X射线显微CT成像技术在金属文物制作工艺研究与腐蚀状态评估中的应用

金属腐蚀过程不仅受环境等外部因素的影响,制作工艺、合金组成及缺陷等内部因素同样起着重要作用。为实现金属文物制作工艺和内部腐蚀状态的可视化研究,运用X射线显微CT对铜镜文物碎片以及出土、海洋出水铁质文物样品进行扫描探测,并结合X射线荧光、X射线衍射等检测手段,开展金属文物材质、工艺及矿化程度的综合分析。结果表明,在显微CT影像重建基础上,通过设定不同的阈值,可实现文物内部缺陷、腐蚀矿化程度等内部信息的测量统计。该方法可为金属文物材质、制作工艺研究和腐蚀状态评估提供无损的研究手段。     

COLD NEUTRON PROMPT GAMMA ACTIVATION ANALYSIS—A NON‐DESTRUCTIVE METHOD FOR CHARACTERIZATION OF HIGH SILICA CONTENT CHIPPED STONE TOOLS AND RAW MATERIALS*

Recently, several archaeometrical projects have been started on the prehistoric collection of the Hungarian National Museum. Among the analytical methods applied, non‐destructive prompt gamma activation analysis has a special importance. We have also tested the potential of this method on chipped stone tools, with the aim of determining their exact provenance. On the basis of major and trace element components, characterizations of stone tools and their raw materials—silicites (flint, chert, radiolarite and hornstone) as well as volcanites (felsitic porphyry and obsidian)—were performed. We discuss some important results concerning each group, as case studies. Compiling the data set of different PGAA analysis series, compositions of 110 samples are reported, including 76 archaeological pieces. In the future, we plan to extend the number of investigated objects in each class.     

X‐RAY SUB‐MICRON TOMOGRAPHY AS A TOOL FOR THE STUDY OF ARCHAEOLOGICAL WOOD PRESERVED THROUGH THE CORROSION OF METAL OBJECTS

Wood preserved in the corrosion layer of two early medieval iron objects was examined using X‐ray tomography. A state‐of‐the art multi‐resolution X‐ray tomography set‐up ( http://www.ugct.ugent.be ) provided virtual cross‐sections of the archaeological wood samples at sub‐micron resolution. These were compared with scans of samples of similar modern wood. These scans demonstrate the power of sub‐micron X‐ray tomography for wood identification, although the process of mineralization pushes this technique to its limits. Furthermore, this technique facilitated appraisal of the mineral content of the archaeological wood, which is useful in selecting the most appropriate strategy for the (preventative) conservation of the archaeological object.     

X-ray and neutron-based non-invasive analysis of prehistoric stone artefacts: a contribution to understand mobility and interaction networks

Carbonate-rich archaeological artefacts are difficult to identify and correlate between them and with raw materials of such heterogeneous geological sources, especially when only non-invasive analysis is possible. A novel combination of X-ray and neutron-based non-invasive analysis is implemented and used for the first time to study prehistoric stone idols and vessels, contributing to culture identity, mobility and interaction in the recent Prehistory of Southern Iberia. Elemental composition was obtained by prompt gamma activation analysis (PGAA) and external beam particle-induced x-ray emission (PIXE); homogeneity of the stone artefacts and the presence/absence of internal fractures were obtained by neutron radiography (NR). These atomic and nuclear techniques, simultaneously used for complementary chemical information, have been demonstrated to be of great value as they provide non-destructive compositional information avoiding sample preparation, crucial in so singular and rare objects. The obtained results, especially of PGAA, are very promising and useful in general assessments of provenance. The stone artefacts show signs of both nearby and long-distance procurement, as well as of unknown attribution.     

Neutron Activation Analysis of Metal Artefacts from the Moche Site,North Coast of Peru

Neutron activation analysis has been used to characterize 60 metal objects from the Moche site, of which four are associated with the Chimú Period, two with the Early Chimú Period and the others with various Moche IV contexts. Different types of utilitarian and non‐utilitarian objects were analysed to identify the metals present, and to investigate their chemical composition and their eventual source. The results clearly indicate the distinction between Chimú and Moche artefacts and confirm the generalized opinion that arsenic bronze was popular after ad 900. They also indicate that gilding copper objects with gold was already a common practice during the Moche era.     

ANALYSIS OF COPPER-BASED METALLIC ARTIFACTS BY PROMPT GAMMA-RAY NEUTRON ACTIVATION ANALYSIS

Non-destructive analysis of the major elements in copper-alloyed artifacts by prompt gamma neutron activation analysis is reported. Copper, zinc, tin and lead were measured in several ancient Roman, Greek and Iranian objects. Good agreement was found in comparison with analysis of similar objects by destructive methods.     

THE USE OF TRACE ELEMENT ANALYSIS OF ENTRAPPED SLAG INCLUSIONS TO ESTABLISH ORE – BAR IRON LINKS: EXAMPLES FROM TWO GALLO‐ROMAN IRON‐MAKING SITES IN FRANCE (LES MARTYS,MONTAGNE NOIRE,AND LES FERRYS,LOIRET)*

Knowledge of the iron trade in ancient times rests on determining the source of the objects recovered during archaeological excavations. Unfortunately, attributing the origin is not always possible using archaeological tools alone. Trace element data of the ore and the archaeological material (reduction and reheating slags, entrapped slag inclusions from the bloom, bar iron and iron blades) from two Gallo‐Roman iron‐making centres, Les Martys (Montagne Noire) and Les Ferrys (Loiret), were determined using ICP–AES/MS and LA–ICP–MS. The results highlight a continuity of composition that makes it possible to establish a link between the initial ore and the semi‐finished iron products.     

Scanning electron microscopy of wood replaced by iron corrosion products

Remains similar to wood in superficial appearance are sometimes observed on the surfaces of corroded iron objects from archaeological deposits. Examination of this material in a scanning electron microscope suggests that deposition of iron corrosion products has occurred within the cell spaces. Subsequently the wood may have decomposed, leaving behind internal cell casts which mirror the original structure.     

Studying the Cannons of Punta Santa Anna,Spain: In Situ Conservation,Promoting Public Access,and Monitoring Iron Corrosion

The 2001 UNESCO convention for the Protection of Underwater Cultural Heritage (UCH) encourages and supports projects that would make accessible to the general public underwater cultural sites. Since 2010 the Catalonian Federation of the World Underwater Federation (FECDAS), have been developing outreach activities with the objective of promoting the protection of the UCH among recreational scuba divers. The purpose of this paper is to introduce one such project, the Punta Santa Anna in Blanes, Spain. This project has three objectives: the promotion of UCH to the general public, the in situ protection of this underwater archaeological site, and a case study on iron corrosion processes. FECDAS/CMAS will create an underwater archaeological park where recreational scuba divers will be able to visit some purposely selected archaeological iron cannons. To expose UCH to the general public will potentially affect the integrity of these artefacts. This risks potential damage and so, with the objective of minimizing potential threats, a series of protective measures and a systematic monitoring programme have been planned. The programme is designed to study the relationship between the underwater environment and the artefacts. The aim is to acquire a better understanding of the corrosion processes of iron objects present in marine underwater sites.     

A Rock‐Magnetic Quest for Possible Ore Sources for the Ancient Iron‐Smelting Industry in the Olkhon Region (Lake Baikal,Siberia)

Rock‐magnetic techniques were used to examine the topsoil layer of Kurma archaeological site (in the Olkhon region, on the north‐western coast of Lake Baikal, Siberia) in an effort to determine the possible sources of iron ores for iron‐smelting centres (at about the bc /ad boundary). Measurements have shown a magnetic enhancement of the topsoil due to magnetite grains resulting from weathering of strongly magnetic crystalline rocks. They have also revealed a preliminary picture of the distribution of strongly magnetic topsoils around the ancient iron‐smelting centres. Perhaps, in addition to traditional sources of raw materials, the ancient metallurgists used black sand talus as an ore deposit.     

ACKNOWLEDGING FIFTY YEARS OF NEUTRON ACTIVATION ANALYSIS IN ARCHAEOLOGY

Neutron activation analysis has been an important analytical technique for chemical characterization studies of archaeological materials since 1957, and remains one of the best analytical approaches for bulk chemical characterization of archaeological ceramics and other materials. This paper introduces a series of reports that document the history of NAA applied to archaeological materials.     

An Analytical Methodology for the Study of the Corrosion of Ferrous Archaeological Remains in Soils

Abstract

In the context of the cultural heritage, a methodology based on ?eld and laboratory approaches is developed for studying the long-term corrosion of iron. Moreover it has been adapted to the study of archaeological artefacts buried in anoxic soils in the speci?c case of in situ preservation. The environmental parameters are determined on the archaeological sites and artefacts are collected and characterized using complementary multi-scale techniques. Moreover, laboratory experiments are performed to locate the reaction sites inside the corrosion layer and to identify its electronic properties. The results allow estimation of a low corrosion rate for iron buried in an anoxic soil (under 2 μm/year) and the proposal of a mechanism based on a decoupling of the anodic and the cathodic sites. Then a diagnosis of the alteration state of the samples is established.     

A PROVENANCE STUDY OF FRENCH LIMESTONE BASED ON VARIABLE SELECTION FROM COMPOSITIONAL PROFILES

The present study shows how multivariate analysis and variable selection techniques can be used in archaeological provenances studies to improve classification performances. Neutron activation analysis (NAA), in combination with stepwise linear discrimination analysis (SLDA) (capable of simultaneously performing variable selection and classification), was applied to differentiate among limestone samples from different quarries across the north of France based on their compositional fingerprint. A hierarchical classification approach was followed, aimed at progressively assigning limestone samples to more specific sources of origin, from the broadest classification units (French regions) to the narrowest ones (individual quarries). The application of the stepwise variable selection procedure to extract the most discriminating compositional variables prior to each classification development allowed us to obtain a perfect separation between the limestone categories considered at every classification stage (all samples were correctly classified and predicted in all cases). The high‐quality results obtained were even more remarkable considering the relatively small number of significant variables selected in each case using the SLDA method. An illustrative example was provided in order to demonstrate that the classification strategy proposed can actually allocate an unknown sculpture to a particular quarry of origin.     

IDENTIFICATION OF FORGERIES BY MEASURING TIN ISOTOPES IN CORRODED BRONZE OBJECTS*

The reliable identification of fakes consisting of bronze often presents problems, because traditional methods such as stylistic studies, optical microscopy, chemical analysis or X‐ray diffraction of the corrosion may not be conclusive. We present a method that is based on the comparison of the tin isotope ratios ¹²²Sn/¹¹⁶Sn and ¹¹⁷Sn/¹¹⁹Sn in the metal and in the adherent corrosion layer. An artificial patina is usually generated within a short time period. It has been observed that such a procedure leads to a depletion of the light tin isotopes in the corrosion layer, while in naturally corroded authentic archaeological objects no isotopic fractionation has been detected. The method has also been applied to archaeological objects and it could be confirmed, among other examples, that the famous ‘Sky Disc of Nebra’ is authentic.     

NO STONE UNBURNED: A COMPOSITIONAL ANALYSIS OF OBSIDIAN MICRODEBITAGE BY LASER ABLATION TOF–ICP–MS

Obsidian is an effective material for the study of prehistoric raw material use and exchange, due to the high degree of homogeneity and redundancy of obsidian materials and manufactured objects in the archaeological record. The destructive nature of many analytical techniques often impedes compositional research because of the damage that may occur to priceless archaeological artefacts. The combination of time‐of‐flight (TOF) ICP–MS with a laser ablation sample introduction system provides a highly efficient means of chemically characterizing obsidian. This study shows that sample size limit capabilities of TOF–ICP–MS analysis of obsidian can reach less than 100 μm. Sampling and analysis of microartefacts enables researchers to overcome problems of sampling bias with very little damage to the valuable existing materials within the archaeological record and expands the potential for chemical compositional analyses in archaeology.     

BRITTLE ARCHAEOLOGICAL SILVER: A FRACTURE MECHANISMS AND MECHANICS ASSESSMENT*

Some archaeological silver objects are found to be brittle. The brittleness is a consequence of long‐term corrosion and microstructural changes. The types and mechanisms of embrittlement are defined and explained. The severity of embrittlement is increased by a larger grain size and by synergistic action of corrosion‐induced and microstructurally induced embrittlement. Micromechanical models of fracture that incorporate the grain size provide an insight into these effects and help to explain why severely embrittled objects are frangible or even friable.     

Electrochemical Characterization and Dating of Archaeological Leaded Bronze Objects Using the Voltammetry of Immobilized Particles

The application of solid state electrochemistry techniques for the characterization and dating of leaded bronze objects is described. Characteristic voltammetric signatures of copper and lead corrosion products were used as markers of more or less prolonged corrosion periods. The proposed methodology was applied to samples from the Roman archaeological sites of Valeria (Spain) and Gadara (Jordan), Roman and medieval sites in Xàtiva (Spain), and modern statuary exhibited outdoors, on the campus of the Universitat Politècnica of Valencia, Spain, covering a time interval between the fourth to second century bc and the 20th century ad . For such samples, the ratio between the signals for copper and lead corrosion products decreased monotonically with the corrosion time. This variation was modelled on the basis of thermochemical and kinetic considerations, the experimental data being consistent with a potential rate law for the corrosion process.     

MATCHING PAST AND PRESENT CERAMIC PRODUCTION IN THE BANDA AREA (GHANA): IMPROVING THE ANALYTICAL PERFORMANCE OF NEUTRON ACTIVATION ANALYSIS IN ARCHAEOLOGY USING MULTIVARIATE ANALYSIS TECHNIQUES*

The transfer of advances in chemometrics into archaeometric research opens up a wide range of new application possibilities in this rapidly developing field. Neutron activation analysis (NAA) of ceramic samples from the Banda Traditional Area (west‐central Ghana) combined with chemometrics allowed us to establish a link between current and ancient systems of ceramics production in the historic settlements of Kuulo Kataa and Makala Kataa. Principal component analysis (PCA) and the soft independent modelling of class analogy (SIMCA) method were applied to the Das Dores Cruz data set in order to unequivocally determine the geographical origin of the diverse archaeological samples. After global autoscaling pretreatment, PCA analysis showed a clear difference between samples from different locations. The classification models obtained by SIMCA showed a classification ability of 100% and a prediction ability of 97.7%, with a mean sensitivity of 84% and a specificity of 100% for the three categories. The application of SIMCA showed that some NAA variables (elements) were more important than others in terms of geographical classification. With the class models that we obtained, we were able to determine the origin of the ancient remains. SIMCA has proved to be a powerful technique for the class modelling of archaeological data.     

The Contribution of Transmission Electron Microscopy (TEM) to Understanding Pre‐Columbian Goldwork Technology

This paper highlights the contribution of transmission electron microscopy (TEM) when combined with scanning electron microscopy and energy‐dispersive X‐ray microanalysis (SEM/XEDS) to characterize objects in archaeology. The application of TEM in archaeology is not yet a common tool, but it may provide data that are significant to understanding pre‐Columbian gold metallurgy, specifically the gilding and silvering methods. Two gilded rods were studied using a combination of TEM and SEM/XEDS techniques. The objects were found at the Atacames archaeological site, in the Esmeraldas region, Ecuador, which was occupied between ad 750 and 1526 by the Atacames culture. The microchemical and structural results of the inner and the external gilded part of the artefacts support the hypothesis of a gold diffusion to the surface enhanced by chemical treatment with chloride‐rich solutions, heating and successive annealing processes. The present study reveals that microstructural investigation by TEM provides useful information with which to investigate the techniques used to modify the chemical surface composition of pre‐Columbian artefacts.     

Chemical and Petrographic Analysis of Pre‐Hispanic Pottery from the Southern Abaucán Valley,Catamarca, Argentina

Neutron activation (NAA) and petrographic analyses were carried out on Late and Inca Period pottery from 15 archaeological sites and several clay samples in the southern Abaucán Valley, Catamarca, Argentina. The results from the NAA and petrographic analyses provide new data concerning local versus non‐local pottery production and vessel exchange for these two pre‐Hispanic cultural periods. The chemical data demonstrate the use of different clay sources over time until the Inca appearance in the region, when a more structured and controlled production is observed. Petrographic analyses show a similar change in the ceramic paste recipes used by ancient potters.