湖北随州曾侯乙墓出土玉器材质分析与产源初探

曾侯乙墓位于湖北省随州市郊,是二十世纪重大考古发现之一,其中出土玉石器数量达五百余件,且种类齐全、工艺精湛。利用现代测试仪器对这批玉石器进行全面而科学的鉴定,对于东周时期曾国用玉水平的研究具有重要的学术意义。为了探知曾侯乙墓出土玉器的玉料类型及透闪石玉料可能来源地,以其中的319件玉器为研究对象,采用宝石学与光谱学的研究思路和方法对这些样品进行无损测试。通过十倍放大镜及天平等常规宝石学检测仪器对样品的表面特征、受沁程度及种类做出初步判断,利用傅里叶变换红外光谱仪（FTIR）和X射线荧光光谱仪（XRF）快速、无损的分析出土玉器样品的矿物相及化学成分。研究结果表明,常规仪器测试结合红外光谱及X射线荧光光谱可以很好的区分出土玉器的材质,在曾侯乙墓出土的319件玉器中,有264件透闪石质玉器,43件大理岩石璧、8件云母质玉器、1件石英岩、1件萤石以及2件水晶环。XRF测试结果显示,透闪石炙玉占全部检测样品的82.8%,其主要化学成分为MgO约占20.03%～27.00%（平均值为24.46%）, SiO₂约56.31%～61.17%（平均值为58.99%）, CaO约14.25%～19.91%（平均值为15.42%）, Fe_TO约0.19%～2.06%（平均值为0.551%）,计算可知m（Mg）/m（Mg+Fe）的值在0.91~0.99之间,其测试结果范围与标准透闪石含量很接近,该批样品中未检测出阳起石质的软玉。其中,大部分优质透闪石质玉器均出土自主墓室,反映出当时人们的用玉水平及用玉习惯。根据已有研究结果,结合化学成分分析及部分具有特征风化皮层及戈壁料特征的样品,推测曾侯乙墓部分出土玉器的玉料来源于甘肃古玉矿。该结论为进一步研究曾国用玉制度和战国时期玉石之路提供了更多的研究资料。     

In situ chemical analysis of modern organic tattooing inks and pigments by micro‐Raman spectroscopy

The chemical composition of tattooing pigments has varied greatly over time according to available technologies and materials. Beginning with naturally derived plant and animal extracts, to coloured inorganic oxides and salts, through to the modern industrial organic pigments favoured in today's tattooing studios. The demand for tattooing is steadily growing as it gains cultural popularity and acceptance in today's society, but ironically, increasing numbers of individuals are seeking laser removal of their tattoos for a variety of reasons. Organic pigments are favoured for tattooing because of their high tinting strength, light fastness, enzymatic resistance, dispersion and relatively inexpensive production costs. Adverse reactions have been reported for some organic inks, as well as potential complications, during laser removal procedures stemming from the unintentional creation of toxic by‐products. Currently, regulatory bodies such as the US Food and Drug Administration have not approved any coloured inks to be injected into the skin, and tattoo ink manufacturers often do not disclose the ingredients in their products to maintain proprietary knowledge of their creations. A methodology was established using micro‐Raman spectroscopy on an animal model to correctly identify the constituents of a selection of modern, organic tattoo inks in situ or post procedure, within the skin. This may serve as a preliminary tool prior to engaging in Q‐switched laser removals to assess the risks of producing potentially hazardous compounds. Likewise, the pigments responsible for causing adverse reactions in some patients may be quickly identified to hasten any corresponding treatment. Copyright © 2008 John Wiley & Sons, Ltd.     

An analysis of bivalve larval shell pigments using micro‐Raman spectroscopy

Micro‐Raman spectroscopy has been used on adult bivalve shells to investigate organic and inorganic shell components but has not yet been applied to bivalve larvae. It is known that the organic matrix of larval shells contains pigments, but less is known about the presence or source of these molecules in larvae. We investigated Raman spectra of seven species of bivalve larvae to assess the types of pigments present in shells of each species and how the ratio of inorganic : organic material changes in a dorso‐ventral direction. In laboratory experiments, we reared larvae of three clam species in waters containing different organic signatures to determine if larvae incorporated compounds from source waters into their shells. We found differences in spectra and pigments between most species but found less intraspecific differences. A neural network classifier for Raman spectra classified five out of seven species with greater than 85% accuracy. There were slight differences between the amount and type of pigment present along the shell, with the prodissoconch I and shell margin areas being the most variable. Raman spectra of 1‐day‐old larvae were found to be differentiable when larvae were reared in waters with different organic signatures. With micro‐Raman spectroscopy, it may be possible to identify some unknown species in the wild and trace their natal origins, which could enhance identification accuracy of bivalve larvae and ultimately aid management and restoration efforts. Copyright © 2014 John Wiley & Sons, Ltd.     

In situ confocal micro‐Raman spectroscopic investigation of rearrangement kinetics and phase evolution of UHMWPE during annealing

Ultrahigh molecular weight polyethylene was investigated using in situ confocal micro‐Raman spectroscopy during annealing at 110.0 °C. Based on the Raman spectra, crystalline, amorphous, and all‐trans noncrystalline fractions were recognized to evaluate rearrangement kinetics during isothermal annealing at 110.0 °C and phase evolution during cooling from 110.0 to 30.0 °C. For the crystalline fraction, a substantial increase from 0.600 ± 0.001 to 0.639 ± 0.008 was observed during the first 24.2 min of annealing; a very gradual increase from 0.639 ± 0.001 to 0.679 ± 0.001 occurred during the following 114.6 min. For the amorphous phase fraction, conversely, a sharp decrease from 0.240 ± 0.000 to 0.213 ± 0.004 was exhibited during the first 24.2 min of annealing, and then, a flat decrease happened from 0.213 ± 0.004 to 0.192 ± 0.001 as time expanded to 138.8 min. For the all‐tans noncrystalline fraction, a gradual decrease was shown from 0.160 ± 0.000 at 0.0 min to 0.128 ± 0.001 at 138.8 min. The rearrangement rate constant K was obtained to be 0.632 by an Avrami equation. During cooling from 110.0 to 30.0 °C, there were two phase evolution regions: region 1 from 110.0 to 90.0 °C and region 2 from 90.0 to 30.0 °C. The crystal lamella thickened faster in region 1 than in region 2. The amorphous layer continually decreased in content in the combined region of 1 and 2. The all‐trans noncrystalline phase obviously decreased in region 1 and then almost maintained a constant level in region 2. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman scattering features of lead pyroantimonate compounds: implication for the non‐invasive identification of yellow pigments on ancient ceramics. Part II. In situ characterisation of Renaissance plates by portable micro‐Raman and XRF studies

The effectiveness of Raman spectroscopy (using a bench‐top system on standard pigments) for the characterisation of modified lead antimonate yellows was demonstrated in the already published Part I. The knowledge gained is employed here for the study of yellow glazes on genuine Renaissance plates with the aim of identifying non‐invasively lead pyroantimonate compounds by portable micro‐Raman equipment. The investigation was carried out directly on site, at the Victoria and Albert Museum (London, UK) and at the Museo Statale d'Arte Medievale di Arezzo (Arezzo, Italy), combining Raman and X‐ray fluorescence analyses. In addition to the spectral features of both unmodified Naples yellow and Sn‐ and Zn‐modified lead antimonate compounds, the Raman patterns related to partially modified pyrochlore structures were observed. For this reason, the possible Sn‐induced modification of Naples yellow by cassiterite (SnO₂), present within the glaze as opacifier was explored on lead antimonate yellow glaze mock‐ups fired at different temperatures. Copyright © 2010 John Wiley & Sons, Ltd.     

Correction for the effect of soil moisture on in situ XRF analysis using low‐energy background

X‐ray fluorescence (XRF) analyses are affected by many matrix and geometrical factors that, generally, are possible to handle in laboratory conditions. However, when in situ analyses are considered, constraints in the measurement conditions make more difficult to handle some factors, such as moisture, affecting the measurement accuracy. Efforts have been made to correct some of the effects by inserting some steps in the sample preparation process. The problem is that each step added in this process, aiming a better precision and accuracy, makes the in situ measurement harder and longer to accomplish, influencing negatively the intrinsic advantages of the in situ measurement. In this work, we propose a method to correct the effect of soil moisture on in situ XRF analysis using low‐energy background. The method demands a simple calibration, after which a long drying procedure is not necessary before measuring the samples. Copyright © 2012 John Wiley & Sons, Ltd.     

In situ monitoring of solid‐state transition of p‐aminobenzoic acid polymorphs using Raman spectroscopy

The purpose of this study is to investigate the mechanism of solid‐state polymorphic transition of p‐aminobenzoic acid (PABA) using in situ Raman spectroscopy measurement. The polymorphic transition experiments were conducted on a micro quartz vessel mounted on a microscope, hot and cold stage, under isothermal conditions. The temperature was precisely controlled by a standalone temperature controller equipped with liquid nitrogen cooling system. The Raman spectroscopy probe was positioned on the surface of the solid sample in the micro vessel. The polymorphic transition progression was in situ monitored and recorded by Raman spectroscopy. Based on the polymorphic transition rate resulted from the quantitative analysis of Raman spectra, the mechanism of solid‐state polymorphic transition of PABA was examined by various empirical kinetic models. An Arrhenius analysis was also performed to calculate activation energies from 134.7 kJ mol⁻¹ to 137.7 kJ mol⁻¹ for the transition. The results demonstrated that in situ Raman spectroscopy is a valuable and accurate technique to probe polymorphic transition process. Copyright © 2009 John Wiley & Sons, Ltd.     

Improvements of the low‐energy performance of a micro‐focus x‐ray source for XRF analysis with the SEM

X‐ray Fluorescence (XRF) with a scanning electron microscope (SEM) is a valuable completion of the analytical capabilities of SEMs. Small and compact micro‐focus x‐ray sources are mounted to the microscope chamber, and the x‐ray spectra are monitored with conventional EDS systems. Up to now the x‐ray tubes used for the micro‐focus x‐ray sources are equipped with beryllium windows about 100 µm thick. The poly‐capillary x‐ray lenses have their transmission maximum at photon energies around 10 keV. It drops down in both low‐ and high‐energy ranges. Hence, L‐radiation from an Mo or Rh target will be strongly attenuated, and the excitation of fluorescence in the soft x‐ray range becomes very ineffective. A new micro‐focus x‐ray source was developed. It is characterised by a lower self‐absorption in the tube target, thin beryllium windows and an x‐ray optics having a large distance between its foci and the maximum of transmission at about 5 keV. Thus K line fluorescence of light elements becomes effectively excited by the L‐radiation from Mo or Rh tube targets. The detection limit for sodium oxide in glass was found to be below 1 mass%. Copyright © 2009 John Wiley & Sons, Ltd.     

Nondestructive analysis of jade artifacts from the Cemetery of the Ying State in Henan Province,China using confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy

Confocal Raman microspectroscopy and portable X‐ray fluorescence spectroscopy were used nondestructively to characterise 18 intact jade artifacts from the Cemetery of the Ying State in Pingdingshan, Henan Province, China. These jade artifacts date from the early to the middle of the Western Zhou Period (the mid‐11^th to the mid‐9^th century BC). Thirteen jade artifacts made of tremolite and two jade artifacts made of actinolite were discriminated from each other by their hydroxyl stretching modes, and a malachite pendant, a muscovite dagger‐axe, and a crystal pendant were also identified. Black graphite was analysed in three jade artifacts composed of tremolite, and the mineralization temperatures were estimated and compared. A red powder was found on the surface of all of the jade artifacts, and this was found to be cinnabar (HgS), which is thought to have been added to the tomb environments during burial ceremonies. The chemical compositions and the possible provenances of the jade artifacts are briefly discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Subsurface analysis of painted sculptures and plasters using micrometre‐scale spatially offset Raman spectroscopy (micro‐SORS)

A recently developed variant of spatially offset Raman spectroscopy (SORS) for the non‐invasive analysis of thin painted layers, micro‐SORS, has been applied, for the first time, to real objects of Cultural Heritage – namely painted sculptures and plasters. Thin layers of paint originating from multiple restoration processes often applied over many centuries have been analysed non‐destructively using micro‐SORS to depths inaccessible to, or unresolvable into separate layers, by conventional confocal Raman microscopy. The concept has been demonstrated on several artistic artefacts of historical significance originating from Italy and dating from the medieval to the 18th century. The technique extends the depth applicability of Raman spectroscopy and with its inherently high chemical specificity that expands the portfolio of existing non‐destructive analytical tools in Cultural Heritage permitting to avoid cross‐sectional analysis often necessitated with this type of samples with conventional Raman microscopy. Currently, the method is non‐invasive only for artworks that can be placed under Raman microscope although there is a prospect for its use in a mobile system with largely removed restrictions on sample dimensions. © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd.     

Identification of pigments from the Shrine of Kaiping Diaolou by micro‐Raman spectroscopy

Shrines (or altars) are constructed in China for worshiping ancestors, Bodhisattva, and God of Wealth. In this work, pigments from the shrine of Kaiping Diaolou tower were analyzed by micro‐Raman spectroscopy, in conjunction with other analytical methods including scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy (EDX) and X‐ray fluorescence (XRF). Paintings of the shrine were composed of 2–3 pigment layers and the total thickness was determined as about 200–300 µm by optical microscopy and SEM, indicating the fine painting skills applied in the construction of the shrine. The green pigments on the surface layer of the green fragment were identified as a mixture of lead phthalocyanine (PbPc) and cornwallite (Cu₅(AsO₄)₂(OH)₄) by XRF and micro‐Raman spectroscopy with two different excitation wavelengths (488 and 785 nm). Underneath the green layer, red and yellow ochre were found. The pigments on the surface layer of red and blue fragments were identified as hematite (Fe₂O₃) and lazurite or synthetic ultramarine [(Na₈(Al₆Si₆O₂₄)S₃)], respectively. Finally, the pigments under the two surface layers were identified by EDX and micro‐Raman spectroscopy as chromium oxide (Cr₂O₃), gypsum (CaSO₄·2H₂O) and calcite (CaCO₃). Copyright © 2011 John Wiley & Sons, Ltd.     

Characterisation of inorganic pigments in ancient glass beads by means of Raman microspectroscopy,microprobe analysis and X‐ray diffractometry

Ancient coloured glass beads from Sri Lanka and Oman were analysed by Raman microspectroscopy for non‐destructive identification of inorganic pigments in the glass. Calcium phosphate (Ca₃(PO₄)₂), cassiterite (SnO₂), cuprite (Cu₂O) and a Pb(Sn,Si)O₃‐type lead tin oxide were found to be used as colouring agents. Moreover, a distinction between lead‐based and alkali‐based glass matrices could be made. Electron microprobe analysis and X‐ray diffractometry were performed to show the capability of Raman microspectroscopy in comparison to these methods for answering archaeometric questions. Copyright © 2006 John Wiley & Sons, Ltd.     

Use of micro‐Raman spectrometry coupled with scanning electron microscopy to determine the chemical form of uranium compounds in micrometer‐size particles

In the frame of nuclear safeguards, knowledge of the chemical form (stoichiometry) of the uranium compounds present in the micrometric particulate material sampled by wiping surfaces in an inspected nuclear facility may point out the industrial process implemented in the installation. Micro‐Raman spectroscopy (MRS) coupled with scanning electron microscopy (SEM) has been used for the first time to analyze micrometer‐size particles of various uranium oxides [UO₂, U₃O₈, UO₃, and UO₄ · 4(H₂O)] deposited on carbon disks. Uranium particles are detected by means of SEM, and Raman analysis is then directly carried out inside the SEM measurement chamber without moving the carbon disk from SEM to MRS. When particles are deposited on appropriate carbon disks (sticky carbon tapes), despite a loss of signal‐to‐noise ratio of about an order of magnitude with regard to the stand‐alone MRS, all uranium oxides are successfully identified in particles by in‐SEM Raman analysis, obtaining similar characteristic bands as the ones obtained with the stand‐alone MRS. Moreover, with the SEM–MRS coupling, particles as small as 1 µm can be analyzed, whereas, without the SEM–MRS coupling, only particles larger than ~5 µm are efficiently analyzed, after localization inside the SEM, transfer of the sample holder into the MRS, and relocation of the particles inside the MRS. Copyright © 2013 John Wiley & Sons, Ltd.     

On‐site Raman and XRF analysis of Japanese/Chinese bronze/brass patina – the search for specific Raman signatures

The assignment of Asian bronzes and brasses is difficult because the copies of ancient pieces have been made a long time ago in different countries. A selection of 30 Japanese and/or Chinese bronzes/brasses are studied on‐site in the storage and exhibition rooms of the Cernuschi Museum, in Paris, using portable Raman and X‐ray fluorescence spectrometers. Attempts are made to identify specific Raman signatures of the patina to detect similarity in a nondestructive procedure. X‐ray fluorescence measurements allow an identification of two brass artefacts and different types of bronze, including lead‐rich and mixed lead–tin–zinc‐rich compositions. The following phases are identified: CuO, Cu₂O, Cu₂S, tin oxides, ZnO, Cu₃(OH)₄SO₄, Cu₄(OH)₆SO₄, 3PbOPbSO₄ H₂O, PbSO₄/PbO, Pb(AsO₄)₃Cl, HgO/HgS. Relics of the mould, retained as concretions at the artefact surface are also identified: TiO₂, SiO₂, and different soda(−lime) glasses. Patina with very similar colour and habit may have different Raman signatures. This study offers tools to classify the artefacts in a noninvasive way. Copyright © 2011 John Wiley & Sons, Ltd.     

In situ monitoring of styrene polymerization using Raman spectroscopy. Multi‐scale approach of homogeneous and heterogeneous polymerization processes

Free radical polymerization of styrene was monitored in situ by combining Raman spectroscopy to other experimental techniques (gravimetry and rheology). Three different processes were investigated: bulk, emulsion and miniemulsion polymerization. A complete analysis of the evolution of Raman spectrum during the course of reaction showed that a lot of information about molecular dynamics could be extracted and related to chemical phenomena. In addition, we report for the first time the coupling of Raman spectroscopy to a rheometer in order to monitor styrene bulk polymerization both at the scale of chemical bonds and at the scale of macroscopic phenomena (viscosity variation). Copyright © 2013 John Wiley & Sons, Ltd.     

Nanomechanics of single silkworm and spider fibres: a Raman and micro‐mechanical in situ study of the conformation change with stress

The combination of micro‐Raman spectroscopy and an advanced universal fibre tester (UFT) made it possible to probe at the nanoscale (through monitoring the modification of chemical bonds) the change in conformation (α‐helix, β‐sheet, etc.), macromolecular fibroin chain orientation and coupling during the application of stress, quantitatively. Different single fibres of silkworms (Bombyx mori, Gonometa rufobrunea, Gonometa postica) and a spider (Nephila madagascariensis) were tested in a dry environment and compared with the behaviour of keratin fibre. As observed previously for single keratin fibres, a direct relationship is observed between nano‐ and micro‐mechanical tensile behaviour. The phase transition plateau, well defined for some pristine B. mori fibres, disappears in degummed fibres, which indicates a structural modification and increasing disorder with chemical treatments. Stress‐controlled micro‐Raman analysis shows that a few modes involving CH₂ and/or amide groups of β‐conformation chains undergo a wavenumber softening during the elastic behaviour (∼0–3%), although most of the modes are not affected. A different behaviour is observed for modes associated with ‘ordered’ and ‘disordered’ β‐sheets and helical chains. Larger softening is observed for lattice modes with increasing stress/strain, as expected. Structural changes and relationships with mechanical behaviour are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of pottery from Republic of Macedonia. III. A study of comparative mineralogical detection efficiency using micro‐Raman mapping and X‐ray diffraction

Point‐to‐point micro‐Raman and X‐ray diffraction (XRD) techniques were employed for characterization of minerals present in the pottery body of 27 glazed Byzantine and Ottoman pottery shreds, excavated at two different archaeological sites in the Republic of Macedonia: in Skopje (Skopsko Kale) and in Prilep (Markovi Kuli and Sv. Atanas Church). The Raman spectra of 18 Byzantine samples (dating from 12th−14th century) and nine Ottoman samples (dating from 17th−19th century) revealed 26 different minerals. XRD measurements were further performed on the same powder samples to validate the mineralogical assessment obtained by point‐to‐point micro‐Raman spectroscopy. Although only 13 different mineral phases were obtained by the XRD, the results obtained from the Raman and XRD spectra for the most abundant minerals in the investigated pottery bodies match quite well. However, the identification of the less abundant minerals in the clay matrixes from the XRD data was very difficult, if at all possible. The results emphasize the specifics of the applied techniques and their limits. Additionally, wavelength dispersive X‐ray fluorescence spectroscopy was used for the elemental analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

In vitro confocal Raman micro‐spectroscopic approach to screen the mode of action of Chinese herbs on oxidative damaged human sperm

This paper presented a rapid and reliable approach to screen the antioxidant active ingredients on human sperm from Chinese herbs by means of confocal Raman micro‐spectroscopy. For the first time with the proposed approach, we performed the studies of rationalizing the active ingredients from several Chinese herbs. In this study, the FeSO₄/H₂O₂‐induced oxidative damaged sperm after co‐culture with compounds or active fraction extracted from some Chinese herbs commonly used in the treatment of male infertility were observed by using confocal Raman micro‐spectroscopy. The Raman spectral fingerprints of the damaged sperm were very different from the normal ones, and the further statistical analysis were successfully used to support the results, these differences were shorten after co‐culture with the compounds or active fraction we had chosen, and the results were almost consistent with the traditional clinical trial results and other published data, all which showed that these compounds or active fraction were the chemogenomics of the Chinese herbs on anti‐oxidative damaged sperm. In brief, we demonstrated that by means of confocal Raman micro‐spectroscopy, in vitro is a rapid, reliable and large‐scale approach to screen the antioxidant active ingredients on human sperm from Chinese herbs. Copyright © 2016 John Wiley & Sons, Ltd.     

In vivo study on the protection of indole‐3‐carbinol (I3C) against the mouse acute alcoholic liver injury by micro‐Raman spectroscopy

Micro‐Raman spectroscopy (MRS) was utilized for the first time to evaluate the effect of indole‐3‐carbinol (I3C) on acute alcoholic liver injury in vivo. In situ Raman analysis of tissue sections provided distinct spectra that can be used to distinguish alcoholic liver injury as well as ethanol‐induced liver fibrosis from the normal state. Sixteen mice with liver diseases including acute liver injury and chronic liver fibrosis, and eight mice with normal liver tissues, and eight remedial mice were studied employing the Raman spectroscopic technique in conjunction with biomedical assays. The biochemical changes in mouse liver tissue when liver injury/fibrosis occurs such as the loss of reduced glutathione (GSH), and the increase of collagen (α‐helix protein) were observed by MRS. The intensity ratio of two Raman peaks (I₁₄₅₀/I₆₆₆) and in combination with statistical analysis of the entire Raman spectrum was found capable of classifying liver tissues with different pathological features. Raman spectroscopy therefore is an important candidate for a nondestructive in vivo screening of the effect of drug treatment on liver disease, which potentially decreases the time‐consuming clinical trials. Copyright © 2008 John Wiley & Sons, Ltd.