同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

粉色水晶内针状包裹体的成分与分布特征研究

粉色水晶内部的针状包裹体常被认为是三组呈三方对称的金红石或蓝线石,至今未有定论。本文选取含有针状包裹体的4颗星光粉晶,利用宝石学显微镜、激光拉曼光谱仪及紫外可见分光光度计对样品进行观察与测试,以确定包裹体的分布特征及矿物种类。无损拉曼测试发现包裹体的特征振动峰949 cm-1、999 cm-1与蓝线石标准峰相匹配,可确定针状包裹体为蓝线石或与其极为相近的矿物。放大检查发现,包裹体直径约0.5μm,长度可达毫米级,近定向分布,整体上呈汇聚状,在某些位置可粗略分为三组,同组针状包裹体近似平行分布。造成六射星光的三组蓝线石立体相交,未观察到明显的三方对称关系,与水晶的结晶习性无直接关系,故认为蓝线石为先成包裹体,在水晶的生长过程中被捕获。紫外可见分光光谱仅显示粉色蓝线石的特征吸收,表明大量的粉色蓝线石包裹体对粉色水晶的粉色有一定贡献。     

Application of Geochemistry and VNIR Spectroscopy in Mapping Heavy Metal Pollution of Stream Sediments in the Takab Mining Area, NW of Iran

This study considered the possibility of using visible and near infrared (VNIR) spectral absorption feature parameters (SAFPs) in predicting the concentration and mapping the distribution of heavy metals in sediments of the Takab area. In total, 60 sediment samples were collected along main streams draining from the mining districts and tailing sites, in order to measure the concentration of As, Co, V, Cu, Cr, Ni, Hg, Ti, Pb and Zn and the reflectance spectra (350–2500 nm). The quantitative relationship between SAFPs (Depth500nm, R610/500nm, R1344/778nm, Area500nm, Depth2200nm, Area2200nm, Asym2200nm) and geochemical data were assessed using stepwise multiple linear regression (SMLR) and enter multiple linear regression (EMLR) methods. The results showed a strong negative correlation between Ni and Cr with Area2200nm, a significant positive correlation between As and Asym2200nm, Ni and Co with Depth2200nm, as well as Co, V and total values with Depth500nm. The EMLR method eventuated in a significant prediction result for Ni, Cr, Co and As concentrations based on spectral parameters, whereas the prediction for Zn, V and total value was relatively weak. The spatial distribution pattern of geochemical data showed that mining activities, along with the natural weathering of base metal occurrences and rock units, has caused high concentrations of heavy metals in sediments of the Sarough River tributaries.     

Composition and origin of the volatile components released from the Pesyanoe aubrite by stepwise crushing and heating

Aubrites are achondritic meteorites (enstatite pyroxenites) that were formed in highly reduced magmatic environments on a differentiated parent body sharing a common oxygen isotope reservoir with enstatite chondrites (EC), Earth and Moon, and could be considered as a geochemical model of the early proto-Earth. Some pyroxenes of the Pesyanoe aubrite have high abundance of gaseous inclusions, captured during the crystallization of the rocks. Investigation of the inclusions by IR spectroscopy reveals presence of OH⁻ groups and C–H bonds. The former are assigned to protonated point defects in enstatite lattice and the latter to compounds occupying void walls. Molecular water and CO₂ were not observed. Volatile components released from the samples of the Pesyanoe enstatite by stepwise crushing and heating are composed of CO₂, H₂O and a non-condensable phase. Hydrogen isotopic composition of volatiles extracted in form of molecular water in Px-separates varies in the range δD = −61 – −84‰ with mean value of δD = −73 ± 16‰ VSMOW and is within the ranges of ECs and Earth’s mantle. The total abundance of H₂ in the pyroxene of Pesyanoe were estimated as at least 0.047 ppm that is too low in comparison with that of enstatite chondrites (≥30 ppm H₂) and could indicate nearly complete degassing of the Pesyanoe primitive precursor material during the Pesyanoe parent body accretion or a mantle degassing in igneous differentiation process. In a last case a primitive precursor could have D/H ratio different from that of enstatite chondrites.     

微波等离子体原子发射光谱法测定偏远矿区海泡石中的主微量元素

海泡石是具有层状结构的含水富镁硅酸盐黏土矿物,其中无机元素含量是揭示其成矿物质来源、成矿流体性质和矿床成因的重要依据,通常采用电感耦合等离子体发射光谱/质谱法(ICP-OES/MS)进行测定,等离子体(ICP)的高温激发会产生成大量谱线干扰,维持ICP稳定工作需使用高纯氩气,持续供气对于偏远矿区海泡石的检测还将面对气体采购和运输不便的问题。本文基于微波等离子体原子发射光谱(MP-AES)的低温激发技术减少光谱干扰,建立了准确测定偏远矿区海泡石中主量元素Mg、Al、Ca、Fe、K、Na和微量元素Cu、Zn、Mn、Pb含量的分析方法。利用硝酸-盐酸-氢氟酸混合酸对海泡石进行微波消解,避免了样品处理过程中分析元素的损失,加快了样品处理速度,同时提高了样品溶液的稳定性。通过选择各元素光谱线的分析波长,并利用快速线性干扰校正(FLIC)技术校正光谱干扰,以Lu为内标元素校正基体效应,提高了灵敏度和准确度。各元素的检出限为0.19～14.6μg/L。海泡石国家标准物质(GBW07138)各元素测定值与认定值的相对误差在-5.0%～6.7%之间。本方法具有检出限低、线性范围宽、结果准确等优点;MP-AES采用自带的氮气发生器为等离子体提供氮气作为工作气,无需引入复杂气体,提高了分析效率,尤其适用于气体采购和运输不便的偏远矿区。     

土壤粒径的光谱响应特性研究

以实验室制备的5个不同粒径水平的土壤样本和室内高光谱数据为基础,通过对光谱数据进行重采样、数学变换等预处理并进行单因素方差分析、相关性分析和回归分析,探讨土壤粒径的高光谱特性,建立了光谱数据预测土壤粒径的校正模型。结果表明,土壤粒径对反射光谱有显著的影响,波长越长影响越大;在全波段范围内土壤粒径和光谱数据都呈负相关关系,对原始光谱数据进行微分变换能增加其与土壤粒径的相关性;以反射率一阶微分建立的回归模型为反演土壤粒径的最佳模型,其建模决定系数■、预测决定系数■、预测相对偏差RPD分别为0.666,0.653,2.043,预测均方根误差RMSE为0.175。     

Retrieving volume FeO and TiO_2 abundances of lunar regolith with CE-2 CELMS data using BPNN method

The volume FeO and TiO_2 abundances(FTAs) of lunar regolith can be more important for understanding the geological evolution of the Moon compared to the optical and gamma-ray results. In this paper, the volume FTAs are retrieved with microwave sounder(CELMS) data from the Chang'E-2 satellite using the back propagation neural network(BPNN) method. Firstly, a three-layered BPNN network with five-dimensional input is constructed by taking nonlinearity into account. Then, the brightness temperature(TB) and surface slope are set as the inputs and the volume FTAs are set as the outputs of the BPNN network.Thereafter, the BPNN network is trained with the corresponding parameters collected from Apollo, Luna,and Surveyor missions. Finally, the volume FTAs are retrieved with the trained BPNN network using the four-channel TBderived from the CELMS data and the surface slope estimated from Lunar Orbiter Laser Altimeter(LOLA) data. The rationality of the retrieved FTAs is verified by comparing with the Clementine UV-VIS results and Lunar Prospector(LP) GRS results. The retrieved volume FTAs enable us to re-evaluate the geological features of the lunar surface. Several important results are as follows. Firstly, very-low-Ti(<1.5 wt.%) basalts are the most spatially abundant, and the surfaces with TiO_2> 5 wt.% constitute less than 10% of the maria. Also, two linear relationships occur between the FeO abundance(FA) and the TiO_2 abundance before and after the threshold, 16 wt.% for FA. Secondly, a new perspective on mare volcanism is derived with the volume FTAs in several important mare basins, although this conclusion should be verified with more sources of data. Thirdly, FTAs in the lunar regolith change with depth to the uppermost surface,and the change is complex over the lunar surface. Finally, the distribution of volume FTAs hints that the highlands crust is probably homogeneous, at least in terms of the microwave thermophysical parameters.     

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。     

不同过滤条件下黄色物质的吸收光谱演化特征分析

在实验室对青岛近岸现场水样进行处理、分析,获得了原始状态下水样和被过滤（0.22μm,0.45μm）黄色物质水样的吸收光谱数据,除进一步验证了黄色物质光谱分布模式外,还测得黄色物质光吸收随滤膜孔径的变化。30个现场样品在波长380nm处吸收系数统计平均值^—Ay（380）分析表明,当使用0.45μm过滤器对水样进行处理,所获得的^—Ay（380）值要比未经过处理的现场水样所测得的^—Ay（380）值高约2.1％;而用0.22μm过滤器对现场水样进行处理,所获得的^—Ay（380）值要比未经过处理的现场样品所测得的^—Ay（380）值高约12．6％,要比用0．45μm过滤器处理的现场样品所测得的^—Ay（380）值高约10.3％,这些数据的获得为现有已获黄色物质数据的“归一化”和统一评判以及未来黄色物质测量数据的准确性判断与比较提供了参考。