RECENTLY IDENTIFIED EGYPTIAN PIGMENTS

On several bowls from Nubia (1600 b.c. ) and on one canopic jar (New Kingdom) huntite, a calciummagnesium-carbonate CaCO₃. 3MgCO₃ was identified by means of X-ray diffraction and infra-red absorption techniques. Vases from the Amarna period (1370 b.c. ) are decorated with a blue paint, which proved to be cobalt-blue. Copper chloride atacamite was used on limestone reliefs from Thebes-West but the green frit chrysocolla occurs more frequently on Egyptian objects as is mentioned in literature.     

Report of the Portable Antiquities Scheme 2010

Abstract

This paper deals with a group of metal tobacco boxes which are probably all of Dutch or German origin. The tobacco box industries of both countries and their backgrounds are considered, as are box design themes, boxes known from archaeological and pictorial contexts, and existing dated or signed examples in the group and in comparable collections. German craftsmen and their workshop techniques are also discussed. The concluding section contains a plea for further information on the various topics dealt with in the paper.     

ROMANO‐EGYPTIAN RED LEAD PIGMENT: A SUBSIDIARY COMMODITY OF SPANISH SILVER MINING AND REFINEMENT*

Samples of red pigment from a group of seven Roman‐period Egyptian mummies, known as red‐shroud mummies, are investigated. Elemental analysis by inductively coupled plasma time‐of‐flight mass spectrometry (ICP–TOFMS) shows that the samples contain mostly Pb (83–92% by weight), along with 0.2–2.0% Sn. All of the samples are found to have similar trace element distributions when normalized to the continental crust, suggesting that they share a common geological origin. Lead isotope ratios are found to match the mixed lead sources typically associated with Rio Tinto, Spain – a site extensively mined for silver during the first century ad . Raman microspectroscopy identifies the major phase of each sample to be red lead (Pb₃O₄) with a minor phase of lead tin oxide (Pb₂SnO₄). Lead tin oxide does not occur naturally, and its incidental occurrence within the sample indicates that the material was heated under oxidative conditions at temperatures in excess of 650°C. In archaeological contexts, the high‐temperature oxidative treatment of lead is typically associated with metallurgical refinement processes such as cupellation. Based on this evidence, it is argued that the pigment was produced out of litharge associated with silver cupellation at the Rio Tinto site.     

The Provenance of Historical Gunpowder from South‐Western Japan: A Stable Isotopic Approach

Stable isotopic analysis was undertaken for the gunpowder ingredients from crude saltpetre and propellants from several types of gun that prevailed during the late 19th century in south‐western Japan. Stable isotopic signatures for δ¹⁵N_{saltpetre nitrogen}, δ³⁴S_{native sulphur} and δ¹³C_{charcoal carbon} in crude saltpetre, gunpowder magazines bearing the trademark of mills from southern Scotland and cartridges for an improved Sharps rifle (with a US trademark) all imply common assemblages from the same source (saltpetre and native sulphur from British India and Sicily, respectively) in the United Kingdom (UK). One Pritchett patron is common for muzzle‐loading Enfield rifles, while the other suggests a four‐allied lead bullet for an unidentified hand gun. Propellants in the Pritchett patron from the same institution also suggest a common source of these rifles. On the contrary, the ingredients for an unidentified rifle and time fuse for a Paixhans gun with unique stylistic devices showed distinctive isotopic signatures, indicating a local Japanese origin. The Pritchett patron from the Kumamoto Museum involved a mixed provenance from the UK and Japan. The stable isotopic analysis provides direct evidence for the ultimate origin of the propellant.     

The stable isotopic composition of historical black powder applicable to a Japanese Tanegashima matchlock

The objective of the present study is to employ stable isotope ratio measurements (δ¹⁵N, δ³⁴S and δ¹³C) of the nitrogen, sulphur and carbon in black powder (a mixture of saltpetre, native sulphur and charcoal) as a means of source identification. A sum total of 20 samples of historical black powder applicable to matchlocks were collected from six locations throughout Japan. This classic type of hand gun prevailed up to the introduction of the modern rifles, with quicker loading and higher efficiency, in the mid‐to‐late 19th century. δ¹³C_{charcoal carbon} values showed the predominant use of C₃ plants as a source material. Except for a few unusual samples with a probable exotic origin, δ¹⁵N_{saltpetre nitrogen} values were largely consistent with those of domestic products using classical biotechnology. The isotopic analysis for native sulphur (δ³⁴S_{native sulphur}) indicates a complicated marketing route.     

The Seasonal Mobility Model for Prehistoric Herders in the South-western Cape of South Africa Assessed by Isotopic Analysis of Sheep Tooth Enamel

A pattern of seasonal mobility between the coast and the hinterland by Khoekhoe pastoralists in the south-western Cape of South Africa was documented at the time of European contact. Because the region is characterized by a mosaic of geological substrates of various ages and vegetation types with different proportions of C₃ and C₄ plants, this mobility model for prehistoric herders can be tested by analysis of carbon, oxygen and strontium isotope ratios in domestic bovid tooth enamel. Isotopic analysis was performed on archaeological sheep, cattle, eland and steenbok teeth from the Late Stone Age site of Kasteelberg on the Vredenburg Peninsula. Sequential sampling of enamel provided a chronological record of the isotopic composition of diet during tooth formation. Results from carbon and oxygen isotope analysis of archaeological and modern steenbok teeth show seasonal variation in the δ¹³C of local pastures in the vicinity of the site (up to 2·9‰ in a single individual), which could be due to seasonal change in proportions of C₃ and C₄ plants and/or seasonal variation in the δ¹³C of C₃ plants. A pattern of seasonal change of 0·9–3·5‰ in the δ¹³C of tooth enamel is also observed in the sheep teeth. This amplitude of variation could be due to local seasonal changes, thus it is not possible, from the δ¹³C values, to infer whether the sheep were moving seasonally. Results from ⁸⁷Sr/⁸⁶Sr analysis of two sheep suggest that one individual stayed all year round on the coast, whereas the other had grazed in the interior for part of its life. Both δ¹³C and ⁸⁷Sr/⁸⁶Sr values measured in a cow tooth suggest that this animal spent part of its life in the interior, even though it died at Kasteelberg. Results on this cow also suggest longer residence within habitats rather than seasonal mobility. A clear pattern of seasonal mobility between the coast and the interior has not been shown for prehistoric pastoralists. However, the pattern of mobility attested in historical times might have developed only later in prehistory, when cattle pastoralism developed in the region.     

Evaluation of Quantitative XRF Analysis Applied to Determine Cobalt Sources in Chinese Blue‐and‐White Porcelain

A method using the ratios between MnO, Fe₂O₃ and CoO to differentiate the cobalt sources for Chinese blue‐and‐white porcelain was developed in Oxford in the 1950s using X‐ray fluorescence (XRF) analysis directly on the glaze. In this paper, six blue‐and‐white porcelain sherds from the Luomaqiao kiln were analysed by XRF on the glaze and by scanning electron microscopy with energy‐dispersive spectrometry (SEM‐EDS) in cross‐section. The ratios between MnO, Fe₂O₃ and CoO calculated by quantitative XRF and EDS analyses are different. The analysis depths for MnO, Fe₂O₃ and CoO are < 60 μm by XRF analysis. However, the average glaze thickness of samples is > 400 μm, and the MnO, Fe₂O₃ and CoO mainly remain in the lower layer of the glaze, which is beyond the analysis depths of XRF analysis. The limitations of major and minor quantitative analyses for differentiating cobalt sources are discussed.     

Geochemistry and origin of natural gases dissolved in brines from gas fields in southwest Japan

Previous geochemical studies indicated that most natural gases dissolved in brines in Japan are of microbial origin, consisting of methane produced via carbonate reduction. However, some of those from gas fields in southwest Japan contain methane relatively enriched in ¹³C, whose origin remains to be clarified. To address this issue, chemical and isotopic analyses were performed on natural gases and brines from the gas fields in Miyazaki and Shizuoka prefectures, southwest Japan. Methane isotopic signatures (δ¹³C ≈ ?68‰ to ?34‰ VPDB; δ²H ≈ ?183‰ to ?149‰ VSMOW) suggest that these gases are of microbial (formed via carbonate reduction) or of mixed microbial and thermogenic origin. The relatively high δ²H‐CH₄ values and their relationship with the δ²H‐H₂O values argue against the possibility of their formation via acetate fermentation. The δ¹³C‐CO₂ values (≈?5‰), together with the slope of the correlation between δ²H‐CH₄ and δ¹³C‐CH₄ (Δδ²H‐CH₄/Δδ¹³C‐CH₄ ≈ 1), contradict the possibility of their formation via carbonate reduction followed by partial oxidation by methanotrophs. The ³He/⁴He ratios of the gases from Miyazaki (≈0.11–1.3 Ra) and their low correlation with δ¹³C‐CH₄ values do not support an abiogenic origin. It is inferred therefore that the high δ¹³C‐CH₄ values of natural gases dissolved in brines from gas fields in southwest Japan are indications of the contribution of thermogenic hydrocarbons, although whether abiogenic hydrocarbons contribute significantly to the gases from Shizuoka requires further investigation. This study has clarified that, for the future exploration of natural gases in southwest Japan, we should adopt the strategies for conventional thermogenic gas accumulations, such as checking the content, type and maturity of organic matter in the underlying sedimentary rocks.     

Diurnal variations of equatorial electrojet parameters derived from POGO solstitial data

The POGO electrojet data have been analysed for the winter and summer solstitial seasons of the two years, 1968 and 1969, respectively. Our analysis yielded a very large number of values (about 432), each of the electrojet half width, w, its peak current intensity, J₀, and its total eastward current, I₊, at 0900–1400 LT in December, and at 1000–1500 LT in June solstitial seasons, respectively. The all-longitude daytime values of the parameters are 246 ± 48 km for w,216 ± 60 A km⁻¹ for J₀, and (58 ± 8) × 10³A for I₊, in December of 1968 and 218 ± 19 km for w, 187 ± 20 A km⁻¹ for J₀, and (45 ± 3) × 10³ A for I₊, in June of 1969, respectively. We therefore present a diurnal study covering the entire Earth, in which for the first time, morning data earlier than 1000 LT are incorporated in the analysis. This has enabled us to chart a clearer picture of the temporal variations of electrojet parameters at two different solstices. This shows that all of the three parameters vary substantially with local time, in such a manner that J₀ and I₊ attain maximal values around local noon, while w is a minimum then, and therefore confirms the finding of Agu and Onwumechili.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.     

Oxygen isotopic evidence of residence and migration in a Greek colonial population on the Black Sea

Oxygen isotope analysis was performed on the enamel of the first and third permanent molars of 60 individuals excavated from the Kalfata-Budjaka necropolis associated with the ancient Greek colony of Apollonia Pontica (5th–3rd centuries BC) on the Black Sea coast of Bulgaria. The objective of this study was to examine the geographic origins and residential histories of these individuals and to compare the isotopic data with archaeological evidence derived from the burials in an attempt to distinguish ‘locals’ from ‘non-locals’. The analysis revealed that 55 of the 60 individuals sampled were either locally born or came from areas outside of Apollonia with isotopically similar δ¹⁸O values. Five individuals were identified as ‘non-local’, and their isotope values suggest that they originated from areas with higher δ¹⁸O_w of precipitation, most likely the Aegean region. Unfortunately, the archaeological evidence associated with these five skeletons provides no clues as to their place of origin.     

The Production and Circulation of Carthaginian Glass Under the Rule of the Romans and the Vandals (Fourth to Sixth Century ad): A Chemical Investigation

Fifty‐seven glass samples from Carthage dating to the fourth to sixth century ad were analysed using the electron microprobe. The results show that these samples are all soda–lime–silica glass. Their MgO and K₂O values, which are below 1.5%, suggest that they were made from natron, a flux that was widely used during the Roman period. The major and minor elements show that these samples can be divided into four groups, three of which correspond to the late Roman period glass groups that were found throughout the Roman Empire: Levantine I, and ‘weak’ and ‘strong’ HIMT. Of particular interest is our Group 2, which is technologically and compositionally similar to HIMT glass and the CaO and Al₂O₃ values of which are similar to those of Levantine I. Glass of similar composition has been reported by several authors and is predominantly found dating from the late fifth to seventh century. This could represent a ‘new’ glass group; therefore further study is needed to determine its origin. Also, this study suggests that the Vandal invasion in North Africa did not disrupt the glass trade between Carthage and the Levantine coast.     

About the origin of high energy electrons in the inner radiation belt

A large flux of > 100 MeV electrons were registered in the inner radiation belt on low-altitude satellites. The origin of that flux is discussed. It appears that slow radial diffusion (D_o = 10⁻¹³ 1/s) gives a low probability for penetration of these electrons to small L from the boundary of magnetosphere because of synchrotron radiation energy losses. It is found that they can enter to the inner belt region without such losses after great magnetic storms when high speed radial diffusion sometimes takes place. Two great storms on 8–9 Feb.] 986 and 24 March 1991 are examples when one can directly observe a penetration of energetic electron fluxes into magnetosphere. The assumption about their Jovian origin is discussed.     

Chemical analyses of organic residues in archaeological pottery from Arbon Bleiche 3, Switzerland – evidence for dairying in the late Neolithic

Fatty acids distribution and stable isotope ratios (bulk δ¹³C, δ¹⁵N and δ¹³C of individual fatty acids) of organic residues from 30 potsherds have been used to get further insights into the diet at the Late Neolithic (3384–3370 BC) site of Arbon Bleiche 3, Switzerland. The results are compared with modern equivalents of animal and vegetable fats, which may have been consumed in a mixed ecology community having agrarian, breeding, shepherd, gathering, hunting, and fishing activities. The used combined chemical and isotopic approach provides valuable information to complement archaeological indirect evidence about the dietary trends obtained from the analysis of faunal and plant remains. The small variations of the δ¹³C and δ¹⁵N values within the range expected for degraded animal and plant tissues, is consistent with the archaeological evidence of animals, whose subsistence was mainly based on C₃ plants. The overall fatty acid composition and the stable carbon isotopic compositions of palmitic, stearic and oleic acids of the organic residues indicate that the studied Arbon Bleiche 3 sherds contain fat residues of plant and animal origin, most likely ruminant (bovine and ovine). In several vessels the presence of milk residues provides direct evidence for dairying during the late Neolithic in central Europe.     

临水窑与介休窑白底彩绘工艺的对比研究

白底黑花装饰风格的瓷器,始终是陶瓷、科技界和陶瓷爱好者关注的热点。临水窑(磁州窑)与介休窑白底黑花风格的瓷器之间有着密切的联系,但是对于两窑产品的科技分析甚少,至于两者的对比研究更是无从谈起。因此,本工作利用岩相分析、SEM-EDS等方法分析了临水窑(磁州窑)、介休窑样品的瓷胎、化妆土及瓷釉的化学成分和显微结构。比较分析显示,两窑样品的瓷胎均为低硅高铝配方,且介休窑瓷胎中的Al2O3含量更高;两窑瓷胎粗糙,Fe2O3、TiO2含量较高,致使其呈浅黄色。瓷胎表面均施有化妆土,所不同的是,介休窑的瓷胎表面施有两层化妆土,其靠近釉的一层化妆土(h2),Fe2O3、TiO2含量极低,靠近胎的一层化妆土(h1),Fe2O3、TiO2含量较高;临水窑样品的瓷胎表面仅施一层化妆土,其Fe2O3、TiO2含量较低,但高于介休窑近釉层化妆土中的相应含量。介休窑瓷釉为典型的高钙釉,而临水窑则为典型的碱钙釉和钙碱釉。不难认识到,介休窑似在临水窑白底黑花及化妆土工艺的基础上,因地制宜,勇于创新,形成了成本低廉、技术先进的两层化妆土工艺,在当地原料较为粗糙的条件下,生产出质量较好的白底釉下彩绘瓷器。     

Mössbauer Spectroscopic and Chromaticity Analysis on the Colourative Mechanism of Ancient Goryeo Celadon from GangJin and Buan

In ancient Goryeo celadon excavated from the kiln sites in the GangJin and Buan areas, the effect of the chemical composition and ionic state of Fe on the colour was evaluated by Mössbauer spectroscopy and chromaticity analysis. According to chromaticity analysis, the L* value (brightness) of the glaze was shown to be affected more by TiO₂ and MnO than by Fe₂O₃, and the body was affected more by Fe₂O₃ than by TiO₂. The a* value was found to be affected by Fe₂O₃ and TiO₂ in the glaze, whereas there was hardly any change in the body according to the composition. As for the b* value, changes due to the composition were shown to be smaller than those for the L* and a* values. According to the Mössbauer spectroscopy results, as the quantities of TiO₂ and Fe₂O₃ are increased, Fe²⁺/Fe³⁺ decreases; while the changes in Fe²⁺/Fe³⁺ with MnO and P₂O₅ are negligible. As the quantity of Fe²⁺/Fe³⁺ increases, the a* and b* values decrease, which results in the change of colour from red–yellow to blue–green. The characteristic green colour can be attributed to increased L* (brightness) and decreased a* and b* values (blue–green shift) due to the reduced Fe ion, which is mainly determined by the TiO₂ and Fe₂O₃ contents.     

The origin of the ancient Egyptian drink Shedeh revealed using LC/MS/MS

Ancient Egyptians were buried with the most precious food and drink as sustenance for their afterlife. One of these was Shedeh, the most valued and appreciated beverage in ancient Egypt. The botanic origin of Shedeh remains unclear as no mention of its raw material has survived. Some scholars have proposed that Shedeh was a pomegranate wine, while others, a grape wine. Presented here is the first ever analytical evidence of Shedeh's origin through the analysis of a sample of a residue from an extraordinarily well preserved Shedeh amphora from King Tutankhamun's collection. The previously developed LC/MS/MS wine markers method for archaeological samples was used and our results reveal Shedeh had a red grape origin.     

Removal of natural organic dyes from wool–implications for ancient textile provenance studies

Ancient wool textiles recovered from archaeological sites are in many cases originally dyed with natural organic dyestuffs from vegetable sources. These include among others woad (Isatis tinctoria L.), weld (Reseda luteola L.), and madder (Rubia tinctorum L.). These dyestuffs could be a threat to the use of the strontium isotopic system as a tracer for provenance studies of ancient wool, because they could potentially contaminate the signature of the textile's raw material. We present a novel method which allows for efficient removal of organic dyestuffs in wool prior to strontium isotopic analysis. Our method is based on an oxidative release of the dyestuff constituents by ammonium peroxodisulfate [(NH₄)₂S₂O₈] solution, combined with hydrofluoric acid (HF) that has shown to effectively remove/dissolve adhering dust micro-particles. Our multi-analytical results show that such a pretreatment is capable of removing >98% of the originally present organic dyestuffs without significantly destroying the wool structure. The strontium isotopic ratios of the residual wool fraction after the application of the pretreatment are sensitive to the origin and, therefore, can be used as tracers for the provenance of the raw material. We propose to apply this method to ancient wool textiles in which positive identification of organic dyestuff constituents by High Performance Liquid Chromatography (HPLC) was made.