

Partitioning of Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺ and Mg²⁺ between olivine and silicate melts has been determined near the join (Mg_0.5·-Fe_0.5)₂SiO₄-K₂O 4SiO₂ and for seven different basaltic compositions. The experiments were made at 1 atm total pressure, 1500-1100°C, and under moderate to reducing oxygen fugacities. The concentration factor, defined as K^MO = (MO)^ol/(MO)^liq (molar ratio), increases markedly for all the cations studied as the olivine component of the liquid decreases. Much of the increase in K^MO is considered as due to the compositional effect of the coexisting liquid: the temperature effect on K^MO is probably opposite to the compositional effect (K^MO decreases as temperature decreases).The partition coefficient K^MO-MgO = (MO/MgO)^ol/(MO/MgO)^liq for the reaction, M_ol²⁺ + Mg_liq²⁺ = M_liq²⁺ + Mg_ol²⁺. is relatively constant over a wide range of SiO₂ content of the liquid, except in the case of Ni²⁺. The partition coefficients have similar ranges both in synthetic and natural rock systems: K^NiO-MgO = 1.8–3.0, K^CoO-MgO = 0.6–0.8, K^FeO-MgO = 0.27–0.38, and K^MnO-MgO = 0.23–0.32. There is a systematic variation in the partition coefficient K^MO-MgO with the composition of liquid; K^MO-MgO increases with increasing SiO₂ content of melt. The partition coefficients for Co²⁺, Fe²⁺ and Mn²⁺ are useful to test the equilibration of olivine with magma of a wide compositional range.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts and aqueous solutions—II. The network modifying effects of Mg2+ , K+, Na+, Li+, H+, OH−, F−, Cl−, H2O,CO2 and H3O+ on silicate polymers

The effect of the group IA and VIIA ions, as well as Mg²⁺, and the molecules H₂O, CO₂, H₃O⁺ and OH^? on the energy of the Si-O bond in a H₆Si₂O₇ cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle.     

矿物发光材料CaS∶Mn2+的合成及其荧光性质

以方解石为原料,使用硫化助熔剂法合成了CaS∶Mn2+磷光体,根据荧光光谱,详细探讨了矿物杂质对其发光性质的影响,指出在矿物材料CaS∶Mn2+体系中,某些杂质离子拓宽了基质的激发带,有利于基质吸收能量及基质→Mn2+发射中心的能量传递,但Fe2+、Co2+、Ni2+等离子降低了Mn2+的发射强度,尤其是Mn2+与它们形成的成对离子中心或离子晶簇,降低了局域对称性,放宽了Mn2+跃迁发射的选择定则,加速了材料发光的衰减过程.     

Microscope-photometric methods for non-destructive Fe2+ – Fe3+ determination in chloritoids (Fe2+, Mn2+, Mg)2 (Al,Fe3+)4 Si2O10(OH)4

Six natural chloritoid crystals with Fe²⁺ and Fe³⁺ contents ranging from 4.15 to 12.81 and from 0.411 to 0.849g-atoms/l, respectively, as determined by means of microprobe and Mössbauer techniques, served as reference material to develop non-destructive microscope-spectrophotometric methods for quantitative Fe²⁺ – Fe³⁺ determinations in chloritoids from unpolarized spectra of (001) platelets. Fe²⁺ concentrations in g-atom/l can be obtained from [ [Fe³⁺]=C₁xD₁/t where D₁ = log₁₀(I_0/I at 28,000 cm^-1 and t=crystal thickness in cm; C₁ is a conttant that may be influenced somewhat by experimental conditions and is found to be 0.002289 with the experimental set-up used in this study. Fe²⁺ concentrations in g-atom/l can be obtained from [Fe²⁺]=C₁xD₁/D₁-C₃ with D₂=log₁₀(I₀/I) at 16,300 cm^?1 and constants C₄ = 45.36 and C₅ = 3.540. Due to the uncertainties in absorbance measurements, D₁ and D₂ and the thickness measurements, the accuracies are ±0.05 and ±0.15 g-atom/l for [Fe³⁺] and [Fe²⁺], respectively. The determinations may be carried out on chloritoid grains in normal thin sections with an areal resolution of ～10 μm.     

An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

室温常压下 Ca2+-Mg2+-HCO31--H2O 体系的试验研究

世界上很多海域中的现代碳酸盐沉积正在形成,如巴哈马滩、美国的佛罗里达湾、古巴的巴塔诺湾、中东的波斯湾等地,以及丹麦的某些近海地区。产于这些海域中的现代碳酸盐沉积物,其矿物组成主要是文石,其次为镁方解石,纯方解石较少,现代白云石沉积更为少见。我国的现代碳酸盐沉积见于南海诸岛及海南岛的沿海地带。作者曾利用粉晶照相鉴定了采自我国南海二十余种珊瑚、瓣鳃类、腹足类、有孔虫等现代海相生物壳体的物相,发现除有孔虫和海胆壳是由镁方解石构成外,其余生物壳体皆由文石构成。     

Thermodynamic model of natural brines accounting for the presence of trace components: II. System Na+, K+, Mg2+ ‖ Cl?, Br?-H2O

This paper reports the calculations of parameters for the Pitzer equation and thermodynamic potentials of solid phases crystallizing in water-salt systems modeling chloride brines taking into account the presence of bromide ions in them. Solubility diagrams were calculated for corresponding ternary and quaternary systems containing chlorides and bromides of sodium, potassium, and magnesium at 25°C. The results of calculations are in adequate agreement with the available published experimental data on solubility and can be used to model salt crystallization during the concentration of seawater and brines. Original Russian Text ? M.V. Charykova, N.A. Charykov, 2007, published in Geokhimiya, 2007, No. 10, pp. 1129–1138.     

腐殖酸与铅锌相互作用的实验地球化学

腐殖酸是沉积有机质的成分。实验证明，腐殖酸对铅锌离子具有强烈的富集能力。通过替代反应初步确定了腐殖酸与Ｐｂ，Ｚｎ之间几种结合方式及各种结合方式占数据和比例；证实富非酸和胡敏酸与Ｐｂ＾２＋，Ｚｎ＾２＋之间形成了两大类络合物：一类其稳定常数小于ＥＤＴＡ－Ｐｂ（Ｚｎ）络合物；另一类稳定常数大于ＥＤＴＡ－Ｐｂ（Ｚｎ）络合物。     

溶出珊瑚砂中Ca~(2+)、Mg~(2+)的动力学实验研究及其影响因素

通过改变固液比、摇床转速、珊瑚砂粒径、温度、溶液pH值及溶液含盐量等参数,对珊瑚砂在水溶液中溶出Ca~(2+)、Mg~(2+)进行了实验,以探讨溶出过程中的动力学规律和影响因素。实验结果表明,珊瑚砂中Ca~(2+)、Mg~(2+)溶出量随反应时间逐渐增大;摇床转速越快、固液比越大、温度越高、溶液pH值越低,Ca~(2+)、Mg~(2+)溶出量越大;当珊瑚砂粒径为2.36~4.75 mm、溶液含盐量为100 mg/L时,Ca~(2+)、Mg~(2+)溶出量最大。统计分析表明,摇床转速、温度及溶液p H值均对珊瑚砂溶出有显著影响,但溶液p H值影响最大。珊瑚砂在水中的溶出过程符合收缩核内扩散模型,表明控制整个溶出过程反应速率的决定因素是内扩散速率;在15~40℃时,珊瑚砂在纯水中溶出Ca~(2+)、Mg~(2+)的活化能分别为78.07和74.91 k J/mol。