NON-DESTRUCTIVE ANALYSIS OF JINGDEZHEN BLUE AND WHITE PORCELAINS

The energy dispersive X-ray fluorescence method is used for the non-destructive qualitative analysis of Jingdezhen blue and white porcelains, which include the imperial wares of the Yongle, Xuande, Chenghua, Jiajing and Wanli periods of the Ming dynasty, the imperial wares of the Kangxi, Yongzheng, Qianlong, Jiaqing, Daoguang and Guangxu periods of the Qing dynasty, and those of the Republic and the contemporary period. The distribution pattern of the X-ray fluorescence intensities of the six characteristic elements for porcelain manufactured at different times has been investigated.     

ENERGY DISPERSIVE X-RAY FLUORESCENCE ANALYSIS OF ANCIENT COPPER ALLOYS: EMPIRICAL VALUES FOR PRECISION AND ACCURACY

Energy dispersive X-ray fluorescence (EDXRF) analyses are compared with neutron activation as well as atomic absorption analyses of ancient copper-based alloys in order to examine their accuracy and to estimate realistic values for precision and sensitivity of EDXRF. The results show that it is possible to obtain reliable data of the surface composition of objects non-destructively. Better results for bulk composition are usually obtained with drill samples where the sensitivity of the method is at least competitive with atomic absorption spectroscopy with flame atomization.     

A STUDY OF ANCIENT CHINESE PORCELAIN WARES OF THE SONG‐YUAN DYNASTIES FROM CIZHOU AND DING KILNS WITH ENERGY DISPERSIVE X‐RAY FLUORESCENCE*

Multi‐variable statistical analysis based on energy dispersive X‐ray fluorescence measurements on both porcelain body and glaze is employed to give clear and consistent classification of porcelain sherds from northern China of different styles from the Song‐Yuan dynasties (Ding and Cizhou styles), and also from the Sui‐Tang dynasties (Xing style). However, the observed separation is less clear for Cizhou style sherds produced at neighbouring kiln sites. Imitation Ding porcelain samples produced by ancient Cizhou potters are also analysed.     

X-RAY MICROANALYSIS OF ANCIENT GLASSY MATERIALS: A COMPARATIVE STUDY OF WAVELENGTH DISPERSIVE AND ENERGY DISPERSIVE TECHNIQUES*

Sensitivity, precision and accuracy of quantitative microanalysis of major, minor and trace elements present in ancient glasses by energy dispersive spectrometry (EDS) is compared to that by wavelength dispersive spectrometry (WDS). Although there are certain problems with EDS due to peak overlaps and background noise, the precision and minimum detection limits of EDS for most of the important elements in ancient glasses were found to compare favourably to those of WDS. Both EDS and WDS, when quantified by comparison to glass standards, can produce reliable results which are adequate for most technological questions.     

DETERMINING POTTERY PROVENANCE: APPLICATION OF A NEW HIGH-PRECISION X-RAY FLUORESCENCE METHOD AND COMPARISON WITH INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS*

A recently developed high-precision X-ray fluorescence (XRF) method, applied for the first time to the study of archaeological pottery, determines the abundances of 13 trace and four major elements from one X-ray spectrum acquired over a 1000 second counting interval. For replicate archaeological samples, the short-term and long-term measurement precisions were close to 1% for the ten elements measured with highest precision. These are comparable to the best results achieved on replicates of clay and pottery standards, and obsidian, using instrumental neutron activation analysis (INAA). High-precision XRF analysis, however, does not require a nuclear facility, and is markedly preferable to INAA in terms of the ease of both sample preparation and analytical procedure. Consequently, element abundance data can usually be provided by a single analyst within a few hours after the start of sample preparation. The accuracy of the method, determined by comparison with data of other workers on eight standard reference materials, averaged 2.4% for the ten best-agreeing elements. The effectiveness of the method for determining pottery provenance is demonstrated for a difficult problem, in which high-precision XRF analysis successfully distinguished the products of two nearby pottery manufacturers in Roman Galilee (Shikhin and Nahif) that had not been clearly differentiated by INAA. The greater effectiveness of high-precision XRF than INAA in this provenance study is a result of the different array of elements measured, and the higher precision obtained for certain elements, by XRF. These results suggest that high precision XRF has potential broad applicability for pottery provenance studies.     

X-RAY FLUORESCENCE CHARACTERIZATION OF MING-DYNASTY PORCELAIN RESCUED FROM A SPANISH SHIPWRECK

A radioisotope induced X-ray fluorescence method was used to measure trace elements in Ming porcelain. Thirty pieces of blue-and-white Chinese porcelain, belonging to the Ch'eng Hua reign (AD 1465-87) and rescued from a shipwreck, were analysed along with two fake reproductions. The measurement system consisted of an Si(Li) detector, a ¹⁰⁹Cd annular source and a personal computer with a non-linear fitting least-square program. The relative intensity ratios of manganese, cobalt, rubidium, strontium, zirconium, and niobium were determined. Rb/Sr and Mn/Co ratios between two to five and two to four respectively correspond to antique porcelain.     

RIETVELD X-RAY DIFFRACTION AND X-RAY FLUORESCENCE ANALYSIS OF AUSTRALIAN ABORIGINAL OCHRES*

Rietveld phase analysis of X-ray powder diffraction patterns and chemical analysis by X-ray fluorescence spectroscopy have been used to characterize a series of red and yellow ochre samples from Aboriginal ochre deposits in South and Western Australia. The ochres were found to have diverse mineralogy, being mixtures of up to seven minerals, and also to have complex trace element signatures. The mineralogical characteristics and geochemistry of the ochres can be used to identify the source quarries. Using this combination of analytieal techniques it may be possible to trace the source of ochres in burial sites and on objects back to the original quarries.     

A TECHNOLOGICAL EXAMINATION OF NINTH–TENTH CENTURY AD ABBASID BLUE‐AND‐WHITE WARE FROM IRAQ,AND ITS COMPARISON WITH EIGHTH CENTURY AD CHINESE BLUE‐AND‐WHITE SANCAI WARE*

Eight sherds of ninth–tenth century ad Abbaesid blue‐and‐white glazed earthenware, excavated in 1931 at Hira in western Iraq, were analysed using, variously, quantitative wavelength‐dispersive spectrometry (WDS) and energy‐dispersive spectrometry (EDS) in association with scanning electron microscopes (SEM), and semi‐quantitative X‐ray fluorescence spectrometry (XRF). In order to compare the compositions of the cobalt pigments used, the glazes of seven complete vessels of eighth century ad Chinese Tang blue‐and‐white sancai were also analysed semi‐quantitatively using XRF. The Abbasid wares were shown to have used traditional Mesopotamian alkali–lime glazes applied to calcareous clay bodies. Half the glazes examined were opacified with tin oxide. Three types of blue decoration (i.e., raised; spreading; and flat, non‐spreading) were produced using a variety of formulations, including a mixture of cobalt pigment with lead oxide. The sources of the ores used for the cobalt pigments have not been identified. However, the analytical data showed that the cobalt ore used for the Abbasid blue‐and‐white ware could be distinguished from that used for the Tang blue‐and‐white sancai by its higher iron content and by the presence of a significant amount of zinc. The use of cobalt‐blue decoration on the ninth–tenth century ad Abbasid ware was anticipated in China by eighth century ad Tang blue‐and‐white sancai wares. However, whether its introduction by the Abbasid potters should be seen as an independent invention that followed the introduction of tin‐opacified glazes in Iraq, or whether it was influenced in some way by Chinese originals, is still unresolved.     

A QUANTITATIVE FABRIC ANALYSIS APPROACH TO THE DISCRIMINATION OF WHITE MARBLES*

Quantitative fabric analysis was applied in order to discriminate better among white marbles from various quarries of archaeological interest. This method provides an effective complementary tool to a characterization based upon petrography, cathodoluminescence microscopy and stable isotopes. Very good discrimination of marbles is achieved with the help of simple variables such as major axis and the shape-specific PARlS-factor. Using quantitative fabric analysis, marbles with similar cathodomicrofacies, as, for example, the Naxian quarries of Apiranthos, Koronos, Flerio and Kinidaros and the quarry of St. Beat (French Pyrenees), can be distinguished from each other. Marbles collected within one quarry may display dissimilar cathodomicrofacies. The common origin of such specimens can be determined with the aid of quantitative fabric analysis, as shown for the quarries of Kinidaros as well as St. Béat.     

THE CHEMICAL COMPOSITION OF BLUE PIGMENT ON CHINESE BLUE‐AND‐WHITE PORCELAIN OF THE YUAN AND MING DYNASTIES (ad 1271–1644)*

The chemical compositions of the glazes and pigments of 39 blue‐and‐white porcelains of Ming Dynasty date and three of Yuan date were examined by SR‐XRF. Both the analysis of the Fe/Mn ratio in the light blue areas of the glaze and a comparison of the Fe/Mn values between light blue, dark blue and clear glaze areas reveals that the samples can be divided into three groups. The results indicate that there are two significant changes of provenance of blue pigment during the Ming Dynasty and that some kinds of pigment were most probably imported from the Middle East. Considering literature records and other scholars’ studies, an outline picture of the pigment used on Chinese blue‐and‐white porcelain produced in Jingdezhen in the Yuan and Ming Dynasties is presented.     

THE CHEMICAL COMPOSITION OF SOME ARCHAEOLOGICALLY SIGNIFICANT FLINT FROM DENMARK AND SWEDEN

Flint was one of the most widely employed raw materials for artefact manufacture in Denmark and Sweden during the Stone Age, and it continued to be used during subsequent periods. Prehistoric flint mining and lithic manufacturing studies in these countries have attracted considerable attention, but there have been no recent attempts to chemically characterize the geological source materials. This paper builds on a pilot study ( Hughes et al. 2010 ) and uses energy‐dispersive X‐ray fluorescence (EDXRF) analysis to determine quantitative composition estimates for nine major, minor and certain trace elements in seven archaeologically significant flint sources in Denmark and Sweden, along with new data on a number of other sources of prehistoric significance. These data provide a geochemical foundation for ongoing research devoted to determining contrasts and continuities in the time and space utilization of flint sources in Scandinavian prehistory.     

NEUTRON ACTIVATION ANALYSIS OF SIXTEENTH- AND SEVENTEENTH-CENTURY EUROPEAN BLUE GLASS TRADE BEADS FROM THE EASTERN GREAT LAKES AREA OF NORTH AMERICA*

Sixteenth- and seventeenth-century European blue glass trade beads from aboriginal sites in the eastern Great Lakes area of North America have been analysed non-destructively using low neutron dose instrumental neutron activation analysis, so that the beads could be returned to their keepers. Dark blue (cobalt-coloured) beads are readily separable from turquoise (copper-coloured) beads. Differences in the chemistries of the turquoise blue beads appear to be useful in separating glass beads from the two centuries. Low calcium, sixteenth-century turquoise beads tend to distintegrate by a leaching of the alkali metals.     

ANALYSING ARCHAEOLOGICAL BASALT USING NON‐DESTRUCTIVE ENERGY‐DISPERSIVE X‐RAY FLUORESCENCE (EDXRF): EFFECTS OF POST‐DEPOSITIONAL CHEMICAL WEATHERING AND SAMPLE SIZE ON ANALYTICAL PRECISION*

Energy‐dispersive X‐ray fluorescence (EDXRF) has been commonly used to determine geological sources of volcanic glass artefacts, but its ability to discriminate between basaltic sources is less developed. We examine the precision and accuracy of non‐destructive EDXRF for basalt artefacts by analysing varying size and weathering characteristics. The experiments identified no appreciable effect in reproducibility or measured composition due to thickness (down to 1 mm) or natural weathering of pre‐contact flake scars for the 17 elements measured in this study. Samples with surface area less than 100 mm², however, show significant variability in measured composition and reproducibility.     

PROVENANCE STUDIES OF KOREAN CELADONS OF THE KORYǑ PERIOD BY NEUTRON ACTIVATION ANALYSIS*

Neutron activation analyses of the body fabric of celadons from the main production sites of the Koryǒ period have shown differences in composition between kilns. Comparison of over 50 celadon objects in the collections of the British Museum with this data base from the production sites has permitted the assignment of over 40 of the pieces to their kiln of origin The majority show the trace element pattern of the Sadangri kilns, a smaller proportion are assigned to Yuchǒnri, while others are assigned to the kilns at Chinsanri (underglaze iron) and Kyǒngsǒ-dong (unglazed). A representative group of Chinese Yue wares arc clearly different from Koryǒ celadons in trace element composition.     

CHEMICAL AND MINERALOGICAL ANALYSES OF GALLO-ROMAN WALL PAINTING FROM DIETIKON,SWITZERLAND

Around 90 samples of Roman wall painting dating from the first to the third century AD were analysed using different analytical techniques: X-ray diffraction, X-ray fluorescence, infrared spectrometry, scanning electron microscopy, energy dispersive spectrometry, optical microscopy and physico-chemical tests. The identified pigments are: ash, calcite, carbon black, celadonite, cinnabar, Egyptian Blue, glauconite, goethite, hematite and red lead. Pigment mixtures were used to get other colours such as brown, pink or purple. Three types of plaster were used: a first, and most dominant, with river sand, a second with crushed tile for damp places and a third, to which cinnabar was exclusively applied, was prepared with crushed calcite crystals.     

LASER ARGON DATING AND GEOLOGICAL PROVENANCING OF A STONE AXE FROM THE STONEHENGE ENVIRONS*

The recently-developed laser microprobe ⁴⁰argon-³⁹ argon technique has been used to give a geological date for a rhyolitic tuff stone axe fragment from the Stonehenge environs. The method requires only milligramme-sized samples and gives dates of sufficient accuracy to aid in provenancing artefacts to sources, as well as information on the heating history of samples. The axe sample is of Lower Carboniferous date (341 ± 5 Ma) and this limits possible sources to outcrops within the Scottish Midland Valley and small altered exposures in Dartmoor. X-ray fluorescence analysis of the axe suggests the Scottish Midland Valley as the more likely source. The laser argon analysis also shows that the implement had not been heated in antiquity. Laser argon-argon dating can, therefore, be a useful tool in artefact study.