Integrated Analytical Techniques for the Study of Colouring Materials from Two Megalithic Barrows

We have determined the composition of rock art pigments from two megalithic barrows located in the north of Portugal. The use of XRD, SEM–EDS and FT–IR spectroscopy confirmed the presence of hematite and kaolinite in the red pigments from the Eireira barrow, and kaolinite in the white pigment from the Leira das Mamas barrow. The organic composition of the pigments was studied by GC–MS, suggesting that the red sinuous lines and dots from the Eireira barrow were prepared with cooked or heated algae and/or aquatic plants, with egg as binder, while the white pigment from the Leira das Mamas barrow revealed a mixture of vegetable oils for kaolinite moulding, which could be stabilized by temporary exposure to high temperatures. The multi‐analytical approach used on this study of megalithic pigments allowed the recovery of important data about north‐western prehistoric communities, namely the way in which they exploited existing resources and their ability to transform them.     

Study of the Technique and of the Materials of a 19th‐Century Polychrome Wood Mask from Papua New Guinea

This paper presents the results of the analysis carried out on a polychrome wood mask from Papua New Guinea during conservation work at Pigorini Museum's restoration laboratory. The significance of this study is that no prior work has characterized the painting materials of Papua New Guinea masks both with spectroscopic and internal microstratigraphic analysis. In fact, these objects were studied especially from an anthropological or conservative point of view and the wood was wrongly defined by its visual appearance. Microstratigraphic and spectroscopic investigations discovered a refined execution technique that up to now has not been demonstrated. The stratigraphy of the painted layers demonstrates a deep knowledge of the materials and of the application techniques on the part of the Papua New Guinea people, together with the ability to foresee the aesthetic result for the artefact. The analysis of the constitutive materials and of the stylistic features supplied valid results in favour of provenance of the mask from Papua New Guinea.     

Glass Beads from 15th–17th Century CE Jar Burial Sites in Cambodia's Cardamom Mountains

A total of 74 glass beads, included as grave goods in 15th–17th century CE jar burials from Cambodia's Cardamom Mountains, were analysed using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS). Several glass types were identified, including two subtypes of high‐alumina mineral soda glass, and lead–potash glass. The final glass type represents a newly discovered and previously unidentified type of high‐alumina soda glass, with high magnesia (m‐Na–Al Mg>). This study represents the first glass data from the mid‐second millennium CE from Cambodia and sheds light on the multiple long‐distance maritime exchange networks in which the upland people buried in the jars were participating.     

Enhancing Understanding of the Emergence of Global Trade: Analysis of 17th‐ to 19th‐Century Spanish Coins Recovered from Western Australian Shipwrecks Using Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry (LA–ICP–MS)

This research uses legacy data from shipwrecks to further our understanding of global silver movement in the 17th to 19th centuries by analysing a collection of silver coins held by the Western Australian Museum. Three hundred and eighty‐nine silver coins were analysed for their trace element fingerprint in order to identify provenance. The coins are a selection from the ships Batavia, Vergulde Draeck, Zuytdorp, Rapid and Correio da Azia, all wrecked off the coast of Western Australia between 1629 and 1816. Analysis was undertaken using laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS), a relatively non‐destructive technique with a sensitivity of parts per million to parts per billion. Data were interpreted using linear discriminant analysis (LDA), which allowed the coins of known provenance to be sorted into identifiable subgroups on the basis of their trace and minor elemental fingerprints, while 27 unidentified coins were compared with this database and their mint of origin predicted. These results have implications for the provenance determination of archaeological artefacts of many materials.     

The Preservation of Invertebrates in 16th‐Century Cesspits at St Saviourgate,York*

The taphonomy of invertebrates from 16th‐century cesspits at St Saviourgate, York, was investigated. Earthworms, fly larvae and puparia are preserved through replication in calcium phosphate, a process facilitated by acidic cesspit pore water and by the presence of abundant organic matter, bones and shells. Features preserved by mineralization include muscles, blood vessels and setae. Non‐mineralized invertebrate remains include puparia and beetles. Py–GC/MS (flash pyrolysis–gas chromatography/mass spectrometry) revealed a very high level of preservation of structural biomolecules, with all the protein and chitin markers that are evident in the living forms still being detectable in the divalent remains.     

An Osteobiography of a 19th‐Century Dog from Toronto,Canada

A 19^th‐century dog burial uncovered from a historical homelot in Toronto, Canada, provided a unique opportunity to reconstruct the individual's osteobiography. Of particular interest are the dog's very large size and a suite of skeletal pathologies. Recovery of a nearly complete skeleton combined with the use of X‐rays and micro‐computed tomography (micro‐CT) allowed for a discriminating differential diagnoses. Stable isotope analyses were applied to investigate questions of diet. Results reveal an individual who suffered greatly from disease towards the end of his life and hint at its owners attitudes towards dogs. The interdisciplinary approach applied to this case study highlights the potential information obtainable from pet burials. We argue that better analyses and reporting of pet burials will help address research questions targeting broader themes related to human–animal relationships. Copyright © 2015 John Wiley & Sons, Ltd.     

Wine Bottles From Lisbon: Archaeometric Studies Of Two Archaeological Sites Dated From The 17th To The 19th Century

Two sets of wine bottles dated between the end of the 17th and the 19th centuries were characterized by means of μ‐PIXE (major and minor elements) and LA–ICP–MS (trace and REE elements). The fragmented wine bottles were recovered from two archaeological contexts in Lisbon and reach a total of 79 fragments. One of the archaeological bottle sets comes from a house structure that collapsed during the major earthquake in 1755, providing a precise terminus ante quem. The second set comes from the exploratory archaeological intervention performed in Rua do Arsenal, where the Côrte‐Real Palace (built in the 16th century), was discovered. From this site, posterior contexts dated up to the 19th century were considered. This systematic study allowed the glass to be identified as high‐lime, low‐alkali (HLLA) for all the considered chronologies. However, the 19th‐century bottles have a different HLLA composition, suggesting the use of synthetic soda. Comparison with data from literature showed some similarity with English, Belgium and French reported compositions. This is the first systematic attempt to characterize the composition of glass wine bottles circulating in Portugal, giving new insights into their probable provenances, and on the exchange between Portugal and its trading allies.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

SCIENTIFIC INVESTIGATIONS OF ANTIQUE LACQUERS FROM A 17TH‐CENTURY JAPANESE ORNAMENTAL CABINET

A recent restoration of a 17th‐century Japanese lacquer cabinet revealed various later treatments over the original black coating to maintain and preserve the high gloss of the oriental cabinet over the course of time and to meet changing tastes. The comprehensive investigation on a series of coating samples was executed by means of two hyphenated techniques: gas chromatography – mass spectrometry (GC–MS) and pyrolysis combined with GC–MS (Py‐GC–MS). The results showed that the original lacquer is based on urushi and linseed oil, while the past interventions are composed of sandarac, shellac and dammar. Additional microscopic studies proved the multi‐layer structure of the lacquer and the use of different pigments.     

Electron Microprobe Analysis of 9th–12th Century Islamic Glass from Córdoba,Spain

Twenty‐six samples from domestic assemblages of 9th–12th century Córdoba were subjected to electron microprobe analysis. The results reveal two main compositional types. The first, encountered in 13 of the samples, seems to result from the combination of plant ashes with high‐impurity sand, and has some contemporary parallels from Syria and Egypt. The second type is a lead–soda–silica glass, encountered in a relatively high proportion of the glasses (11 of the 26 sampled), possibly formed by the addition of lead metal to existing glasses and with very few known parallels. These are among a very small number of results available to date on the chemical composition of glasses from medieval Spain, and the presence of a high proportion of lead–soda–silica glasses is particularly interesting, possibly indicating a technological practice unique to, or originating in, the western Muslim world.     

Pb and Sr Isotopes and the Provenance of the Painting Materials of Cornelius Krieghoff in 19th‐Century Canada

Radiogenic lead and strontium isotope data are presented for lead‐ and calcium carbonate/barium sulphate‐containing paint and ground samples from 15 paintings, executed between 1844 and 1871, by 19th‐century Canadian artist Cornelius Krieghoff. Like many artists of this era, Krieghoff used lead‐based pigments such as lead white, chrome yellow and Naples yellow, and extenders such as calcium carbonate and barium sulphate. The lead isotope analyses of the majority of these pigments are consistent with the isotopic compositions of lead mined from European lead deposits in England and/or Germany. However, three samples from Krieghoff's early career yield lead isotope compositions that are much more radiogenic than European sources. The lead isotope compositions of these three samples are consistent with the addition of a more radiogenic lead component that is similar to the lead derived from North American lead deposits in Missouri and Illinois (Mississippi Valley Pb–Zn type deposits). The strontium isotope compositions of the extenders suggest that the raw materials for calcium carbonate or barium sulphate extenders were largely derived from Palaeozoic to modern‐day marine environments. This study shows that pigments manufactured from North American lead were being incorporated into Canadian paintings as early as 1844.     

Polychromy Analysis on Cypriot Archaic Statues by Non‐ and Micro‐Invasive Analytical Techniques

The polychromy of limestone and terracotta statues from Cyprus attributed to the sixth to fifth centuries bc is analysed using non‐ and micro‐invasive techniques in order to shed light on the use of pigments during the studied period. The strengths and limitations of these methods for the present application are discussed. The identified pigments are iron‐containing compounds (red, yellow, green earths and iron–manganese black). No copper‐containing compounds were detected on the studied objects, despite the wide availability of copper minerals in Cyprus.     

High‐boron and High‐alumina Middle Byzantine (10th–12th Century ce) Glass Bracelets: A Western Anatolian Glass Industry

The trace element boron is present in most ancient glasses as an impurity, and high boron (≥ 300 ppm) marks raw material sources that are geologically specific and relatively uncommon. Recent analyses of Byzantine glass with high boron contents suggest that glass‐making was not limited to the traditional regions of the Levant and Egypt, and a production origin in or near western Anatolia is proposed. Glass bracelets from ?i?n al‐Tīnāt in southern Turkey give fresh evidence for the production and circulation of high‐boron glasses that closely correlates with object typology. The patterning of findspots suggests that high‐boron glass was closely connected to the Byzantine world.     

A MULTI‐ANALYTICAL APPROACH FOR THE CHARACTERIZATION OF COMMODITIES IN A CERAMIC JAR FROM ANTINOE (EGYPT)*

This paper describes a multi‐analytical chemical study performed on the original, almost totally conserved, content of a small ceramic jar from the Antinoe archaeological site (fifth to seventh centuries ad, Roman Egypt) and now belonging to the archaeological collection of the Istituto Papirologico ‘Girolamo Vitelli’ (Florence, Italy). Scanning electron microscopy with an energy‐dispersive X‐ray spectrometer (SEM–EDX), Fourier transformed infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) were all used to characterize the inorganic components of the archaeological material. The organic substances were analysed using FTIR, direct exposure mass spectrometry (DE–MS) and gas chromatography – mass spectrometry (GC–MS). The inorganic component essentially consisted of halite (NaCl). Among the NaCl crystals, lamellar elements were identified. They were chemically characterized by carbonato‐apatite and showed a concentric morphology typical of the scales of small fish. The most prevalent organic constituents of the sample were monocarboxylic acids, α,ω‐dicarboxylic acids, and cholesterol and its oxidation products. The organic material composition was consistent with the occurrence of lipids of animal origin. In addition, diterpenes related to pine pitch were also identified. The overall results suggest that the material recovered in the small ceramic jar found in Antinoe is a residue of fish‐based pickles such as garum, muria, allex and liquamen, which were commonly used in Roman times.     

Characterization of Pigment and Binder in Badly Conserved Illuminations of a 15th‐Century Manuscript

In this work we report a pre‐restoration spectroscopic study by a multi‐technique approach on the green pigment and the binder used in illuminations in a codex of the late 15th century. Our analysis aimed to characterize the badly deteriorated parts of the codex, mainly the green parts, by electron paramagnetic resonance (EPR), X‐ray diffraction (XRD), X‐ray fluorescence (XRF) and infrared spectroscopy (ATR‐IR). We will show that a combined study by EPR and IR spectroscopies on model systems allowed us to refine the general information obtained with the other techniques and to identify the binding media surrounding the chromophore Cu(II) ion.     

The Faragola Ceramic Collection: Ceramic Production,Consumption and Exchange in Seventh‐Century Apulia

A collection of 30 ceramic samples, 16 of coarse wares and 14 of fine painted wares, have been investigated by optical microscopy, scanning electron microscopy, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry and neutron activation analysis. Further samples of clayey sediments, both locally outcropping and found within the settling tank, have been submitted to the same analytical techniques for comparison with the ceramic collection. The results demonstrated that local clayey sediments were used as received for the production of coarse wares. The same raw materials were sieved and/or refined by decantation for the production of fine painted wares, which, in fact, provided results that were perfectly comparable with those for the clayey raw materials found within the settling tank. The Faragola productions were distinguished from the neighbouring Apulian productions according to petrographic features (the presence of leucite‐bearing volcanic rocks and Mn‐rich wads) and their bulk chemical composition.     

Developmental Fusion of the Malleus and Incus in a Late 19th‐Century Case of Aural Atresia

A pathological condition, aural atresia, was discovered associated with human remains recovered from a late 19^th‐century Catholic cemetery 2 km south of Battleford, Saskatchewan, Canada. Aural atresia, a congenital condition that results in a non‐existent external auditory meatus, was apparent on the right temporal bone of the remains of a young adult male. A complete osteological and contextual assessment, which included the use of a SkyScan 1172 micro‐CT scanner on the pathological incus that was recovered, indicated that the right incus and malleus had fused during early embryological development. The artifacts associated with this individual included a pocket mirror that may have represented a connection to the practice of oralism due to the discouragement of sign language by the authorities in that time period. The combination of advanced bone imaging and a complete contextual analysis suggests a differential diagnosis of nonfunctional hearing associated with the right ear, and the individual may have used a different means of communication. Copyright © 2011 John Wiley & Sons, Ltd.     

The Yenikapı 12 Shipwreck,a 9th‐Century Merchantman from the Theodosian Harbour in Istanbul,Turkey: construction and reconstruction

Shipwreck Yenikap? 12 was discovered in Yenikap?, Istanbul, Turkey in 2007 during rescue excavations carried out by Istanbul Archaeological Museums. The majority of the bottom of the shipwreck, found within the sediment‐filled Theodosian Harbour, is intact and part of the cargo was found in situ. According to the results of reconstruction studies, YK12 was a small merchantman working coastal waters, approximately 9.24m in length and 2.64m in breadth. The shipwreck is dated to the 9th century AD and was built with a mixed construction using the shell‐based method for the lower hull.     

Identification of Green Pigment Used in Persian Wall Paintings (ad 1501–1736) Using PLM,FT–IR,SEM/EDX and GC–MS Techniques

The technique of oil painting was introduced to Iran via a cultural exchange with Europe in the Safavid period (ad 1501–1736). Since the first attempt at scientific conservation of wall paintings in Iran in the 1960s, the nature of green pigment used in Persian wall paintings has not been clear, although work on contemporary miniature paintings has identified malachite and verdigris. PLM, FT–IR, SEM/EDX, GC–MS and the study of contemporary historical treatises of the Safavid period were the main tools used in the present study to identify the green pigments in Persian (oil‐based) wall paintings. Eight samples taken from the two famous Safavid buildings, Chehel Sotoon Palace and the Sukias House in Isfahan, were analysed. Here, the identification of copper‐based pigment and of verdigris in oil as oleate amends the existing knowledge of the green pigment used in these paintings. It also suggests that oleate was introduced to Persian artists via the European influence on Persian painting as a result of cultural exchange in the Safavid period, when the technique of Persian painting changed from tempera to oil painting. However, as verdigris in oil and resin can appear as oleate over time, it is unknown whether the Persian artists did this deliberately or accidentally.