热红外光谱的石榴子石亚类识别方法

高光谱技术快速、无损、精确探测矿物,能够清楚的反映矿物化学成分的改变。石榴子石在热红外波段具有诊断性的三峰式特征。反射峰波长与化学成分关系密切,所以可以依据石榴子石在热红外波段的光谱特征开展其亚类分类研究。钙铬榴石和锰铝榴石反射峰位置易于与其他亚类区分,而铁铝榴石和镁铝榴石、钙铁榴石和钙铝榴石的反射峰位置有较大重叠区域,无法直接判别,因此亟需一种基于热红外光谱的快速、准确识别石榴子石亚类的分类方法。基于热红外光谱库中85个不同类型的石榴子石样本数据获取其3个反射峰位置及波长差值信息,利用非线性BP神经网络、聚类分析以及多元线性判别分析3种方法开展石榴子石亚类识别实验,并运用精确率、召回率和F1值进行分类精度评价。结果显示：BP神经网络算法分类的精确率、召回率和F1值均能达到100%,铁铝榴石和镁铝榴石、钙铁榴石和钙铝榴石得到很好地区分;聚类分析和多元线性判别分析分类的精确率、召回率和F1值分别为86.1%、80%和79.2%,84.2%、80%和79.5%,这两种方法对反射峰重叠的铁铝榴石和镁铝榴石、钙铁榴石和钙铝榴石分类效果不好,因此BP神经网络更适合石榴子石亚类识别。本研究利用BP神经网络强大的非线性自动映射能力,找到了石榴子石热红外谱段反射峰位置与亚类类型之间复杂的映射关系,证明了BP神经网络方法与热红外光谱特征结合使用的可行性与优越性,为石榴子石亚类识别提供了快速有效的技术支撑,同时为其他矿物的快速有效识别提供了良好的技术启示。     

江西朱溪钨矿床矽卡岩矿物热红外光谱学特征研究

朱溪钨矿床白钨矿化与矽卡岩化密切相关,白钨矿多与石榴子石、透辉石等矽卡岩矿物一起产出。该研究对朱溪典型矽卡岩矿物如石榴子石、透辉石、符山石、硅灰石、阳起石等进行显微红外光谱测量和电子探针分析,探究朱溪矽卡岩矿物的热红外光谱特征及其对成矿的指示意义,并建立朱溪地区的矽卡岩矿物热红外光谱库。结果表明,朱溪钨矿床石榴子石主要为钙铝—钙铁榴石系列,在800和920 cm^-1附近存在一大一小两个吸收峰,在880 cm^-1附近存在特征吸收谷;当石榴子石成分中钙铝榴石含量大于50%时,石榴子石特征吸收谷位于880～900 cm^-1,当钙铝榴石含量小于50%时,石榴子石吸收谷位于865～875 cm^-1。随着Al₂O₃含量增加,其特征吸收谷向高波数方向移动,钙铝榴石偏向高波数,钙铁榴石偏向低波数;辉石主要为透辉石—钙铁辉石系列,在850～950 cm^-1波数范围内存在诊断式、呈阶梯状降低的吸收峰,且在1 050 cm^-1处存在吸...     

钙铝榴石-钙铁榴石的拉曼光谱特征

通过对钙铝榴石 -钙铁榴石的拉曼光谱研究发现 ,从钙铝榴石到钙铁榴石 ,随着矿物结构中铁的含量的增加 ,他们的拉曼光发生规律性的变化 ,即所有的峰向低波数方向发生漂移 ;同时 ,由于铁含量的不同使得石榴石晶体结构中O -Si-O与O -Y -O之间的键角发生了一定的变化 ,在其拉曼光谱谱图上表现为铁的含量越高 ,[SiO4 ]四面体和Y -O八面体的两个弯曲振动峰分裂得越明显。     

石榴石金属离子含量与拉曼位移的定量关系研究

本文通过研究RRUFF数据库中12件石榴石样品的拉曼光谱,发现随着金属离子相对含量的变化,特征峰的拉曼位移有规律地偏移,并据此建立了镁铝榴石-铁铝榴石系列中样品的二价阳离子铁镁含量比率与硅氧四面体旋转振动和Si-O伸缩振动拉曼位移的线性关系模型,相关系数分别为0.979和0.986,并用交叉验证法检验了线性模型的可靠性。本文提出的利用拉曼位移进行相对定量分析的方法,可以为拉曼光谱的定量分析提供新的研究思路。     

高压下石榴子石结构和弹性的第一性原理研究

石榴子石是上地幔和地幔转换带的重要成分,掌握其高温高压下的物性演化特征对了解地幔物质组成、结构以及动力学过程具有重要意义。为此,利用第一性原理计算了0～16 GPa压力下铝系列和钙系列常见的6种榴石(镁铝榴石、铁铝榴石、锰铝榴石、钙铬榴石、钙铝榴石和钙铁榴石)的晶体结构和弹性性质。结果表明:铝系列榴石的晶胞体积小于钙系列榴石;除镁铝榴石外,铝系列榴石的密度高于钙系列榴石。在石榴子石压缩过程中,多面体体积变化率由大到小依次为[XO_8]十二面体、[YO_6]八面体、[SiO_4]四面体,且变化率之比接近3∶2∶1,表明石榴子石的压缩机制主要受其结构中的十二面体控制。键角方差的变化表明:高压可以使钙系列榴石的四面体和八面体变得更加规则;而铝系列榴石则与其不同,高压下铝系列榴石的四面体变得更加不规则。研究发现:石榴子石的体弹模量随着铁铝榴石含量的增加而增大,随着钙铬榴石和钙铝榴石含量的增加而减小;而剪切模量则随着钙铝榴石含量的增加而增大,随着铁铝榴石和钙铬榴石含量的增加而减小。除镁铝榴石外,铝系列榴石的波速整体小于钙系列榴石。通过计算结果发现,石榴子石及其固溶体的波速在410 km附近与地球典型波速模型有交点,证明了石榴子石是地幔中的重要组分,且不同组成的石榴子石及固溶体的存在可能对地球地幔的波速结构产生重要影响。     

石榴子石热红外波谱特征研究

近年来短波红外高光谱技术已成功应用于含水含羟基蚀变矿物及矿床学研究,但是对于不含水不含羟基矿物探测效果不好,而热红外高光谱技术可以弥补这一技术缺陷,对于含Si_nO_k,SO₄,CO₃和PO₄等原子基团的矿物具有良好的应用前景。石榴子石是一种重要的含Si_nO_k 基团的岛状结构硅酸盐矿物,根据成分可分为钙铝榴石、钙铁榴石、镁铝榴石、铁铝榴石及锰铝榴石等不同端元,石榴子石成分对成矿温压环境及成矿中心预测具有重要的研究意义。目前针对石榴子石热红外波谱特征研究非常欠缺。故采集不同成分、不同颜色石榴子石样品16件,创新性地运用美国Agilent4300热红外波谱仪开展热红外波谱特征研究,同时运用美国Niton手持式XRF分析仪开展石榴子石同一测量位置的SiO₂,MgO,Al₂O₃,K₂O,CaO和Fe₂O₃等主量元素含量测试,并分析波谱吸收位置与主量元素含量之间的关系。结果表明石榴子石在热红外波段10~13 μm具有左高右低的双峰式诊断性波谱特征,在11.5 μm附近呈现一个主吸收谷,在12 μm附近有一个次级吸收谷,且主吸收谷及次级吸收谷波长位置与石榴子石Al₂O₃和Fe₂O₃含量具有良好的相关性,相关系数大于0.9,即波谱吸收谷的波长位置与Al₂O₃含量具有线性负相关关系,与Fe₂O₃含量具有线性正相关关系。据此研究结果,可以快速开展石榴子石矿物成分的野外鉴定,还可以快速开展矽卡岩矿床野外蚀变分带研究,进而指导找矿勘查。揭示了不同成分石榴子石矿物的热红外波谱特征,对其他架状硅酸盐、岛状硅酸盐、单链状硅酸盐、碳酸盐、硫酸盐矿物的热红外波谱特征研究具有重要的指导意义。     

泥质岩体系高温高压变质过程中温度对石榴子石Fe-Mg分异的影响（英文）

在700~780℃、2.1~2.9GPa温压范围内,对天然泥质岩体系进行了高温高压实验,对体系中生成的石榴子石的Fe-Mg组成受温度的影响进行了研究。实验产物中石榴子石主要以MgO和FeO为主要组成。石榴子石中镁铝榴石和铁铝榴石含量高于88%(质量分数),钙铝榴石和锰铝榴石含量低于12%。石榴子石中FeO和MgO含量与温度呈现明显线性关系,但与压力没有呈现线性关系。研究结果确定了具有复杂化学组成的天然泥质岩体系中石榴子石Fe-Mg组成特征随温度的变化趋势,为确定泥质岩原岩组成的榴辉岩相岩石的变质温度提供了实验研究结果。     

河南固始侯古堆一号墓出土东周玉器的科技分析

古代玉器不仅是装饰品,其中还蕴藏着丰富的文化内涵。为探究春秋时期河南地区出土玉器在矿物属性、制作工艺、器物功能等之间存在的关系,选取了河南固始侯古堆一号墓（M1）出土的10件玉器,应用X射线荧光光谱（XRF）、共焦显微激光拉曼光谱（LRS）、超景深光学显微系统等光学无损分析技术,结合扫描电子显微镜（SEM）和硅胶覆膜技术对其进行了综合性分析。首先通过光谱信息获知样品的化学成分和物相结构,对样品进行了基本的矿物学表征,明确其矿物种类;再利用超景深光学显微镜对样品进行观察,利用硅胶覆膜技术复刻出样品中典型的钻孔痕、切割痕和阴刻痕,并进行二次观察和测量,综合判断出其加工工艺,并统计了刻痕深度、切口角度、浅浮雕高度等相关数据。结果表明：此玉器的矿物种类包括透闪石和云母两种,透闪石质的样品多为礼器,云母质的样品为葬玉。从阴刻工艺、钻孔工艺、切割及打磨工艺和其他特殊工艺这四方面对加工工艺进行了分析,阴刻加工工具分为手持硬质工具和砣具两种,此批样品中以砣具为主;总结了两种不同加工工具雕刻产生的阴线在表面痕迹、切口角度和刻痕深度中的规律性变化;钻孔方式均为双面对钻,钻孔工具均为实心钻具,部分样品钻孔时添加了解玉砂;多数样品经过了打磨抛光,对其中一件未完全加工完成的样品开片痕迹进行了分析,判断所用开片工具为硬质片状工具。另外对其他特殊加工工艺进行探讨,讨论了两种浅浮雕工艺的差异,以及实心钻定位技术在掏膛工艺中的应用。上述结果说明古代玉器制作工艺的选择受玉料矿物属性和玉器器型功能的影响,并结合已有研究结果,探讨了春秋末年中原地区治玉过程中玉料的来源、墓主生活年代及片切割工具的变革等问题。     

拉曼光谱在鸡血石鉴定中的应用

利用激光显微拉曼光谱仪,对市场上俗称"鸡血石"的6块产地不同的样品进行测试分析。测试得到6块样品的特征拉曼光谱,可为无损鉴定提供一定参考。临安市昌化镇玉岩山的3块鸡血石样品的"血"为同一种矿物,均为辰砂(Hg S);"地"包括地开石、高岭石、明矾石或石英等不同的矿物成分。临安市潜川镇紫溪村的鸡血石样品"血"为赤铁矿(α-Fe2O3),"地"为纯度较高的地开石。桂林鸡血石样品"血"为赤铁矿,而"地"是硬度较高的石英。贵州鸡血石样品的"血"是辰砂,"地"是黑色、灰色的碳酸盐矿物。各样品测得的X射线粉晶衍射数据结果与激光显微拉曼光谱数据一致。     

黑龙江穆棱地区宝石级石榴石的宝石学及谱学特征

对黑龙江穆棱新生代玄武岩产出的宝石级石榴石进行了宝石学常规测试、电子探针测试、拉曼光谱、红外光谱和紫外-可见光谱测试,以获得该区石榴石的宝石学特征和谱学特征。化学成分分析表明,该区石榴石为镁铝榴石,含有Fe,Ca,Mn,Cr,Ti等杂质元素。其平均晶体结构化学式为 (Mn_0.022Ca_0.455, Fe2+_0.720, Mg_1.793)_∑=2.990(Ti_0.003Cr_0.009Fe3+_0.062Al_1.951)_∑=2.025(SiO₄)₃。拉曼光谱分析表明该区石榴石存在混合相,由石榴石桥氧振动引起的拉曼位移峰反映出该特征。镁铝榴石桥氧弯曲振动拉曼位移峰位于560 cm-1(A₁g模)和641 cm-1(E_g+F₂g模),钙铝榴石和铁铝榴石桥氧弯曲振动E_g+F₂g模形成的拉曼位移峰分别位于507和486 cm-1。官能团区红外光谱显示该区镁铝榴石中不存在分子水,但少数镁铝榴石中存在少量的结构水,它们在3 585,3 566和3 544 cm-1处形成阶梯状的弱小吸收峰。该区镁铝榴石多为褐红色,其颜色由杂质离子Cr3+,Fe3+,Mn2+产生。紫外-可见吸收光谱显示,Fe3+的电子跃迁致570,521和502 nm吸收峰,Mn2+的电子跃迁致460和430 nm吸收峰,Cr3+电子跃迁致690和367 nm吸收峰。     

A pigment (CuS) identified by micro‐Raman spectroscopy on a Chinese funerary lacquer ware of West Han Dynasty

A blue pigment was identified by micro‐Raman spectroscopy, X‐ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) and X‐ray diffraction (XRD). The test sample, a funerary lacquer tray, belongs to West Han Dynasty (206 BC–AD 8) of China and was decorated with faint blue patterns. The result from Raman spectroscopy showed that the faint blue is covellite (CuS) due to the presence of a characteristic peak at 474.5 cm⁻¹, which further was confirmed by XRF, SEM–EDX and XRD. This research indicated that CuS had been used as a blue pigment to decorate lacquer wares from the West Han Dynasty in China. Copyright © 2009 John Wiley & Sons, Ltd.     

显微拉曼光谱在宝石鉴定中的应用

探讨了用显微共焦拉曼光谱仪鉴定宝石的可行性、可靠性。结果表明,根据对宝石本体的拉曼测量很容易识别真假宝石。而用显微共焦系统对微小包裹的测量可提供宝石是天然或人造的信息,甚至可追踪天然宝石的产地。我们还注意到,与拉曼谱同时记录到的光荧光谱也是有关样品的珍贵信息,有时也可据此判明宝石是天然的还是人工合成的     

Investigation of Ancient Chinese Potash Glass by Laser Ablation Inductively Coupled Plasma Atomic Emission Spectroscopy

In the present study, laser ablation inductively coupled plasma atomic emission spectroscopy (LA-ICP-AES) was successfully used to classify 26 ancient potash glass beads. These samples, mainly dated from the Han Dynasty to the Jin Dynasty, were from several provinces of both China and Vietnam. Quantitative analyses were done with both weathered and polished samples in order to consider the effects of surface weathering. Based on the characteristics of major, minor, and trace elements, we divided the samples into three subgroups (the percentage for each subgroup was 50%, 42%, and 8%, respectively) and also determined their main colorants. The results obtained provide new clues to trace the possible producing centers of ancient potash glasses in Asia. This study also reveals a complex network related to the trade of ancient potash glasses.     

湖北襄樊出土有色玻璃串饰的检测分析

运用X射线衍射(XRD)和X射线荧光光谱(XRF)等手段,对湖北襄樊一处时代在东汉末年至魏晋初年之间贵族墓出土的不同颜色玻璃珠串饰进行了物相和成分分析.结果表明,这些玻璃珠属于低铅的PbO-SiO2系统配方,各种助熔剂的含量都很低,且矿物原料比较纯,杂质含量低;古代玻璃中常见的铜、铁等致色元素含量很低,而铋的氧化物含量...     

Application of a portable XRF spectrometer for classification of potash glass beads unearthed from tombs of Han Dynasty in Guangxi,China

Thirty‐seven glass beads excavated from the Han Dynasty tombs in Hepu county, Guangxi, China, were analyzed using a portable X‐ray fluorescence (PXRF) spectrometer. Reference sample Corning glass D is used to check precision and accuracy of the equipment for major and minor components. The results of inductively coupled plasma atomic emission spectroscopy and PXRF are compared to evaluate the quality of equipment for trace elements. Combined with the contents of Al₂O₃ and CaO, a new criterion of subgroup division for potash glass based on the levels of trace elements (Rb and Sr) is proposed. The correlations of Rb and K, Rb and Al, and Sr and Ca are discussed. It is thought that saltpeter was the main flux used to produce potash glasses of different groups. The positive correlation between Rb and Al, and Rb and K indicates that potassium aluminosilicate minerals may be used as raw minerals for potash glasses of group II. The results indicate that the levels of Rb and Sr can be very helpful in subgroup definition and provide useful clues to the raw materials used for glassmaking and provenance study of the potash glass found in Guangxi, China. Copyright © 2013 John Wiley & Sons, Ltd.     

拉曼光谱法鉴定文物及艺术品中染料的研究进展

中国是丝绸之路的发源地,染色历史源远流长。文物及艺术品中的有机染料蕴含着制作年代、原料来源、染色工艺及保存状况等丰富的信息,但因染料成分复杂、含量低、易于降解,其鉴定一直是文物分析领域的难点。拉曼光谱作为一种指纹光谱在文物及艺术品中染料分析方面具有独特的优势。系统阐述了显微拉曼光谱法(MRS/μ-Raman)、近红外傅里叶变换拉曼光谱法(NIR-FT-Raman)、表面增强拉曼光谱法(SERS)、共振拉曼光谱(RRS)法的原理、特点、局限性以及在染料鉴定中的研究进展和发展方向; 分类归纳总结出了黄栀子、姜黄等染料的拉曼光谱特性; 对比分析了紫茜素在采用不同波长激光器激发下的荧光现象; 介绍了以自制的灰绿色银胶颗粒为基底,联合薄层色谱(TLC) 分离技术及SERS鉴定茜草中的色素,表明银溶胶微粒产生的表面增强效应可显著降低拉曼光谱荧光背底。指出拉曼光谱作为一种快速、便捷的结构定性测试手段在文物和艺术品染料分析中应用前景广阔,提出多种拉曼光谱技术相结合、拉曼光谱技术与分离技术相结合以及拉曼光谱技术与远距离传导技术相结合是拉曼光谱技术的发展趋势。     

LA-ICP-AES分析丝绸之路且末出土玻璃器成分特点

位于丝绸之路南道上的新疆且末古国扎滚鲁克墓地M133墓和M49墓分别出土了一批珍贵的玻璃料珠和一件玻璃杯,时代为东汉-南北朝时期(公元1～6世纪)。利用激光刻蚀电感耦合等离子体发射光谱(LA-ICP-AES)对这批样品进行化学成分分析,并讨论了这一方法的优势与准确性。分析数据显示,这批样品具有典型的西方钠钙玻璃的成分特点。根据现代西方古代玻璃研究体系中助熔剂的不同,这批玻璃又划分为泡碱玻璃和植物灰玻璃两类,并对玻璃成分的相似性与差异进行探讨。该研究以玻璃为载体反映了且末古国与西方的贸易与文化交流的历史,而且为玻璃的产地来源与制作工艺研究提供了重要的参考。     

A Raman spectroscopic study of the Mapungubwe oblates: glass trade beads excavated at an Iron Age archaeological site in South Africa

Oblate seed beads (2–4 mm) excavated on Mapungubwe hill, an Iron Age site in South Africa, were analysed with Raman microscopy and supportive techniques to determine the glass technology and pigments used to produce the beads. The Raman spectra and XRF analysis of the beads classify the glass as a typical soda/lime/potash glass similar to Islamic glass from the 8th century (Ommayad), but with higher levels of aluminium, iron and magnesium. The turquoise, bright green, bright yellow and orange colours were obtained by utilizing a combination of cassiterite (SnO₂) and lead tin yellow type II (PbSn_1−xSi_xO₃). Doping with cobalt and manganese produced dark blue and plum‐coloured beads. The Fe‐S chromophore was detected through its resonance‐enhanced spectrum in the black beads. Corrosion of the black beads was investigated and an organic phase detected on the beads, which might have influenced the corrosion process. This detailed profile of the glass technology used to produce the Mapungubwe oblates might eventually help to determine their provenance. Copyright © 2007 John Wiley & Sons, Ltd.     

Micro‐Raman investigations on inclusions of unusual habit in a commercial tanzanite gemstone

The vibrational properties of submillimetre size inclusions of unusual habit in a commercial tanzanite gemstone were investigated by confocal Raman microspectroscopy with the aim of probing both their chemical composition and crystal structure. Highly contrasted Raman spectra were recorded in confocal conditions from several inclusions incorporated at different depths, ranging between a few microns to some tens of microns beneath the gemstone surface. The observed spectral features were identified as specific markers of hematite (α‐Fe₂O₃). Their unambiguous assignment has been inferred by comparing our experimental findings with the literature data recorded either in single crystals of hematite or in other iron oxides and oxyhydroxides. Our results rule out the presence of any pseudomorphic variety of hematite in the investigated gemstone, while confocal micro‐Raman spectroscopy definitively proved itself as a very reliable, relatively costless and noninvasive tool for unambiguous identification of subsurface regions of gemstones. Copyright © 2011 John Wiley & Sons, Ltd.     

Wide area illumination Raman scheme for simple and nondestructive discrimination of seawater cultured pearls

Raman spectroscopy, along with discriminant partial least squares (PLS), was successfully used to discriminate among three different groups of cultured pearls (fresh water, Akoya and South seawater). The discrimination between Akoya and South seawater pearls using XRF (X‐ray fluorescence), one of the most frequently adopted analytical methods in pearl analysis, has been especially difficult owing to their similar mineral compositions. The selective Raman features helped in effectively discriminating between these two pearl groups. The difference in the intensities of the CaCO₃ bands of Akoya and South seawater pearls provided a valuable clue. Along with the selective Raman feature, a reproducible Raman spectral collection achieved using a wide area illumination (WAI) scheme played an important role in the determination of the pearl groups, although the pearls were hard‐surfaced, round, solid samples of different sizes and surface shapes. Unwanted spectral variation originating from sensitivity to sample placement relative to the focal plane and from unsuccessful sample representation due to the probing of a localized area, factors that could possibly deteriorate Raman reproducibility, were substantially lessened using the WAI scheme. ATR (attenuated total reflection) IR spectroscopy requiring direct contact with the pearl could be inadequate for discrimination or classification where large numbers of repeating and reproducible measurements are required. Copyright © 2009 John Wiley & Sons, Ltd.