Wall Paintings from the Roman Emona (Ljubljana,Slovenia): Characterization of Mortar Layers and Pigments

This study concerns the investigation of mortar layers and pigments of wall paintings from the Roman town of Emona (Ljubljana, Slovenia). Fragments of wall paintings consist of up to three preserved mortar layers. The mineralogical–petrographic compositions of the mortars were determined by means of optical microscopy and FT–IR spectroscopy. The investigated samples were divided into several groups based on similar thicknesses of the mortar layer, the binder colour and the composition of an aggregate. Furthermore, the results of mercury intrusion porosimetry showed that mortar layers consisting of carbonate grains exhibited lower porosity with respect to layers with mainly silicate grains, which is attributed to the angular shapes of carbonate aggregate. This is in accordance with the drilling resistance measurement system test (DRMS), confirming that layers with angular carbonate grains are harder than those with addition of rounded silicate ones, due to the good packing effect. The wall paintings were mainly executed using the fresco technique, while for some details secco was used. The identified pigments were red and yellow ochre, green earth, Egyptian blue, carbon black and lime white; all of them belonged to the so‐called austere pigment, which is quite common in Roman wall paintings.     

Where Do the Lead Ingots of the Saintes‐maries‐de‐la‐mer Wreck Come From? Archaeology Compared With Physics

The lead isotope compositions of many different samples from lead ingots of Roman age from two relicts (from Cabrera, and from Saintes‐Maries‐de‐la‐Mer) of the Western Mediterranean have been measured. Other lead isotope analyses of ores, metals or lead ingots from mines of Sierra Morena and from Cartagena and Sardinia have been accomplished. All the lead isotope measurements have been performed at the Joint Research Centre of the European Union, Ispra (Va), Italy. The samples have been prepared in a class 100 clean room, using only ultrapure reagents and FEP materials. In view of the archaeological arguments, it was possible to believe that the Roman lead ingots of the Saintes‐Maries‐de‐la‐Mer 1 wreck came from Spanish lodes, as well as those of the Cabrera 5 wreck. In fact, while the comparison between the first group of ingots (Cabrera 5) and the lead from Sierra Morena is consistent, the correspondence between the second group of ingots (Saintes‐Maries‐de‐la‐Mer 1) and the Cevennes ores (southern France) gives rise to several problems concerning the archaeological and physical origins. These problems are discussed.     

Baseline data for Andean paleomobility research: a radiogenic strontium isotope study of modern Peruvian agricultural soils

While the use of radiogenic strontium isotope values to examine paleomobility is increasingly common in the Andes, and beyond, many questions about baseline variability remain. To better understand baseline radiogenic strontium isotope compositions in the Andes, we present new ⁸⁷Sr/⁸⁶Sr values from Peruvian soil samples. Modern soil samples were collected from agricultural fields from the following areas in central and southern Peru: Arequipa, Atico, Camaná, Chala, Cusco, Ica, Ilo, Lima, Mejía, Moquegua, Nazca, Ocoña, Palpa, Pisco, Puno, Tacna, and Yauca. Samples were partially dissolved to better approximate the bioavailable strontium. Radiogenic strontium isotope values from the partially dissolved soil samples range from ⁸⁷Sr/⁸⁶Sr?=?0.70202 to 0.71894 and, for all soil samples, have a mean of ⁸⁷Sr/⁸⁶Sr?=?0.70773?±?0.00166 (1σ, n?=?114). In general, the ⁸⁷Sr/⁸⁶Sr values measured for soil samples collected from modern agricultural fields reflect the expected ⁸⁷Sr/⁸⁶Sr values based on bedrock geology. Comparing our new soil data with published radiogenic strontium isotope data for bedrock, soil, water, and faunal samples provides constraints on the regions in the Andes that can, and cannot, be distinguished through radiogenic strontium isotope analysis.     

Isotopic Composition of Lead in Copper Ores and a Copper Artefact from the La Profunda Mine (León,Spain)

This paper continues the characterization of the lead isotopic fingerprint of ancient copper mines in the north‐west of Spain. In this work, the lead isotopic compositions found in copper ores from the La Profunda mine are presented. Azurites and malachites sampled from this deposit were subjected to lead isotope analysis by multicollector ICP–MS. The results showed a clear radiogenic lead signature compatible with the presence of uranium‐rich minerals (such as zeunerite) in the same mining complex. Moreover, a rare copper artefact, found in the galleries of the mine during its modern exploitation, was also analysed and showed that local mineral was used for its manufacturing.     

Roman lead mining in Germany: its origin and development through time deduced from lead isotope provenance studies

High precision lead isotope analysis by Multi Collector Inductively Coupled Plasma Mass Spectrometry was applied to the investigation of more than 240 Roman lead objects from several archaeological sites in Germany, in order to obtain information on the pattern of Roman mining activity and ore processing in the area. Measurements of ore samples from German deposits east (Siegerland, Lahn-Dill, Ems) and west of the Rhine (Eifel, Hunsrueck) were made and supplemented with data from literature to create a data bank of lead isotope ratios of European lead occurrences. Comparing the isotope ratios of lead objects with those from German ore deposits shows that the source of over 85% of the objects is Eifel ore deposits, but that, in the early years, the Romans also imported lead from the Southern Massif Central and later from Britain.     

Identifying locals, migrants, and captives in the Wari Heartland: A bioarchaeological and biogeochemical study of human remains from Conchopata, Peru

The site of Conchopata in the central Peruvian Andes was the secondary center in the heartland of the Wari Empire (AD 600–1000), and in this study we examine whether this urban locale was populated by locals, voluntary migrants from distant regions, and/or captives who were forcibly brought to Conchopata. We examine radiogenic strontium isotope ratios from 72 dental enamel and bone samples representing 31 formal burials and 18 human trophy heads to distinguish between locals and non-locals, and we examine skeletal and archaeological data to establish whether non-local persons were voluntary migrants or captives. We also describe a new, straightforward technique in the evaluation of radiogenic strontium isotope ratios to assist in detecting non-locals when large datasets are available.Results show that natal Conchopata inhabitants should exhibit radiogenic strontium isotope ratios that range from ⁸⁷Sr/⁸⁶Sr = 0.70548 to ⁸⁷Sr/⁸⁶Sr = 0.70610. Thus, among the 31 burials, 29 exhibit local values, suggesting that Conchopata was not a cosmopolitan center to which numerous foreigners migrated; rather, it was populated by local peoples, likely the descendants of the preceding Huarpa culture. The two individuals with non-local radiogenic strontium isotope ratios are an infant and a 17–22 years old female. The archaeological context suggests that the female may have been taken captive for subsequent sacrifice, as she was interred in front of the ritual D-shaped structure in which decapitated human heads (trophy heads) and sacrificed camelids were deposited. Among the 18 trophy heads sampled, 14 have non-local values, confirming previous studies of smaller samples that suggested that Wari warriors travelled to other locales and took captives—both adults and children—for subsequent transformation into trophy heads. Additional analyses of bone-tooth pairs from a subsample (12 burials and six trophy heads) shows that the burial group was much more sedentary (homogenous radiogenic strontium isotope ratios in bones and teeth) and the trophy head individuals were much more mobile (heterogenous radiogenic strontium isotope ratios in bones and teeth). Overall, the multiple lines of evidence support the notion that the Wari Empire occasionally used militaristic means, combined with elaborate ritualism, to subjugate other populations, a tactic that may have helped Wari establish and maintain control in particular regions in the Andes.     

The Volterran Urns: Etruscan Painting and Travertine Supply

The artistic evolution of the Volterran cinerary urns is a good representation of Etruscan painting from the fourth to the first century bc . The interest generated by this type of object directed our research towards the study of the Volterran artefacts, including the analysis of the pigments as well as that of the rocks used for the coffers. The entire colour range shown by the painted urns has been sampled and investigated through Raman microscopy and scanning electron microscopy. Rock samples were taken both from the urns and from outcrops in ancient carbonate rock quarries near Volterra, from where they may potentially have been sourced. A set of 30 samples was collected and submitted to stable carbon and oxygen isotope analyses. The results obtained showed that the pigments used for the decoration of the Volterran urns were basically constituted by red ochre, Egyptian blue, carbon black and gypsum. The identification of lead‐based pigments and barium sulphates further informed us about old restorations undergone by several urns. As far as the provenance issue is concerned, the isotopic data indicate that the rocks used for the four urns were favourably comparable to those outcropping at Pignano, while two other urns were more similar to those sampled along the Elsa River at Colle Val d'Elsa.     

山东青州龙兴寺部分北齐佛造像石材及朱砂颜料分析研究

山东青州龙兴寺窖藏佛教造像出土于1996年,造像雕刻技艺精湛,数量多,贴金彩绘丰富,展现出一种特殊的佛教造像艺术特征。一些佛像由于长期掩埋和历史上遭到破坏,彩绘发生了褪色、变薄、起翘等现象。为了弄清佛造像彩绘颜料和结构,本研究采用三维视频显微镜、显微拉曼光谱分析、扫描电镜-能谱、偏光显微镜等仪器分析颜料的结构和化学组成。分析结果表明,龙兴寺佛造像红色颜料为辰砂(Hg S)与铅白(2PbCO_3Pb(OH)_2)混用;地子主要为铅白,经过对该批出土佛造像残碎的石块做薄片处理做偏光显微分析,得到造像石材的主要矿相为含菱铁矿、生物碎屑、白云石的泥晶灰岩(灰岩即石灰石)。     

Early Renaissance Production Recipes for Naples Yellow Pigment: A Mineralogical and Lead Isotope Study of Italian Majolica from Montelupo (Florence)

The Naples Yellow pigment was apparently used for the first time by the Egyptians, as a glass‐colouring agent. Also known in the Mesopotamian and Roman cultures, the recipe was lost in Western Europe between the fourth and the 16th centuries ad . The recipe for the production of lead antimonate recently discovered in the ‘Codice Calabranci’ (second half of the 15th century) at Montelupo, a small town near Florence (Italy) known for its large‐scale ceramic production, possibly represents the very first evidence of the reintroduction of Naples Yellow in Western Europe after a long period of absence. The major‐element composition of the lead antimonate pigment in the Montelupo ceramics of the 15th and 16th centuries is in accordance with the ‘Codice Calabranci’ recipes. Lead isotope analyses indicate that the lead used to produce the yellow pigments and the underlying glaze of the Montelupo majolica did not come from the Tuscan mining districts, but was possibly imported via Venice from more distant lead sources in Turkey.     

Invasion of a karst aquifer by hydrothermal fluids: evidence from stable isotopic compositions of cave mineralization

Mineral deposits in the Cupp‐Coutunn/Promeszutochnaya cave system (Turkmenia, central Asia) record a phase of hydrothermal activity within a pre‐existing karstic groundwater conduit system. Hydrothermal fluids entered the caves through fault zones and deposited sulphate, sulphide and carbonate minerals under phreatic conditions. Locally, intense alteration of limestone wall rocks also occurred at this stage. Elsewhere in the region, similar faults contain economic quantities of galena and elemental sulphur mineralization. Comparisons between the Pb and S isotope compositions of minerals found in cave and ore deposits confirm the link between economic mineralization and hydrothermal activity at Cupp‐Coutunn. The predominance of sulphate mineralization in Cupp‐Coutunn implies that the fluids were more oxidized in the higher permeability zone associated with the karst aquifer. A slight increase in the δ³⁴S of sulphate minerals and a corresponding δ³⁴S decrease in sulphides suggest that partial isotopic equilibration occurred during oxidation. Carbonate minerals indicate that the hydrothermal fluid was enriched in ¹⁸O (δ¹⁸O_SMOW ～ + 10‰) relative to meteoric groundwater and seawater. Estimated values for δ¹³C_DIC (δ¹³C_PDB ～ ? 13‰) are consistent with compositions expected for dissolved inorganic carbon (DIC) derived from the products of thermal decomposition of organic matter and dissolution of marine carbonate. Values derived for δ¹³C_DIC and δ¹⁸O_water indicate that the hydrothermal fluid was of basinal brine origin, generated by extensive water–rock interaction. Following the hydrothermal phase, speleothemic minerals were precipitated under vadose conditions. Speleothemic sulphates show a bimodal sulphur isotope distribution. One group has compositions similar to the hydrothermal sulphates, whilst the second group is characterized by higher δ³⁴S values. This latter group may either record the effects of microbial sulphate reduction, or reflect the introduction of sulphate‐rich groundwater generated by the dissolution of overlying evaporites. Oxygen isotope compositions show that calcite speleothems were precipitated from nonthermal groundwater of meteoric origin. Carbonate speleothems are relatively enriched in ¹³C compared to most cave deposits, but can be explained by normal speleothem‐forming processes under thin, arid‐zone soils dominated by C4 vegetation. However, the presence of sulphate speleothems, with isotopic compositions indicative of the oxidation of hydrothermal sulphide, implies that CO₂ derived by reaction of limestone with sulphuric acid (‘condensation corrosion’) contributed to the formation of ¹³C‐enriched speleothem deposits.     

Problems of Analysis by FTIR of Calcium Sulphate–Based Preparatory Layers: The Case of a Group of 16th‐Century Portuguese Paintings

This paper provides a contribution to FTIR analysis of calcium sulphate‐based grounds of paintings when a mixture of compounds with different degrees of hydration is present. The study is based on the analysis with that technique, electron microscopy coupled with energy‐dispersive X‐ray spectrometry and X‐ray diffraction of both the grounds of 16th‐century Portuguese paintings and reference samples prepared with anhydrite and calcium sulphate dihydrate bound in an animal glue solution. It is shown that the interpretation of the degree of hydration of calcium sulphate ground samples using FTIR cannot be based solely on the study of the hydroxyl bands, as is usual in routine work, but that small deviations of the S–O vibration bands are an important indicator of the presence of anhydrite in the grounds.     

Provisioning Inka feasts at Tiwanaku, Bolivia: the geographic origins of camelids in the Pumapunku complex

While political integration can be achieved by many means, here we focus on the use of feasting and statecraft in the Inka Empire of the Andean Late Horizon (c. AD 1400-1532) in South America. In order to examine Inka political integration of the Lake Titicaca Basin of Bolivia, we examine paleomobility and paleodiet through radiogenic strontium and stable oxygen and carbon isotope data in archaeological camelid remains from the site of Tiwanaku. Mean radiogenic strontium isotope values from all archaeological camelid enamel and bone samples is ⁸⁷Sr/⁸⁶Sr = 0.70998 ± 0.00179 (1σ, n = 48), mean stable oxygen isotope values from a sub-set of archaeological camelid enamel and bone samples is δ¹⁸O_{carbonate (VPDB)} = −10.0‰ ± 2.6‰ (1σ, n = 18) and mean stable carbon isotope values from a sub-set of archaeological camelid enamel and bone samples is δ¹³C_{carbonate (VPDB)} = −9.0‰ ± 1.7‰ (1σ, n = 18). While many camelids consumed in these feasting events were likely local to the Lake Titicaca Basin, others came from a variety of different geologic zones, elucidating our understanding of Inka statecraft and the role of feasting in political integration in empires in the past.     

Assessing the life history of an andean traveller through biogeochemistry: Stable and radiogenic isotope analyses of archaeological human remains from Northern Chile

Bioarchaeology and biogeochemistry can elucidate aspects of individual life histories that are often lost in the archaeological record. Here, we use stable and radiogenic isotope analyses of enamel, bone and hair to reconstruct paleodiet and paleomobility in an adult male interred along a pre‐Columbian route connecting the northern Chilean coast to the inland Loa River Valley. Although this well‐preserved burial included mortuary goods typical of coastal cultures, it was discovered in a vast, uninhabited part of northern Chile's hyper‐arid Atacama Desert. Variation in carbon and nitrogen isotopes reflects dietary differences, while strontium and oxygen isotopes vary geologically and geographically. We use these data to examine paleodiet and paleomobility and to assess whether this was a coastal traveller seeking provisions from the interior or vice versa. Enamel stable isotope analysis is consistent with the consumption of a mixture of terrestrial and marine resources during the first years of life. Bone stable isotope analyses indicate habitual consumption of marine foodstuffs over the last 10–30 years of this individual's life. Interestingly, stable isotope analysis of hair samples provides more fine‐grained information on this individual, suggesting movements between the coast and highlands in the months before his death. Radiogenic strontium isotope data are consistent with residence on the coast or in the Atacama Desert, but are lower than strontium isotope values from higher altitudes. These dietary and geological patterns are reconcilable with coastal residency; the isotopic data are consistent with foodstuffs and textiles found with the burial. Therefore, we argue that this individual was regularly moving from the coast to inland areas, crossing the hyper‐arid Atacama Desert by following strategic interzonal routes that provided access to particular resources. Copyright © 2010 John Wiley & Sons, Ltd.     

青海瞿昙寺壁画颜料的研究

通过对青海瞿昙寺画郎和建筑彩绘所用的22个绘画颜料样品的 x-射线衍射和同位素 x 荧光分析.共分析出20多种无机矿物颜料,此外.还有蓝钯、黄钯有机颜料。本文对这些颜料的分析结果进行丁综合论述.并与敦煌石窟、麦积山石窟、炳灵寺石窟等的彩绘颜料进行了研究。     

Analytical study of Roman and Arabic wall paintings in the Patio De Banderas of Reales Alcazares’ Palace using non-destructive XRD/XRF and complementary techniques

A portable XRD/XRF system and complementary laboratory techniques were employed to improve the knowledge of the procedures used to create Roman and Arabic wall paintings. Integrated physico-chemical investigations were conducted on fragments of artworks collected from the archaeological excavation of the Patio de Banderas in the Reales Alcazares’ Palace of Seville (Spain), and a comparative study on the pigments from both historical periods was performed. As a result, pigments such as vermilion, red ochre, yellow ochre, green earth, Egyptian blue, carbon and phosphor-based black pigments were detected in Roman samples; however, in the Arabic fragments, only haematite was observed. In addition, the size and shape of the particles of the wall paintings were studied with an XRD 2-dimensional detector and SEM-EDX.     

Lead isotope and metal source of Shang bronzes: a response to Sun et al.’s comments

In this brief response to Sun et al.’s ( 2018 ) comments on our paper, we re‐emphasize that archaeological, chemical and isotopic evidence are all relevant to the discussion about the metal source of the Shang period with highly radiogenic lead isotope ratios. The southern African bronzes have much lower lead contents and quite different lead isotopic signatures than the Shang bronzes. More importantly, there was no metallurgy of any kind in southern Africa before c.200 ce , so southern Africa cannot possibly be the source of Shang bronze, which date to about 1500 to 1000 bce .     

Characterization and origin of black and red Magdalenian pigments from Grottes de la Garenne (Vallée moyenne de la Creuse-France): a mineralogical and geochemical approach of the study of prehistorical paintings

Pigments sampled from wall paintings and from crayons taken on the floor, at the Grottes de la Garenne (Saint-Marcel – Indre, France) have been analyzed and characterized by infrared spectroscopy, Raman micro-spectroscopy, X-ray diffraction, ICP/MS and analytical TEM. The red pigment used for the wall paintings is mainly composed by hematite, clays, carbon matter and carbonates. Results on the red pigments show that the compositions of the paintings are similar to that of some crayons. Regarding these analyses, their origin is compatible with local siderolithic facieses. Analysis of black pigments shows that they are made of cryptomelane, pyrolusite, clays, carbonates and carbon matter. It shows also that paintings and some crayons compositions are compatible. On the contrary of red pigments, the origin of black pigments is probably allochtonous. Indeed, the traces of thallium detected in cryptomelane, the cerium anomaly and the absence of iron are not compatible with local facieses or other sites from the French Massif Central.     

Physico‐Chemical Characterization of Pigments and Binders of Murals in a Church in Ethiopia

Here, we report the physico‐chemical characterization of wall paintings from the Petros and Paulos church in Ethiopia. This work represents the first technical study of paintings located in Ethiopia, rather than paintings in museum collections outside the country, using diverse analytical techniques. In situ examination with a portable X‐ray fluorescence spectrometer (pXRF) was followed by analysis of samples using optical microscopy (OM), scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM/EDS), micro‐Raman spectroscopy (MRS), attenuated total reflection – Fourier transform infrared spectroscopy (ATR‐FT–IR), X‐ray powder diffraction (XRD) and pyrolysis gas chromatography – mass spectrometry (Py‐GC/MS). The paint stratigraphy, the compositions of the support material, the preparatory and painting layers were studied, as well as the morphology of the pigment particles. The results revealed the use of earth pigments and carbon black. The preparatory layer was uncommon; composed of dolomite, clay rich in clinochlore and sand, in contrast to the more common gypsum and calcite. The binder and the stratigraphic analyses suggested a distempera technique.     

Element localization in archaeological bone using synchrotron radiation X-ray fluorescence: identification of biogenic uptake

Trace element analysis related to archaeological bone is viewed as one way to determine levels of element exposure in past populations. This area of research is complex because there is the potential for the incorporation of trace elements from the burial environment into archaeological bone. We tested the hypothesis that matching the spatial distribution of trace elements within cortical bone with the biological structures would provide evidence of biogenic uptake. We examined samples from a non-segregated Royal British Naval cemetery (1793–1822) in Antigua, West Indies. A key historical question related to this population was the extent of exposure to lead and the resulting health effects. Images from conventional light microscopy (histological) analysis of the bone samples were matched with elemental maps of calcium, strontium, and lead that were created through the use of synchrotron radiation X-ray fluorescence (SR-XRF). Biogenic uptake of both strontium and lead was indicated based on the localization of these trace elements within discreet microstructural elements. The successful integration of histological information with XRF data is a powerful technique for the interpretation of past biological events through trace elements.     

Micro‐Raman And Micro‐Stratigraphic Analysis Of The Painting Materials In The Rock‐Hewn Church Of The Forty Martyrs In Şahinefendi,Cappadocia (Turkey)

This paper presents the results of analyses carried out on the paintings on the rock‐hewn walls of the Forty Martyrs church at ?ahinefendi in Cappadocia (a UNESCO World Heritage Site), a central region of Turkey, performed during conservation work from 2007 to 2012. The micro‐samples were investigated by spectroscopic, micro‐stratigraphic and scanning electron microscopy analysis in order to study the painting technique, the materials and the degradation products. The micro‐stratigraphic analysis showed a white, sometimes pinkish, plaster. Micro‐Raman analysis, performed on cross‐sections of the mortars, enabled the detection of calcite, gypsum, anhydrite and calcium oxalate. Scanning electron microscopy and energy‐dispersive spectroscopy revealed a similar composition among all investigated phases, aside from minor differences such as the presence of diatoms in the second and third phases and of biotite, lime lumps and plants fragments in the fourth one. Apart from traditional pigments of medieval wall paintings, micro‐Raman analysis revealed the presence of lead‐based compounds and jarosite.