State of Molecules and Ions in the Structural Channels of Synthetic Beryl with an Ammonium Impurity

The contents of the structural channels of beryl, grown hydrothermally from an ammonium-containing solution, were investigated by IR and EPR spectroscopy. Using IR spectroscopy we found that water molecules, ammonium ions, and a small number of HCl molecules enter the structural channels of beryl in the course of mineral growth. In these beryls, the ammonium ions play the role of alkali cations. The ammonium ions are as rigidly fixed in the lattice as are water molecules; they are eliminated by calcination at high temperatures close to the decomposition temperature. On exposure to radiation at 77 K, the paramagnetic NH ₃ ⁺ and H⁰ radicals are stabilized in the structural channels of beryl. In addition to the known H⁰ radical, other states of atomic hydrogen, interacting with medium protons, are observed as well. For one of the additional radicals, H_b, we suggest the model of atomic hydrogen stabilized at the center of a silicon-oxygen ring with two water molecules in adjacent cavities.     

The Crystal Growth and Characteristics of Etched Figures on c { 0001 } Face of Tabular Beryl Crystal from Pinwu, China

板状绿柱石产于花岗岩云英岩化边部或晶洞壁的白云母-钠长石-绿柱石-水晶的矿物组合中,钠长石呈自形晶,绿柱石的洁净度与透明度相对较差。晶体测量表明,晶体的单形晶面发育依次为c{0001}→s{11 2-1}→p{10 1-1}→m{10 1-0}→v{21 3-1}、n{45 9-4}、a{11 2-0}。微分干涉显微镜（DIC）及扫描电镜（SEM）研究表明：各单形晶面上生长纹（微形貌）反映面网结构的对称性,c{0001}单形晶面上的六边形溶蚀坑（50～170μm）是由平行晶体C轴的各单形晶面生长层从晶体中心向外叠堆组成,层生长机理制约晶体生长全过程,平行双面（c）的生长层较薄（5～8μm）且较稳定,六方双锥（s）生长层较厚且圆滑,六方柱（m）生长层由晶体中心往外其厚度由厚逐渐变薄（12～20μm）,台间隔由窄变宽。晶体溶蚀是从面网密度最大的c{0001}开始,溶蚀面积依平行双面（c）、六方双锥（s）单形晶面由大变小,六方柱（a）、复六方双锥（v、n）单形晶面因面网密度小而未受到溶蚀。据矿物共生组合、流体包裹体均一法测量与拉曼光谱（LRS）分析表明板状绿柱石是在中–高温（303℃）、过饱和度较大、成矿介质的钠长石化发育且热动力环境相对稳定的条件下形成,气液包裹体主要由H2O、CO2及微量CH4、N2组成,CO2及微量CH4、N2可能与碳酸盐围岩有关。     

水热法合成红色绿柱石的光谱特征研究及应用

采用常规宝石学测试方法,配合紫外可见光谱技术（UV-Vis）及傅里叶变换红外光谱技术（FTIR）,对美国犹他州天然红色绿柱石及俄罗斯水热法合成红色绿柱石的宝石学特征、紫外可见吸收光谱特征、中红外光谱（MIR）特征及近红外光谱（NIR）特征进行了综合对比研究。结果表明,常规宝石学测试方法很难将上述两类宝石区别开来;紫外可见光吸收光谱对鉴定天然和合成红色绿柱石的能力很有限;同时这两种宝石的中红外吸收光谱（MIR）没有明显的特征差异,其吸收位置和吸收强度基本一致。但在2 000~9 000 cm-1红外波段,天然红色绿柱石与水热法合成红色绿柱石的吸收频率差异明显,因此具有独特的鉴别特征。进一步研究表明,天然红色绿柱石在3 500~4 000 cm-1之间没有强吸收峰,几乎不含结构水,但在3 300~3 600 cm-1之间有非常弱的吸收带（峰值为3 418 cm-1）,因此有可能有其他形式的水。水热法合成红色绿柱石样品的近红外光谱特征表明,其在3 500~4 000 cm-1之间及5 000~5 800 cm-1之间均显示有强烈的水的振动吸收：其在5 000~5 800 cm-1有弱的Ⅰ型水吸收峰和强Ⅱ型水吸收峰,可以归属为分子水的弯曲和伸缩的合频振动;其在7 000~7 500 cm-1之间显示的弱Ⅰ型水的吸收峰和强的Ⅱ型水的吸收峰可以归属为水的倍频振动。因此,水热法合成红色绿柱石中的结构水归属Ⅰ型水与Ⅱ型水的混合型,其在3 500~4 000及5 000~5 800 cm-1范围水的近红外吸收光谱特征可作为区别天然和水热法合成红色绿柱石的依据。通过紫外可见光光谱、中红外光谱以及近红外光谱等光谱分析手段可以初步判断红色绿柱石中是否含水、水的赋存状态、以及不同类型水的相对强度和频率,为区分天然与水热法合成红色绿柱石提供诊断性证据。     

Solid-Phase Spectrophotometric Determination of Beryllium at ng mL−1

Abstract

A microdetermination method at ng mL^?1 level for beryllium by solid-phase spectrophotometry was been developed. Chrome Azurol S was used as chromogenic reagent to form a blue complex which was easily and strongly sorbed and concentrated on a dextran-type anion-exchange resin. The resin-phase absorbances at 594- and 800 nm were measured directly. Beryllium could be determined over the 1.5 - 15.0 ng mL^?1 range with a RSD of 2.7 % by using 100 mL of sample solution. The detection limit was 0.21 ng mL^?1. By using only 10 mL of sample solution, the calibration graph was linear over the concentration range 10–85 ng mL^?1, the RSD being 1.2 %. The method was applied to the determination of beryllium in underground and mining waste water samples and in beryl mineral.     

Analysis of Possible Ways for Removing Fluorine from the Complex Beryllium-containing Raw Material at UMP JSC

The justification of the need to remove fluorine from the complex beryllium-containing concentrates during their treatment before the stage of beryllium hydroxide precipitation is given. The analysis of possible ways of fluorine elimination from beryllium raw materials has been carried out.     

The Unusual Mössbauer Spectrum of Beryl

The Mössbauer spectra of several aquamarine samples have been obtained in the temperature range of 4.2–500 K. A common feature observed in all room-temperature spectra is the presence of an asymmetric Fe²⁺ doublet (ΔE _Q～2.7 mm/s, δ～1.1 mm/s), with a very broad low-velocity peak. This asymmetry is not caused by preferred orientation since the spectrum collected under the magic angle did not show any difference in the line intensities, nor is it caused by the superposition of a Fe³⁺ doublet. At 4.2 K the spectrum of a deep-blue beryl could be well fitted with three symmetrical doublets, with the major Fe²⁺ doublet accounting for 87% of the total spectral area. At 14 K the symmetry remains, but at 30 K the low-velocity peak is again broad. Surprisingly, the spectrum at 500 K also shows a broad, but symmetrical doublet, with a clear splitting of the lines indicating the presence of at least two Fe²⁺ components. The room-temperature spectrum obtained after the 500 K run shows the same features as before the heating. A meaningful fit for the room-temperature spectrum, as well as an explanation for the temperature dependence of the Mössbauer spectra, are discussed.     

绿柱石的原位高压X射线研究

 采用同步辐射光源和金刚石对顶砧（DAC）技术,对绿柱石进行了室温下的原位高压能散X射线衍射（EDXD）研究,实验的最高压力为19.2 GPa。在实验压力范围内,未观察到绿柱石发生相变,轴压缩率c大于a;在小于9.3 GPa的压力范围内,其体积压缩率符合二阶Murnaghan状态方程,而压力在9.3～19.2 GPa范围内时,其体积压缩率有所增加,且体积-压力关系近乎线性变化。     

水热法合成蓝绿色绿柱石的宝石学及光谱学特征

针对新出现在市场上的一种水热法合成蓝绿色绿柱石,运用LA-ICP-MS、红外光谱、拉曼光谱、紫外-可见光谱进行系统研究,旨在获得其宝石学及谱学特征,探讨颜色成因,为检测机构鉴定该合成宝石提供参考数据.结果表明,样品折射率为1.570～1.576,与天然绿柱石相近,内部含特征的水波纹状生长纹理,可作为主要鉴定特征之一.L...     

绿柱石晶体的水热法生长及特征研究

采用温差水热法,以分析纯的Al(OH)3和BeO以及无色纯净的石英为原材料,球形和//s(1121)的片状无色绿柱石为籽晶,在复杂的盐酸混合溶液中生长了无色透明的绿柱石晶体.利用双圈反射测角仪、电子探针、X射线衍射仪和红外光谱仪等仪器,对合成绿柱石晶体的形态、成分及晶体结构进行了详细的研究.结果表明,合成的绿柱石晶体为六方短柱状,主要发育平行双面c{0001}、六方柱m{1010}、a{1120}和六方双锥p{1011}四种单形.合成的绿柱石晶体的成分中(Na2O+ K2O)的质量分数约为0.59;,且c0/a0值为0.9988,可归属于"正常"绿柱石向"四面体"绿柱石的过渡范畴.在中性或弱碱性环境体系中,通过调整绿柱石中各成分的百分含量,有望在更低的温度、压力条件下合成出高质量的板柱状绿柱石晶体.