A Raman investigation on the boron form occurring in salt lake brine during evaporation

Boron resources are abundant in Da Qaidam salt lake of Qaidamu Basin. It has been given great attention for the polyborate species present in brine. In this study, the Raman spectroscopy was applied to investigate the existing-form of boron in brine during evaporation. The prepared solutions of MgO·2B2O3-H2O, MgO·2B2O3-MgCl2 -H2O, and MgO·2B2O3-MgSO4-H2O was also evaporated and recorded to study the influence of boron concentration, pH, and electrolytes on the borate speciation in brine. The mononborates of B(OH)3 and B(OH)4- were found to be the only forms present in the original salt lake brine. Brine evaporation promotes the formation of polyborate anions B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- and also disappearance of the B(OH)4- ion in brine with boron concentration of more than 11 g/L in B2O3. The pentaborate ion of B5O6(OH)4- was sensitive to the solution pH and found to be appeared under the pH value of 8.0. While the hexaborate ion of B6O7(OH)62- was observed more dependent on the electrolyte of magnesium chloride due to its special properties, such as promoting boron accumulation, lowering solution pH, and also the strong af?nity for water molecules, which is beneficial to the polymerization of borate ions in brine. The interaction mechanisms among polyborate anions during evaporation had also been proposed.     

东昆仑造山带海德乌拉铀矿床成矿流体特征研究

东昆仑造山带海德乌拉铀矿床是近些年西北地区最新探明的与火山岩有关的独立铀矿床,该矿床的发现为东昆仑造山带探寻热液型铀矿床提供了指示意义。本文选择与海德乌拉铀矿成矿期相关的透明矿物（粉红色方解石、紫黑色萤石及石英）作为研究对象,系统地开展C- H- O同位素和流体包裹体研究,查明该矿床成矿流体的来源与性质,并探讨矿床成因。研究结果表明,海德乌拉铀矿床成矿期石英中主要为H2O气液两相包裹体,少见CO2- H2O两相包裹体;在粉红色方解石脉、紫黑色萤石脉中流体包裹体均含H2O气液两相包裹体,在粉红色方解石脉中偶见纯液相包裹体,均未见到纯气相及含固相包裹体。成矿期粉红色方解石、紫黑色萤石及石英中包裹体均一温度范围分别为133~187℃（均值163℃）、127~204℃（均值169℃）、183~287℃（均值219℃）,盐度范围分别为1. 40%~7. 02%NaCleq（均值3. 65%NaCleq）、0. 53%~3. 06%NaCleq（均值1. 26%NaCleq）、7. 17%~17. 26%NaCleq（均值为11. 46%NaCleq）。流体包裹体气相成分以H2O为主,另含少量CO2等。C- H- O同位素实验数据表明,流体中δ13CFluid- V- PDB、δDFluid- V- SMOW、δ18OFluid- V- SMOW值的变化范围分别为1. 59‰~1. 00‰、71‰~63‰、0. 03‰~3. 72‰,表明成矿流体并非单一来源,可能为大气降水与岩浆水混合来源。此外,沥青铀矿的沉淀主要是由于流体与围岩的相互反应所引起的物理化学条件变化加上流体沸腾/CO2去气,最终导致了沥青铀矿等成矿物质发生大规模的卸载与沉淀。     

南海IODP 349航次基底玄武岩中碳酸盐岩脉的岩石学特征*

国际大洋发现计划(International Ocean Discovery Program, IODP)349航次在南海东部次海盆和西南次海盆残留扩张脊附近的U1431和U1433站位首次钻取基底玄武岩, 通过对16块基底玄武岩内的碳酸盐岩脉薄片镜下观察以及激光拉曼光谱分析, 揭示碳酸盐矿物为方解石和文石, 为典型的洋壳低温热液蚀变次生矿物。U1431站位碳酸盐岩脉为独立的方解石脉、文石脉交替出现; 而U1433站位则存在方解石脉、文石脉和方解石-文石共生脉三种情况。此外, U1431站位在基底~42.1m处出现了平行的方解石脉和文石脉, 揭示U1431存在不同来源热液的多期活动, 即可能存在多次或多阶段不同的热液注入。U1431和U1433站位的碳酸岩脉中, 文石的矿物集合体形状基本一致, 呈块状、纤维状和放射纤维状; 而方解石存在差异, U1431的方解石以斑块状、块状、粒状和纤维状出现, 而U1433的方解石仅出现块状。U1431站位的碳酸盐岩脉的丰度明显高于U1433站位。这些均揭示U1431站位的低温热液活动强, 而U1433站位则相对弱。两个站位的热液活动不同很可能是由于区域地质环境的差异造成——U1431附近的巨大海山为其提供了热液补给, 而U1433远离热液的补给/渗漏点。     

Improvement in the calculation of anti-Stokes energy transfer and experimental justification based on Er0.01YbxY1 - 0.01 - xVO4 crystal

The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{ΔE / kT} from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er_0.01Yb_xY_{1 - 0.01 - x}VO₄ crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.     

boldmath Investigation of inter-molecular hydrogen bonding in the binary mixture (acetone + water) by concentration dependent Raman study and ab initio calculations

This paper reports that vibrational spectroscopic analysis on hydrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.     

Temporal electronic structure of non-resonant Raman excited virtual state of P-nitroaniline by 514 nm excitation via bond polarisabilities

We have studied the temporal bond polarisabilities of para-nitroaniline from the Raman intensities by the algorithm proposed by Wu et al. in 1987 (Tian B, Wu G, Liu G 1987 J. Chem. Phys. 87 7300). The bond polarisabilities provide much information concerning the electronic structure of the non-resonant Raman excited virtual state. At the initial moment by the 514.5 nm excitation, the tendency of the excited electrons (mapped out by the bond polarisabilities) is to spread to the molecular periphery, and the electronic structure of the Raman virtual state is close to the pseudo-quinonoidic state. When the final stage of relaxation is approached, the bond polarisabilities of those peripheral bonds relax faster than those closer to the molecular core, the phenyl ring. The molecule is in the benzenoidic form as demonstrated by the bond polarisabilities after relaxation.     

Field experiments of multi-channel oceanographic fluorescence lidar for oil spill and chlorophyll-a detection

A Multi-channel Oceanographic Fluorescence Lidar (MOFL), with a UV excitation at 355 nm and multiple receiving channels at typical wavelengths of fluorescence from oil spills and chlorophyll-a (Chl-a), has been developed using the Laser-induced Fluorescence (LIF) technique. The sketch of the MOFL system equipped with a compact multi-channel photomultiplier tube (MPMT) is introduced in the paper. The methods of differentiating the oil fluorescence from the background water fluorescence and evaluating the Chl-a concentration are described. Two field experiments were carried out to investigate the field performance of the system, i.e., an experiment in coastal areas for oil pollution detection and an experiment over the Yellow Sea for Chl-a monitoring. In the coastal experiment, several oil samples and other fluorescence substances were used to analyze the fluorescence spectral characteristics for oil identification, and to estimate the thickness of oil films at the water surface. The experiment shows that both the spectral shape of fluorescence induced from surface water and the intensity ratio of two channels (I ₄₉₅/I ₄₀₅) are essential to determine oil-spill occurrence. In the airborne experiment, MOFL was applied to measure relative Chl-a concentrations in the upper layer of the ocean. A comparison of relative Chl-a concentration measurements by MOFL and the Moderate Resolution Imaging Spectroradiometer (MODIS) indicates that the two datasets are in good agreement. The results show that the MOFL system is capable of monitoring oil spills and Chl-a in the upper layer of ocean water.     

深海热液区主要成分的高温高压拉曼光谱分析

模拟深海热液口环境(最高压力40 MPa,最高温度350℃),对深海热液区的主要成分CO2、CH4及其混合物的水溶液在不同压力和温度条件下的拉曼光谱进行探测和分析,结果显示:常温低压下CO2水溶液的Fermi双峰分别位于1 384.9 cm-1和1 278.3 cm-1处,CH4的水溶液拉曼峰υ1位于2 912.1 cm-1处,均比其气相的拉曼频移小;常温下CO2和CH4水溶液的拉曼特征峰随压力(≤40 MPa)的变化均不明显;在40 MPa的压力下随着温度的升高(≤350℃),CO2水溶液的Fermi双峰分别向高波数区移动了约3.4 cm-1和7.0 cm-1,而CH4水溶液的拉曼峰υ1向低波数区移动了约3.1cm-1;混合后升温过程中CO2的双峰分别向高波数区移动了约4.3 cm-1和3.8 cm-1,CH4的特征峰υ1向低波数区移动了4.5 cm-1。说明在室温到350℃范围内温度的变化对CO2和CH4水溶液拉曼频移有影响,频移量与温度线性相关,而压力在≤40 MPa范围内的改变对拉曼频移影响不明显。     

利用U—1000型激光拉曼探针测定流体包裹体气体成分的研究

本文利用U－1000型激光拉曼探针成功地测量出单个流体包裹体中H2S、CH4、CO2气体成分，并讨论了包裹体中这些气体的拉曼谱峰位移与包裹体内压的关系，分析了影响激光拉曼探针定量测定包裹体气相成分的取面积和拉曼定量因子因素。     

琥珀的拉曼光谱及荧光测量研究

本文利用激光拉曼光谱研究了琥珀的化学组成,表明拉曼光谱研究琥珀的有效方法。利用MPV-3显微光度计作荧光测量表明荧光测量是可判别琥珀的真伪及评价琥珀质量的好坏的。