激光电离飞行时间质谱技术用于古代瓷片中元素的检测及元素成像分析

采用自制激光电离飞行时间质谱(LI-TOF-MS)及多元素成像体系,尝试分析了古瓷片中的多种元素.对一块北宋龙泉青瓷瓷片及一块仿古青瓷瓷片样品进行了表面元素分析,所得多元素半定量分析结果表明,这两种瓷片的胎体和釉面中所含元素的种类及含量存在差异;同时对一块明代青花瓷片进行表面多元素成像分析,获得Co,Mn,Fe,Ni,Ba,Ca,Mg,Na,Al,Si,P,K,Cu,Zn和Rb的元素成像图.     

Study of provenance character on ancient porcelain of Yue Kiln at Silongkou with NAA

Chemical composition is an important information of studying the provenance character of ancient pottery and porcelain. The ancient celadon samples produced in Later Tang (850–907 A.D.) to Former Southern Song (1127–1279 A.D.) have been analyzed with NAA. Its provenance characteristic was compared with that of Hongzhou Kiln of Jiangxi Province and Yaozhou Kiln of Shanxi Province in this paper. The experimental data were studied with statistic methods. The results indicated that the chemical compositions of ancient porcelain body samples made in three kilns were different. The difference is able to be identified. The porcelain body materials of both Silongkou Yue Kiln and Hongzhou Kiln were similar. The samples of Yaozhou kiln in north of China existed obvious difference.     

Study on the provenance of ancient Yaozhou celadon made at Lidipo and Shangdian during Kin period using nuclear technology

Yaozhou Kiln at Lidipo and Shangdian are two independent porcelain kiln groups of Yaozhou kiln series in Shanxi Province. Both of them were consisted of some individual porcelain kilns. The samples of 20 pieces of porcelain sherds produced in Shangdian and 43 pieces of porcelain sherds made in Lidipo sites which produced in Kin Dynasty (1115–1234 A.D.) have been collected. The main chemical compositions in body were determined by X-ray fluorescence (XRF). The contents of trace elements were measured using neutron activation analysis (NAA). Principal component analysis (PCA) and stepwise discriminant analysis were used to study the provenance characteristic of these samples. The results indicated that the main components and trace elements in the specimen can be used to reveal the provenance characteristic.     

Analytical characterization of paintings on pre-Roman pottery by means of spectroscopic techniques. Part II: Red, brown and black colored shards

As a part of a systematic study aimed at assessing the chemical composition of ancient pigments as well as at collecting information useful for the understanding of the technical aspects related to pottery preservation and decoration, the results of analysis performed on red, brown and black pigments decorating pre-Roman pottery excavated in thirteen different tombs unearthed in the archaeological zone of Canosa (Puglia, Italy) are presented. Both surface (XPS) and bulk (FT-IR) spectroscopies were used which gave complementary information and XRD was used in some cases to further support the spectral assignments. Results suggested that the shards characterized by “nominally” the same color could be differentiated by the chemical composition of the pigmented layers; in particular, the shards exhibiting the red pigment could be divided into three groups containing, respectively, either hematite or ochre plus other substances not related to the color but of great concern for the understanding of ancient techniques used for color preparation. Manganese oxides were found to be the basis of the brown pigments, which could be divided into three groups on the basis of Mn and Fe contents. Either magnetite or carbon of vegetable origin was found in the black-pigmented layers. Furthermore, an attempt was made to find a possible correlation between this classification and the results of a provenance study carried out on the same pool of shards analyzed in the present investigation.     

Analytical characterization of paintings on pre-Roman pottery by means of spectroscopic techniques. Part II: Red, brown and black colored shards

As a part of a systematic study aimed at assessing the chemical composition of ancient pigments as well as at collecting information useful for the understanding of the technical aspects related to pottery preservation and decoration, the results of analysis performed on red, brown and black pigments decorating pre-Roman pottery excavated in thirteen different tombs unearthed in the archaeological zone of Canosa (Puglia, Italy) are presented. Both surface (XPS) and bulk (FT-IR) spectroscopies were used which gave complementary information and XRD was used in some cases to further support the spectral assignments. Results suggested that the shards characterized by “nominally” the same color could be differentiated by the chemical composition of the pigmented layers; in particular, the shards exhibiting the red pigment could be divided into three groups containing, respectively, either hematite or ochre plus other substances not related to the color but of great concern for the understanding of ancient techniques used for color preparation. Manganese oxides were found to be the basis of the brown pigments, which could be divided into three groups on the basis of Mn and Fe contents. Either magnetite or carbon of vegetable origin was found in the black-pigmented layers. Furthermore, an attempt was made to find a possible correlation between this classification and the results of a provenance study carried out on the same pool of shards analyzed in the present investigation. Received: 28 May 1999 / Revised: 6 August 1999 / Accepted: 21 August 1999     

Comparative analysis of ancient ceramics by neutron activation analysis,inductively coupled plasma-optical-emission spectrometry,inductively coupled plasma-mass spectrometry,and X-ray fluorescence

The accurate measurement of the maximum possible number of elements in ancient ceramic samples is the main requirement in provenance studies. For this reason neutron activation analysis (NAA) and X-ray fluorescence (XRF) have been successfully used for most of the studies. In this work the analytical performance of inductively coupled plasma-optical-emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) has been compared with that of XRF and NAA for the chemical characterization of archaeological pottery. Correlation coefficients between ICP techniques and XRF or NAA data were generally better than 0.90. The reproducibility of data calculated on a sample prepared and analysed independently ten times was approximately 5% for most of the elements. Results from the ICP techniques were finally evaluated for their capacity to identify the same compositional pottery groups as results from XRF and NAA analysis, by use of multivariate statistics.     

Nuclear activation methods for the characterization of fossil fuels

A review is presented on the use of neutron activation analysis (NAA) for the analyses of coal, oil shale, tar sands and petroleum. Fast NAA has been widely used for the determination of oxygen, and to a limited extent, of other elements such as nitrogen and silicon. Reactor NAA followed by instrumental counting, and in specific cases, after radiochemical separations is discussed. Thermal and epithermal neutrons are both used. Limited use of the²⁵²Cf source has been made in fuel analysis. A complementary technique to NAA is the photon-activation analysis with linear accelerator. It can determine over thirty elements, many of them not possible to do by NAA. Round-robin analyses of standard coal, fly ash, or oil shale samples indicate nuclear activation methods are comparable in accuracy and precision to X-ray fluorescence or atomic spectrometric methods for most elements.     

X-ray emission fluorescence (XRF) analysis of origin of raw materials of light dark reddish brown porcelain and porcelain with black flower on a white background of Dangyangyu kiln

Dangyangyu kiln was an important civil porcelain production place in the North China during the Song Dynasty. In order to find out the source of raw materials of the porcelain body and glaze and their classification relationship so as to correctly distinguish them, we have used XRF to determine the major chemical elements of some porcelain samples with light brown and samples with black flower on a white background. Dynamic fuzzy cluster analysis was applied to the data. Results indicate that the origin of raw materials of light brown porcelain body samples is comparatively more concentrated, while that of the porcelain with black flower on a white background is scattered about. The origin of the body materials of those two kinds of porcelain samples is obviously different. The origin of raw materials of light brown porcelain samples is comparatively concentrated and stable, while that of the porcelain with black flower on a white background is scattered about, moreover, the origin of glaze raw materials and the formula of the two kinds are obviously different. The origin and formula of the light brown porcelain with white glaze in the interior are close to those of the white glaze of porcelain with black flower on a white background, but they are not entirely identical.     

Use of NAA in marine environment and in archaeology in Greece

Neutron activation analysis (NAA) is a very sensitive and accurate multielement analytical method that is widely applied to the investigation of environmental and archaeological problems. The first part of this paper is a review of pollution studies of toxic trace elements in sediments, seawater and marine organisms of Saronikos Gulf, Greece by NAA. The second part of this paper is a review of provenance studies based on minor and trace element research in ancient ceramics, obsidian, flint, limestone, marble and lead by Instrumental NAA, performed at the NCSR Demokritos.     

The problem of multivariate classification of samples with radial (or V-shaped) chemical data

On the basis of the results of previous studies, the problem of multivariate classification in the presence of the so-called radial or V-shaped data has been briefly re-examined. Taking into account that the radial data, in the absence of preliminary transformations, usually lead to classifications of samples meaningless from a chemical point of view, five different data transformations have been evaluated and compared in the case of both hypothetical and real samples (real samples, in particular, consisted of archaeological ceramic shards to be classified on the basis of provenance). The following transformations have been used: closure to 100, log row centering, log double centering, row centering, and double centering. The transformed data were then classified by means of hierarchical clustering and principal component analysis (PCA). It has been demonstrated that only the first three transformations lead to correct classifications of radial data, and the causes of this fact have been explained.     

Characterization of simulated vitrified highly active waste and its leachates by neutron activation

Neutron activation analysis (NAA) methods have been developed for the simultaneous determinations of multielement concentrations in various types of glass and their leachates. The epithermal instrumental NAA (EINAA) method involves the irradiation of samples in a Cd-shielded site for 2–5 min in order to determine levels of of up to 13 elements through their short-lived nuclides. Another 15 elements can be measured via their long-lived nuclides using conventional instrumental NAA (INAA). Accuracy of the methods have been evaluated by analyzing certified reference materials. The limits of detection for all elements are reported. The methods have been applied to sodium borosilicate and sodium calcium aluminosilicate glass samples in order evaluate their suitability as a host matrix for immobilizing high level radioactive waste.     

Provenance studies of pottery fragments from medieval Cairo, Egypt

In the analysis of archeological pottery fragments, instrumental neutron activation analysis has been utilized to establish the elemental concentrations of up to 37 chemical elements for each of 53 archeological pottery samples from medieval Cairo, Egypt, and one additional sample of Chinese porcelain. These elemental concentrations have been utilized in a statistical analysis procedure in order to determine similarities and correlations between the various samples. Multivariate analyses have been used to quantitatively determine these interrelationships. This methodology successfully separated the Egyptian samples into two broad categories: (1) polychrome decorated ceramic ware and (2) monochrome celadon ware. In addition the methodology successfully identified the one unique sample of Chinese porcelain. Several samples appeared to be either a mixture of categories or outliers in the data set and were not attributable to any distinct category.     

Opportunities for innovation in neutron activation analysis

Neutron activation laboratories worldwide are at a turning point at which new staff has to be found for the retiring pioneers from the 1960s–1970s. A scientific career in a well-understood technique, often characterized as ‘mature’ may only be attractive to young scientists if still challenges for further improvement and inspiring new applications can be offered. The strengths and weaknesses of neutron activation analysis (NAA) are revisited to identify opportunities for innovation. Position-sensitive detection of elements in large samples, Monte Carlo calculations replacing the use of standards, use of scintillator detectors and new deconvolution techniques for increasing the sensitivity are examples of challenging new roads in NAA. Material science provides challenges for the application of NAA in both bulk samples, ultrathin layers and ultrapure materials.     

An EPR study on ancient and newly synthesised Egyptian blue

Two sets of ancient roman Egyptian blue (EB) samples and one set of EB samples synthesised in our lab, were analysed by EPR spectroscopy, a technique not commonly used in this field. The spectroscopic parameters obtained were used to attempt the discrimination of the provenance and of the manufacturing techniques of the investigated samples.The results obtained show that EPR technique could be very useful for this purpose.Furthermore, the similarity of the obtained parameters between the ancient and new samples testify the successful attempt to reproduce the EB according to the chemical knowledge.     

Application of INAA to ancient bricks for grouping study using trace elements

The paper presents the chemical composition analysis results of 57 ancient clay bricks obtained from Buddhist sites of two major locations of Andhra Pradesh, India. Samples were analyzed by instrumental neutron activation analysis (INAA) using high flux reactor neutrons and high resolution gamma ray spectrometry. Major, minor and trace concentrations of 23 elements were determined by relative method of NAA. For the grouping/provenance study, statistical cluster analysis was performed using concentrations of 14 selected elements namely Sc, Cr, Fe, Co, Zn, Cs, La, Ce, Eu, Tb, Yb, Lu, Ta and Th. The cluster analysis results indicated two major groups, which are in good agreement with the collection history of samples. Accuracy of the method was evaluated by analyzing two IAEA reference materials, RMs SL-1 and Soil-7.     

Chemical characterisation of ancient pottery from south of Italy by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) Statistical multivariate analysis of data

Chemical characterisation has been carried out on 58 fragments of archaeological pottery from pre-classical sites in Apulia and Lucania, regions in southern Italy. Fourteen elements were determined by atomic emission spectroscopy by using inductively coupled plasma source. Statistical techniques, such as principal component analysis and clustering analysis, have been utilised to define grouping of different pottery items. Tests performed showed that the analysed shards were differentiable mainly by age and provenance.     

Radiochemical determination of trace noble metals in silver artefacts

Radiochemical separations are essential for the determination of trace elements in silver artefacts by neutron activation analysis due to the high levels of both short and long-lived activities produced by the matrix, but the sensitivity of the technique permits the examination of small samples. The noble metals are considered most significant from a diagnostic standpoint, and radiochemical techniques have been developed for their determination in samples of a few milligrams. Methods have been investigated for the determination of Pd, Rh, Ir and Pt in samples removed from museum specimens of known provenance.     

Neutron activation analysis applications at the Savannah River Site using an isotopic neutron source

NAA using ²⁵²Cf is used to address important areas of applied interest of the Savanah River Site (SRS). Sensitivity needs for many of the applications are not severe; analyses are accomplished using a 21 mg ²⁵²Cf NAA facility. Because NAA allows analysis of bulk samples, it offers strong advantages for samples in difficult-to-digest matrices when its sensitivity is sufficient. Following radiochemical separation with stable carrier addition, chemical yields for a number of methods are determined by neutron activation of the stable carrier. In some of the cases where no suitable stable carriers exist, the source has been used to generate radioactive tracers to yield separations.     

Neutron activation analysis investigations in updating REE composition of gabbro GOG-1 reference sample: A comparison with SIMS and ICP-AES data

An updata REE measurement of gabbro GOG-1 was carried out by means of neutron activation analysis (NAA). The availability of high amounts of rock powder allowed the sample to be well ground and homogenized before analysis. Homogeneity tests, carried out on different aliquots, show that GOG-1 samples can be considered homogeneous when over 50 mg aliquots of rock powder are employed for analytical work. Results from ICP-AES and SIMS investigations of REE in gabbro GOG-1 are in quite good agreement with NAA data and support the possibility of employing GOG-1 rock samples as reference material for geoanalysis.