The effect of thermal treatment on the 57Fe Mössbauer spectrum of beryl

Mössbauer spectra (MS) of blue, green and yellow beryl (ideally Be₃Al₂Si₆O₁₈) containing approximately 1% of iron were obtained at 295 and 500 K. Room temperature (RT) spectra of both blue and green samples showed 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. There is no clear evidence for the presence of a ferric component. The MS of the yellow sample at RT consists of an intense central absorption with parameters typical for Fe³⁺ (ΔE _Q~0.4 mm/s, δ~0.29 mm/s), plus an apparently symmetrical Fe²⁺ doublet. This sample acquires a light-blue shade upon heating in air at about 620 K. Thermal treatments at high temperatures caused no significant changes in the MS, but the green and yellow beryl acquire a blue colour. All these results are interpreted in relation to the existence of channel water and the distribution of iron among the available crystallographic sites.     

单柱离子色谱测定二氧化锰产品中无机阴离子杂质

采用了单柱离子色谱法测ＭｎＯ２产品中无机离子杂质；提出了消除干扰的可行途径，将Ｌａ（ＯＨ）３加入后能同时消除进样峰的干扰和溶剂峰的出现。选用１．７５ｍｍｏｌ／Ｌ邻苯二甲酸１．７５ｍｍｏｌ／Ｌ三羟甲基氨基甲烷为混合淋洗剂测定Ｆ＾－，Ｃｌ＾－，ＮＯ３＾和ＳＯ＾２－４，其标准加入回收率为９５％－１０５％；ＲＳＤ（ｎ＝７）为２．４７％－８．０８％。     

细度和染色杂质对方解石白度的影响

方解石经超细粉碎后通过水力分级分成若干粒级；考察细度对方解石白度的影响；运用高梯度强磁选考察弱磁性染色杂质对方解石白度的影响。     

Characterization of beryl (aquamarine variety) from pegmatites of Minas Gerais,Brazil

Eight samples of the beryl variety aquamarine were selected from four pegmatites in the Governador Valadares and Araçuaí regions in northeastern Minas Gerais State, Brazil. These samples were fully characterized by chemical analysis, infrared and UV-visible spectroscopy, thermal analyses, and high-temperature X-ray diffraction (from room temperature up to 800 °C). Several physical and chemical properties of beryl were found to depend on the amount of water and ions residing in the structural channels. The thermal expansion coefficients from room temperature to about 800 °C are temperature-independent, with αa ? ?3.2 × 10^?6 ° C^?1 and αc ? ?8.7 × 10^?6 ° C^?1. The contraction of both a and c unit-cell parameters with increasing temperature and the shift of the infrared band centered at about 1200 cm^?1 were tentatively ascribed to interactions between channel water and the silicate rings.The color of beryl seems to be dictated by the relative proportions of Fe³⁺ in the octahedralsites and of fe²⁺ in the channels. Thus, deep-blue samples have little Fe³⁺, whereas greener samples have more Fe³⁺ or less channel Fe²⁺.     

绿柱石中隧道水的红外光谱

应用富时叶变换红外谱仪研究了三个启三绿柱石样（包括原样与热处理）。将３４３５ｃｍ＾－１宽吸收带归属于与铁离子成键的水。谱图表明隧道水的大量脱去是在８００℃以上的温度开始的,对于富碱样品,更可能是在１０００℃以后开始。隧道中碱金属离子的阻塞作用是造成绿柱石隧道水难以失去的重要原因．     

戊基磷酸二戊酯萃取色层分离-电感耦合等离子体质谱法测定铀产品中9种杂质元素

铀产品中杂质元素的含量测定在核法证学溯源分析或燃料元件厂质量检验中具有重要应用价值,保证测量的准确度主要在于控制流程空白、提高杂质元素的回收率。本文建立了戊基磷酸二戊酯(UTEVA)树脂快速分离铀与杂质元素、电感耦合等离子体质谱法(ICP-MS)测定杂质元素含量的系统流程。结果表明,UTEVA树脂对铀的吸附能力强,铀样品取样量为16.43 mg时,全流程对铀的去污因子大于3×105,9种杂质元素(锰钼镍铜铬铝钛钒镉)的回收率为95.1%~105.1%,国家标准物质GBW04205中杂质元素的分析结果与参考值在不确定度(k=2)范围内一致。本工作建立的分离流程对铀的去污效果好,特别适用于样品量少的情况下铀中杂质元素的分析,为核法证分析最终的归因溯源或燃料质量检验提供了技术支持。     

The positions of H+, Li+ and Na+ impurities in beryl

Electron Paramagnetic Resonance (EPR) measurements show that Li⁺ impurities are located at two different positions in beryl, one in the crystal lattice and the other in the crystal channel. The position of the Li⁺ impurity in the lattice is generally assumed to be at the site of a missing Be²⁺ ion. It is shown that this is not the case, but that the Li⁺ ion is located in a tetrahedron formed by the oxygens of one side of the Be tetrahedron and the nearest oxygen in the channel ring. This Li site has the coordinates (0.423, 0.344, 0.167) and can only be occupied when the neighbouring Be site is empty. There are four such sites around every Be tetrahedron at the distance of 1.46 Å from the Be site. The distance from the Li site to the oxygens of the Li tetrahedron is 1.84 Å. This compares favourably with the much smaller distance of 1.65 Å in the Be tetrahedron. Protons in beryl are trapped at or near these Li sites. Na⁺ is known to be located at the 2b position at the center of the silicate rings, where it is stabilized by one water molecule located at each of the two surrounding 2a sites. This is also the position of Li⁺ in the beryl channel. It is found that the presence of Na⁺ in the ring of six oxygens reduces the radius of this ring. The Na⁺ impurity has also been supposed to be located at position 2a alone and at 2b stabilized by only one water molecule. It is now proposed that Na⁺ and H₂O are located together in the Al–Be plane when only one water molecule is associated with Na⁺. The water oxygen is located at or near 2a and Na is closer to the Be site in tetrahedral beryl and closer to the Al site in octahedral beryl. It is proposed that the water protons are also located in the Al–Be plane, which would mean that there exists a third type of water in beryl. The origin of protons and OH^? ions in beryl is discussed and it is suggested that the plugs in the beryl channels are CO ₃ ^2? ions. Diffusion of OH^? ions and natural radiation may have led to the creation of NO₃ and the blue colour of Maxixe beryl.     

The orientation and vibrational states of H2O in synthetic alkali-free beryl

 The polarized single-crystal Raman spectra of synthetic H₂O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H₂O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν₁) at 3607 cm⁻¹ and an IR-active asymmetric stretch (ν₃) at 3700 cm⁻¹ at room temperature. At low temperatures this ν₃ mode is observed in the Raman. Weak ν₁ and ν₃ modes of a second type of H₂O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H₂O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν₁ mode of H₂O are similar to, but not exactly the same as, those of a free H₂O molecule. The Raman measurements indicate that the H₂O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H₂O could be observed as overtones with the internal H₂O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm⁻¹. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm⁻¹ in energy (i.e., T_z). The energies of the librational modes are about 210 cm⁻¹ for R_x and 190 cm⁻¹ for R_y. Received: 8 April 1999 / Accepted: 5 April 2000     

Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na⁺ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm⁻¹. On the basis of experimental and theoretical studies, we assigned these pairs of bands to the ν₁ and ν₂ modes of doubly coordinated type II H₂O and to singly coordinated type II H₂O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750°C, suggested the dehydration of type I and type II water, respectively.     

Vibrational states of H<Subscript>2</Subscript>O in beryl: physical aspects

Single-crystal polarized Raman spectra (3,000–4,000 cm⁻¹ at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be₂Al₃Si₆O₁₈·xH₂O, to determine the behavior of H₂O molecules of both Type I and Type II in the cavities. At low temperature, the H₂O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H₂O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm⁻¹. Water Type II is characterized by a free rotation with respect to the C ₂ molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.