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.     

Ablation Characteristic of Ilmenite using UV Nanosecond and Femtosecond Lasers: Implications for Non‐Matrix‐Matched Quantification

Ilmenite (FeTiO₃) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised ⁵⁷Fe and ⁴⁹Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm^?2 and fs‐LA‐ICP‐MS.     

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.     

阿尔金山两侧盐湖物质来源、成钾作用及其控制因素研究

塔里木盆地东部的罗布泊盐湖和柴达木盆地西部的盐湖分别位于阿尔金山两侧,均产出有大量富钾卤水,在油气藏开采中还伴随产出富钾油田水.为探讨阿尔金山两侧盐类资源富集机制及其控制因素,综合分析了罗布泊盐湖、柴达木盆地西部盐湖以及油田水的水化学和氢氧同位素地球化学特征,发现:富钾卤水的形成除依靠地表汇入水体的蒸发浓缩作用外,罗布泊晶间水、柴达木晶间水和油田水氢氧同位素均可演化至δD=-30‰,δ18 O=7.5‰左右,可能是深部流体上涌补给的结果.同时,根据87 Sr/86 Sr值并结合δ11 B、3 He/4 He同位素特征确认了盐湖成矿与深部流体有关,且指示罗布泊盐湖更具深源特征.深部流体对于两侧盆地成盐富钾有关键性作用,罗布泊盐湖可能接受深部流体补给,柴达木盆地西部富钾盐湖卤水多数可接受油田水的补给,而少部分可能接受深部流体补给.     

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。     

新疆奇台县黄羊山石墨矿床特征、物质来源及成因

黄羊山石墨矿床位于新疆东准噶尔造山带南部的卡拉麦里地区东南段,是近年来新发现的国内外首个产于花岗岩体中的超大型石墨矿床。成矿地质条件、矿床地质特征研究表明,该矿床与黄羊山碱性花岗岩体具有密切的时空及成因联系,矿石具独特的球状构造,球体中石墨与长英质矿物及磁黄铁矿、黄铜矿等金属硫化物密切共生。为确定黄羊山石墨矿床的成因和成矿物质来源,本文开展了球状矿石中的石墨拉曼光谱分析和C同位素测试,对与石墨密切共生的金属硫化物开展S-Pb同位素分析。结果表明,黄羊山矿床球状矿石不同部位石墨的拉曼谱峰相似,显示具有很高的结晶程度,估算结晶温度为750～800℃;7件石墨样品的δ~(13)C值在-19.27‰～-19.90‰,分布非常集中,介于岩浆碳值和有机碳值之间,表明具有两者的混合来源。4件磁黄铁矿样品的δ~(34)S值集中在-2.3‰～-2.9‰之间,接近原始地幔值;在Pb同位素构造环境判别图解上,Pb同位素比值(~(206)Pb/~(204) Pb=18.114～19.040,~(207)Pb/~(204) Pb=15.448 ～ 15.543,~(208) Pb/~(204)Pb=38.253～38.915)显示较好的线性关系,延伸方向与地幔演化曲线的延伸方向基本一致;S-Pb同位素测试结果表明,与石墨共生金属硫化物具有幔源特征。综合黄羊山矿床成矿地质条件、成矿特征、石墨及共生硫化物的物质来源等研究结果,本文初步认为,黄羊山石墨矿床形成于碱性花岗岩的岩浆作用阶段,矿石中的金属硫化物来自岩浆混合作用中的幔源基性端元,碳质由于岩浆同化混染作用达到饱和,在硫化物的催化下沉积形成石墨。     

短波红外光谱、X射线荧光光谱、黄铁矿热电性分析在胶东新城金矿田深部找矿中的应用

胶东半岛是我国最重要的金矿集区之一,其矿床是典型受北东向断裂构造(焦家断裂带、三山岛断裂带和招平断裂带),以及次生断裂构造(如望儿山断裂和灵北断裂等)控制的矿床类型。前人在该区域做了大量研究,但主要集中在地表和浅层成矿段,对于深部成矿规律与预测的研究相对较少。新城金矿田是胶东半岛的特大型金矿之一,由新城矿床、曲家矿床和招贤矿床三部分组成。由于受到焦家断裂带控制,在招贤矿区中的科研深钻达到2 500 m以下,为我们研究深部成矿规律提供了良好的样品。本文通过该地区蚀变矿物的短波红外光谱特征(short-wave infrared spectroscopy,SWIR),并结合X 射线荧光光谱(X-ray fluorescence spectrometry,XRF)法和黄铁矿热电性法,选取该地的不同成矿阶段的蚀变岩石和典型载金矿物黄铁矿,并在三维环境中,定量化分析了主要的蚀变矿物——白云母族的短波红外光谱的特征值,揭示其找矿规律与指示意义,进一步提取矿床中蚀变矿物的找矿标志。研究结果表明:(1)在靠近焦家主断裂构造蚀变岩型矿体的位置,伊利石结晶度(≥1.2)和绢云母Al—OH吸收位置(≥2 205 nm)偏高,而在远离焦家主断裂构造蚀变岩型矿体的位置伊利石结晶度和绢云母Al—OH吸收位置偏低,分别为0.2~1.2和2 198~2 205 nm。(2)X 射线荧光光谱结果提取了该地区20种元素含量,通过对元素的主成分分析和聚类分析, Al—OH吸收峰位置偏移与Al、K、Si含量变化有一定相关性。(3)黄铁矿热电性导型在近焦家主断裂构造蚀变岩主要为P型,远离主断裂的主要为N型。在新城矿区的Ⅰ号和Ⅴ号矿体的顶部到底部整体呈现N-P→P→P-N→N→N-P→P-N和P-N→N-P的规律;在招贤矿区中绝大部分是P型。剥蚀度整体处于在25%~50%,因此在新城矿区约-800 m以下和招贤矿区约-1 500 m以下,仍有较好的深部找矿前景。整体上P型黄铁矿成矿温度主要为180~250 ℃,N型成矿温度主要区间值在380~460 ℃;利用温度场进行三维插值建模,其与三维矿体品位模型空间展布趋势一致。本文综合研究方法为深部矿产资源评价提供新的研究思路,将光谱数据、地化数据等多维度信息集成整合,同时使用三维模型可视化功能,对于矿产模型定量化构建具有重要参考价值。     

地幔平衡部分熔融和岩浆分离结晶成因岩浆岩的判别

本文在讨论Ⅰ型（地幔平衡部分熔融成因）和Ⅱ型（岩浆分离结晶成因）岩浆岩元素丰度关系公式的基础上，建立了Ⅰ型和Ⅱ型岩浆岩系成因判别公式及判别法则。