不同地区恐龙化石的显微激光拉曼光谱研究

研究了7个恐龙化石样品在较高波数段的显微激光拉曼光谱,化石样品来自不同地区并且属于不同的骨骼部位。显微激光拉曼光谱表明,这7个恐龙化石的拉曼特征峰的峰位十分相似,但峰形有差别。进一步的比较分析还发现,不同源地相同骨骼部位的拉曼峰峰形比较相似,例如不同地区的脊椎头化石图谱比较相似,肢骨头化石的拉曼峰峰形也比较相似。实验结果表明,在1 000～1 800 cm-1波数段内的拉曼特征峰,主要与原骨骼所属的部位有关,与化石的源地关系不太大。785 nm的拉曼光谱不能区分恐龙化石的源地,但可以在较小的地质区域内区分化石骨骼的部位。     

Principal component analysis‐assisted energy dispersive X‐ray fluorescence spectroscopy for non‐invasive quality assurance characterization of complex matrix materials

The analytical challenges in direct quality assurance analysis of complex matrices (extreme matrix effects, spectral overlap, poor signal‐to‐noise ratio (SNR) for trace analytes, ‘dark matrix’, imprecise geometry, need for sample integrity) by energy dispersive X‐ray fluorescence (EDXRF) spectrometry necessitate development of novel techniques for material characterization. We demonstrate the utility of principal component analysis (PCA) in isotope‐excited EDXRF spectrometry of a complex matrix (in this case lubricating oil) in the context of a newly developed EDXRF and scattering (EDXRFS) technique. Lubricating oil quality may be interpreted in terms of its viscosity, anti‐wear, anti‐oxidation, and anti‐rust properties, which are detectable via B, Ca, Mg, Zn, Fe, Na additives (quality markers). Our method involves simultaneous non‐invasive acquisition of both fluorescence and scatter spectra from samples held in a propylene dish, and their modeling in a reduced multidimensional space for an interpretable overview that is analytically more useful than, and complementary to, fluorescence peak‐based quantitation of the additives; by this method, only Fe and Zn are directly detectable, but with SNR of the fluorescence peak 15–20 times poorer compared with analysis after sample digestion. Although Fe and Zn cannot distinguish the various lubricating oil brands, it can differentiate authentic from adulterated. The method was however found to be analytically useful when combined with PCA: various brands of lubricating oil were discriminated in addition to the detection of adulteration. PCA processing of the spectra showed that the most important quality assurance spectral signature information responsible for the success is contained in the scatter region (low‐Z elements). Evaluation of the performance of the method with respect to SNR (i.e. analysis time and therefore speed) showed that there was no significant difference in method performance of analysis live time in the range 100–1000 s, showing proof of concept for rapid characterization of complex matrix materials by PCA‐assisted EDXRFS. Copyright © 2012 John Wiley & Sons, Ltd.     

A rapid,non‐destructive method of detecting diagenetic alteration in fossil bone using Raman spectroscopy

Biogenic isotopes of analytical interest may be stripped from bone during burial, reducing the utility of fossil specimens for paleobiological and paleoenvironmental reconstruction. Denudation of the bone lattice coupled with the addition of exotic ions can influence the Raman spectra of fossil bone. Modern bone samples (n = 43) were used to establish an unaltered bone standard, and a suite of synthetic apatite samples were produced to simulate the addition of various ions into the bone mineral lattice. Diagenetic alteration produces distinct spectral characters, providing qualifications for major ionic substitution, ionic heterogeneity, the abundance of structural carbonate, the presence of calcium carbonate and the presence of luminescent ions. Spectral indicators (proxies) provide the means of rapidly and nondestructively evaluating the degree of alteration and thus the analytical utility of fossil bones, potentially avoiding exhaustive and destructive analysis on finite material. Copyright © 2007 John Wiley & Sons, Ltd.     

Energy‐dispersive x‐ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

The elemental composition (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Ba, Nd and Pb) of modern coloured glasses was obtained by energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry. This non‐destructive technique is frequently used in the analysis of historical glass objects. Two reference glasses were also measured to assess the overall accuracy of the EDXRF method. Reference and unknown glasses were analysed without any preparation. The coloured glass samples studied belong to the Glass Museum of Marinha Grande and were chosen from two distinct collections, which were characterized by the different concentrations of some elements (K, Ti, Cr, Mn, Fe, Ba and Pb). The determined major elements allowed the identification of two raw materials used in glass manufacture, sand and lime. Multivariate statistical analysis, namely principal component extraction, simplified the identification of some of the colouring chemical elements, associating them with the different colours of the glass objects. Copyright © 2003 John Wiley & Sons, Ltd.     

无损光谱技术在彩绘陶质文物分析中的应用进展

彩绘陶质文物拥有丰富的信息内涵,对于研究我国古代历史文化、经济商贸、科学技术发展起到极其重要的作用。但由于彩绘陶质文物的珍贵性和不可破坏性,普通分析技术难以满足其测试要求,近年来无损光谱技术被引入文物分析检测领域并逐渐得到应用。本工作从彩绘颜料分析、陶胎分析以及器物信息提取等三个方面阐述了激光拉曼显微光谱、激光诱导击穿光谱、能量色散X射线荧光光谱等无损光谱技术应用的现状、方法原理、特点及局限性,并对无损光谱技术在彩绘陶质文物分析中的应用进行了展望。     

Characterizing arsenic in preserved hair for assessing exposure potential and discriminating poisoning

Advanced analytical techniques have been used to characterize arsenic in taxidermy specimens. Arsenic was examined to aid in discriminating its use as a preservative from that incorporated by ingestion and hence indicate poisoning (in the case of historical figures). The results are relevant to museum curators, occupational and environmental exposure concerns, toxicological and anthropological investigations. Hair samples were obtained from six taxidermy specimens preserved with arsenic in the late 1800s and early 1900s to investigate the arsenic incorporation. The presence of arsenic poses a potential hazard in museum and private collections. For one sample, arsenic was confirmed to be present on the hair with time‐of‐flight secondary ion mass spectrometry and then measured with neutron activation analysis to comprise 176 µg g^?1. The hair cross section was analysed with synchrotron micro‐X‐ray fluorescence to investigate the transverse distribution of topically applied arsenic. It was found that the arsenic had significantly penetrated all hair samples. Association with melanin clusters and the medulla was observed. Lead and mercury were also identified in one sample. X‐ray absorption near‐edge spectroscopy of the As K‐edge indicated that an arsenate species predominantly existed in all samples; however, analysis was hindered by very rapid photoreduction of the arsenic. It would be difficult to discriminate arsenic consumption from topically applied arsenic based on the physical transverse distribution. Longitudinal distributions and chemical speciation may still allow differentiation.     

Mapping prehistoric ghosts in the synchrotron

The detailed chemical analysis of fossils has the potential to reveal great insight to the composition, preservation and biochemistry of ancient life. Such analyses would ideally identify, quantify, and spatially resolve the chemical composition of preserved bone and soft tissue structures, but also the embedding matrix. Mapping the chemistry of a fossil in situ can place constraints on mass transfer between the enclosing matrix and the preserved organism(s), and therefore aid in distinguishing taphonomic processes from original chemical zonation remnant within the fossils themselves. Conventional analytical methods, such as scanning electron microscopy (SEM) and pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) have serious limitations in this case, primarily, an inability to provide large (i.e., decimeter) scale chemical maps. Additionally, vacuum chamber size and the need for destructive sampling preclude analysis of large and precious fossil specimens. However, the recent development of Synchrotron Rapid Scanning X-ray Fluorescence (SRS-XRF) at the Stanford Synchrotron Radiation Lightsource (SSRL) allows the non-destructive chemical analysis and imaging of major, minor, and trace element concentrations of large paleontological and archeological specimens in rapid scanning times. Here we present elemental maps of a fossil reptile produced using the new SRS-XRF method. Our results unequivocally show that preserved biological structures are not simply impressions or carbonized remains, but possess a remnant of the original organismal biochemistry. We show that SRS-XRF is a powerful new tool for the study of paleontological and archaeological samples.     

Facile residue analysis of recent and prehistoric cook stones using handheld Raman spectrometry

We performed food residue analysis of fire‐cracked rock (FCR) from experimental and prehistoric earth ovens using a handheld Raman spectrometry. Progress in modern optical technology provides a facile means of rapid non‐destructive identification of residue artifacts from archaeological sites. For this study spectral signatures were obtained on sotol (Dasylirion spp.) experimentally baked in an earth oven as well as sotol residue on an experimentally used processing tool. Inulin was a major residue component. The portable handheld Raman spectrometer also detected traces of inulin on experimental boiling stones used to boil commercially obtained inulin. The Raman spectra of inulin and sotol may be useful as signatures of some wild plant residues in archaeology. Spectroscopic analysis of millennia‐old FCR from prehistoric archaeological sites in Fort Hood, TX revealed the presence of residues whose further identification requires improvement of current optical methods. Copyright © 2014 John Wiley & Sons, Ltd.     

EDXRF and multivariate statistical analysis of fragments from Marajoara ceramics

In this work, 102 fragments of Marajoara ceramics, belonging to the National Museum collection (Rio de Janeiro, Brazil), were analyzed using energy dispersive X‐ray fluorescence (EDXRF) and principal component analysis (PCA) in order to identify possible groups of samples that present similar behaviors or different characteristics. This information will give an important aid to a more accurate classification of these artifacts. The EDXRF measurements were carried out with a portable system developed in the Nuclear Instrumentation Laboratory consisting of an Oxford TF3005 X‐ray tube, with W anode, and an Si‐PIN XR‐100CR detector from Amptek, working at 25 kV and 100 µA, acquisition time of 600 s and a beam collimation of 2 mm. PCA applied to the X‐ray fluorescence results revealed a clear cluster separation to the samples. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of fossil bones by synchrotron radiation micro‐spectroscopic techniques and scanning electron microscopy

Earlymost Villafranchian fossil bones of an artiodactyl and a perissodactyl from the Milia excavation site in Grevena, Greece, were studied in order to evaluate diagenetic effects. Optical microscopy revealed the different bone types (fibro‐lamellar and Haversian, respectively) of the two fragments and their good preservation state. The spatial distribution of bone apatite and soil‐originating elements was studied using micro‐X‐ray fluorescence (µ‐XRF) mapping and scanning electron microscopy. The approximate value of the Ca/P ratio was 2.2, as determined from scanning electron microscopy measurements. Bacterial boring was detected close to the periosteal region and Fe bearing oxides were found to fill bone cavities, e.g. Haversian canals and osteocyte lacunae. In the perissodactyl bone considerable amounts of Mn were detected close to cracks (the Mn/Fe weight ratio takes values up to 3.5). Goethite and pyrite were detected in both samples by means of metallographic microscopy. The local Ca/P ratio determined with µ‐XRF varied significantly in metal‐poor spots indicating spatial inhomogeneities in the ionic substitutions. XRF line scans that span the bone cross sections revealed that Fe and Mn contaminate the bones from both the periosteum and medullar cavity and aggregate around local maxima. The formation of goethite, irrespective of the local Fe concentration, was verified by the Fe K‐edge X‐ray absorption fine structure (XAFS) spectra. Finally, Sr K‐edge extended XAFS (EXAFS) revealed that Sr substitutes for Ca in bone apatite without obvious preference to the Ca₁ or Ca₂ unit‐cell site occupation.     

Focusing synchrotron radiation using a polycapillary half‐focusing X‐ray lens for imaging

An imaging system based on a polycapillary half‐focusing X‐ray lens (PHFXRL) and synchrotron radiation source has been designed. The focal spot size and the gain in power density of the PHFXRL were 22 µm (FWHM) and 4648, respectively, at 14.0 keV. The spatial resolution of this new imaging system was better than 5 µm when an X‐ray charge coupled device with a pixel size of 10.9 × 10.9 µm was used. A fossil of an ancient biological specimen was imaged using this system.     

原位能量色散X射线荧光分析中岩样基体效应及其修正研究

原位能量色散X射线荧光现场分析岩样矿物成分时,岩样基体效应会对测量结果产生影响。本文以Cu元素作为待测元素,研究了17种不同岩样基体对原位能量色散X射线荧光分析Cu元素特征X射线强度的影响及其修正方法。采用蒙特卡罗方法模拟获得了Cu元素含量相同的17种不同岩样测量谱线,综合各类岩石元素构成的相似性,并依据模拟谱线Cu元素Kα射线强度与谱线参数之间的相关性,反映了原位能量色散X射线荧光分析岩样Cu元素的基体效应并不完全受岩体元素构成或岩石分类的控制,需要依据岩石样分析谱线参数的相关性进行归类讨论。针对基体影响Cu元素特征射线强度相似的15种岩样进一步研究,并对Cu元素特征X射线与谱线主要参数的主成分进行分析,发现散射本底、X光管靶材料特征X射线及其非相干散射峰强度能够很好的描述Cu元素特征X射线强度受岩样基体影响的变化,据此可以对基体效应影响相似的岩体进行Cu元素测量结果修正。采用本文方法同样也能为不同岩性岩体其他待测元素基体效应的修正提供参考。     

Handheld XRF analysis of the old Mexican feather headdress in the Weltmuseum Vienna

Within a trans‐disciplinary project between Mexico (Instituto Nacional de Antropología e Historia) and Austria (Weltmuseum Wien), the feather headdress, a unique and most renowned pre‐Columbian ‘Arte Plumaria’ artifact from the 16th Century was studied extensively. Among other investigations concerning the materiality of the headdress, noninvasive handheld X‐ray fluorescence (XRF) analysis was carried out with a handheld instrument to detect the possible presence of inorganic pesticides and pigments and to verify the composition of the metal decorations. The measurements provided rich qualitative and even quantitative information. The use of inorganic pesticides (arsenic, bromide and lead containing compounds), the composition of the original gold decoration plates and the later added brass plates were confirmed. A method was established to define the thickness of the gilding of the later added plates. There was not found evidence on the use of inorganic pigments to produce marks on the constructive parts of the headdress. Handheld XRF measurements can be extremely useful for noninvasive on site investigation of sensitive museum artifacts, but generally require the application of a thorough analytical methodology for the proper interpretation and quantification of the results. Copyright © 2014 John Wiley & Sons, Ltd.     

Inclusions and metal composition of ancient copper‐based artefacts: a diachronic view by micro‐EDXRF and SEM‐EDS

A diachronic view of the metallurgy in the Portuguese territory during the first three millennia after its appearance in the Iberian Peninsula is presented based on the current state of the art. Results of micro‐energy dispersive X‐ray fluorescence (micro‐EDXRF) analyses made on metal artefacts to determine their composition and scanning electron microscopy with energy dispersive analysis (SEM‐EDS) analyses to study microstructural features as inclusions are shown to illustrate trends and specificities of each chronological period. Generally, in early periods, namely during the Copper Age and first stages of the Bronze Age, unalloyed copper and arsenical copper were at use, and only by the Late Bronze Age (LBA) did tin bronze substitute almost completely the previous role of copper. In the Early Iron Age, during the Orientalising period, a general decrease in the average tin content in bronzes seems to happen. Regarding the inclusions observed in the metal matrix, these seem to suffer a diversification with the appearance of tin bronzes. By the Copper Age, only Cu? O and Cu? As? O inclusions are observed, while by the LBA Cu? S inclusions become regular, besides others less frequent, as Sn? O, Cu? S? Fe and Pb globules. Overall, with the present analytical study, the complementary character of micro‐EDXRF and SEM‐EDS in the study of ancient metals is demonstrated, providing a first general overview of the ancient metallurgy at the Portuguese territory which is of key importance to specific investigations of the future. Copyright © 2011 John Wiley & Sons, Ltd.     

Sulfur determination on stone monuments with a transportable EDXRF system

An important part of the world's cultural heritage is represented by stone monuments. A very dangerous weathering process that deteriorates stone monuments and is caused by human activity is air pollution. One of the worst pollutants for stone monuments is associated with sulfur compounds, especially with gypsum. Gypsum is a rather soluble compound that may be washed away by rain. It leaves the surface of the stone clean but eroded and open to new corrosive processes. With transportable energy dispersive x‐ray fluorescence (EDXRF) instruments it is possible to conduct in situ investigations, mappings, registrations and evaluations of the stone‐degradation phenomena related to sulfate formation on stone and stone‐like materials by quantifying sulfur concentrations directly associated with the presence of gypsum. The EDXRF instrument used in this project is a commercial system comprising a miniaturized low‐power, air‐cooled tungsten x‐ray tube and a silicon drift detector (SDD) Peltier‐cooled detector. The EDXRF instrument was calibrated using a series of standard samples specifically developed for this project with a sulfur content ranging from 0.5 to 15%. Correlating the sulfur peak counts with sulfur concentrations, a straight calibration line (R² = 0.9985) was obtained. Several high voltage levels of the x‐ray tube were tried to define the best operating conditions. The silicon escape peak of calcium had to be accounted for owing to its interference with the sulfur peak. In this paper we shall discuss the working method adopted and the results achieved following the examination of a number of stone monuments such as the “Fanciulla di Anzio” and other ancient Roman statues housed in the Roman National Museum, and the Sarcophagus of Pope Boniface VIII sculpted by Arnolfo di Cambio and situated in the Crypt of the Vatican Basilica. Copyright © 2007 John Wiley & Sons, Ltd.     

Linear quantification calibration of crystallinity at subpercent and its evaluation based on spectral and spatial information inherited in Raman chemical images

In this paper, the author reported two methods to extract spectral or spatial information inherited in the Raman chemical images for linear quantification calibration of crystallinity. The two approaches reported quantification results according to the spectral mean score of overall pixels or the spatial percentage of the pixels with a score greater than and equal to the threshold of the chemical images, respectively. From this study, it can be concluded that, first, sampling method for data collection in mapping has to be optimized to achieve linear quantification calibration through simple univariate analysis approaches. Second, the ordinary way of evaluating/validating a linear quantification technique by best linear correlation coefficient (R²) and root‐mean‐square error of calibration is disputable and has to be reconsidered. Lastly, with further consideration of root‐mean‐square relative error of calibration and predicted crystallinity at subpercent, it was found that the spectral mean score method cannot generate reliable quantification results at subpercent crystallinity. Copyright © 2014 John Wiley & Sons, Ltd.     

SXRF分析恐龙脊椎头化石微量元素

利用同步辐射X射线荧光成像方法(SXRF)检测了二件不同地区的脊椎头恐龙化石,在每件化石截面上的二个不同区域分别获取了8种元素的分布图及其荧光光谱。在两件样品靠外层的骨密质部位,发现有较密集的稀土元素Y(钇)。在姜驿恐龙化石中Y的富集,来自于化石的成岩过程,在元素分布图中与稀土元素Y共生的含Ca化合物是氟磷酸钙。武定田心恐龙脊椎头化石中,在稀土元素钇的富集的区域,其它元素包括Ca的含量均特别少。此种稀土元素的富集可能是由于化石中含有分解不完全的有机物的吸附所致。在姜驿恐龙脊椎头化石中,微量元素Mn、Fe和Al属于共生矿物;As、Sr、Y元素集中分布在化石的外边缘处,也是三者共生。在田心恐龙脊椎头化石中,微量元素Mn、Fe和Al属于共生矿物,Sr、Y元素共生,Cu元素的分布相对集中。研究表明,恐龙化石中矿物的元素含量及其分布与骨骼所属的部位无关,只与源地有关。恐龙化石中稀土钇富集的地方,呈现白色。同步辐射X射线荧光探测法,能原位、快速、无损地检测出化石样品各种元素的荧光光谱,给出恐龙化石元素分布的二维信息,对于分析恐龙化石所蕴含的侏罗纪时期的古地质特征和古生物信息,给出了重要的依据。     

Chemical Analysis of Hydroxyapatite Artificial Bone Powders by Energy Dispersive X-Ray Fluorescence Spectrometry(EDXRF)

Stoichiometric hydroxyapatite (HA) nanoparticles were synthesized by a wet chemical method. Calcium nitrate tetra hydrate used as calcium source and dibasic ammonium phosphate used as phosphorous source. Calcium nitrate tetra hydrate and dibasic ammonium phosphate solutions were prepared by dissolving the salts in distilled water. Stoichiometric hydroxyapatite nanoparticles used by artificial bone powders and synthesized by a wet chemical method were analyzed using EDXRF method.The concentrations of K, Ca, Ti, V, Cr, Fe, Ni, Cu, Sr and Pb for artificial bone powders have been determined. Besides, Calcium contents were evaluated according to the agitation time and temperature in the production process.     

Increased strontium uptake in trabecular bone of ovariectomized calcium‐deficient rats treated with strontium ranelate or strontium chloride

Based on clinical trials showing the efficacy to reduce vertebral and non‐vertebral fractures, strontium ranelate (SrR) has been approved in several countries for the treatment of postmenopausal osteoporosis. Hence, it is of special clinical interest to elucidate how the Sr uptake is influenced by dietary Ca deficiency as well as by the formula of Sr administration, SrR versus strontium chloride (SrCl₂). Three‐month‐old ovariectomized rats were treated for 90 days with doses of 25 mg kg^?1 d^?1 and 150 mg kg^?1 d^?1 of SrR or SrCl₂ at low (0.1% Ca) or normal (1.19% Ca) Ca diet. Vertebral bone tissue was analysed by confocal synchrotron‐radiation‐induced micro X‐ray fluorescence and by backscattered electron imaging. Principal component analysis and k‐means clustering of the acquired elemental maps of Ca and Sr revealed that the newly formed bone exhibited the highest Sr fractions and that low Ca diet increased the Sr uptake by a factor of three to four. Furthermore, Sr uptake in bone of the SrCl₂‐treated animals was generally lower compared with SrR. The study clearly shows that inadequate nutritional calcium intake significantly increases uptake of Sr in serum as well as in trabecular bone matrix. This indicates that nutritional calcium intake as well as serum Ca levels are important regulators of any Sr treatment.     

In vivo EDXRF scanning analysis of human nail

This paper presents the results of a new technique for in vivo energy dispersive X‐ray fluorescence (EDXRF) scan analysis, applied to human fingernails. The scan employs a specially designed EDXRF spectrometer, which allows a concentration profile of the elements detected in a human nail. In order to carry out this technique, a group of nail fragments taken from different people was analyzed. The elements S, Ca, Cu, Fe, Cu, Zn, and Pb were detected in most of the samples. A bidimensional (x, y) scan was also performed on a whole removed nail in which the 2D spatial distribution of the detected elements was observed. Significant differences in some of the detected elements were noted. Minimum time of average detection per element was determined, based on the EDXRF spectra of the nail fragment. The time required to obtain an in vivo element profile of a typical nail was thus determined, applying the same geometry and acquisition conditions for all cases. The dose that the person undergoing this type of EDXRF scan analysis would be exposed to was also determined. Exposure time does not exceed 15 s, and the calculated administered dose is in the surface nail region of 0.1 mGy/s. The results of this study demonstrate that it is possible to carry out an in vivo X‐ray fluorescence scan analysis. This information may be used in different fields of medicine, such as nutrition and toxicology, and in other areas that establish a correlation between the concentration of the detected elements and certain diseases. Nail and hair are known to be ‘accumulating tissues’ unlike bodily fluids. In some aspects, nail analysis can be equal to a blood test. Copyright © 2014 John Wiley & Sons, Ltd.