Characterization of organic media in the wall-paintings of the “Palace of Nestor” at Pylos,Greece: evidence for a secco painting techniques in the Bronze Age

This paper presents the results of an investigation of organic binding media detected in samples from the Mycenaean wall-paintings at the “Palace of Nestor” in Pylos (Western Messenia, Greece): samples dated from the Late Bronze Age (ca. 1200 BC). This is the first scientific study to be conducted on organic binding media in Mycenanean painting, and it is a study that aims to contribute significantly towards our understanding of the original painting techniques used during the Bronze Age. The analytical procedures employed for the detection and characterization of the organic substances preserved within the paint layers (proteinaceous materials, lipids and plant gums), were based on chromatography/mass spectrometry techniques (PY–GC/MS, GC/MS). The most significant results, highlighting an a secco painting technique, are herein reported and discussed.     

Environmental impacts around the time of Norse landnám in the Qorlortoq valley,Eastern Settlement,Greenland

Palynology, radiocarbon dating, and open-section stratigraphies from archaeological trenches are used to examine the impact of human activity around the time of Norse landnám on vegetation and landscape associated with a small farm (Ø34) in the Qorlortoq valley, Eastern Settlement, Greenland (61° N 45° W). Peat deposits from a mire abutting the Norse ruins revealed a discontinuous palaeoenvironmental record containing a possible hiatus from ca. AD 410–1020. Palaeovegetational data were recovered either side of this period. Pollen assemblages suggest that open Salix scrub dominated the landscape during the pre-settlement phase. The later phases of landnám resulted in the creation of hay fields and heavily-grazed grassy heath. Site abandonment is reflected by a re-expansion of Salix. This occurs shortly before the onset of deposition of a Sphagnum peat, dated to cal AD 1420–1630 (2σ) and reflecting an increase in mire surface wetness, probably in response to a deteriorating climate. Radiocarbon dates were obtained on peat and plant macrofossils sampled from either side of the proposed hiatus at two different but closely-spaced (<20 m) locations across the mire. These produced significantly different dates for the cessation of peat formation in the pre-landnám period (cal BC 2130–1770 and cal AD 240–410 respectively), but near-synchronous dates for the recommencement of peat growth (cal AD 890–1150 for peat and a probably more reliable interval of cal AD 1020–1190 based on plant macrofossils). It is suggested that this hiatus may represent the first direct evidence for peat cutting in Norse Greenland.     

Changes in shell gathering in an early agricultural society at the head of Ise Bay,Japan

We examined changes in shell gathering in an early agricultural society at the head of Ise Bay, Japan based on the analysis of almost 20,000 individual shell remains from four coastal settlements. We analyzed historical changes in the composition and size range of the shell species Meretrix lusoria. The most common species went from Crassostrea gigas in the early Middle Yayoi period (about 400–350BC) to M. lusoria in the mid-Middle Yayoi period (about 320–200BC). It is possible that the seacoast tideland, an environment suitable for C. gigas, was buried in sediment from the rivers and thereby transformed into muddy sand bottoms, an environment more suitable for M. lusoria. We also analyzed historical changes in the size range of M. lusoria. The mean size of M. lusoria increased significantly from the early Final Jomon (about 1250–1000BC) to the late Early Yayoi (about 500–400BC), from the late Early Yayoi to the early Middle Yayoi, and from the early to the mid-Middle Yayoi periods. Evidence suggests that during the Yayoi period, the demand for shells decreased and therefore, the pressure to collect M. lusoria also decreased. We concluded that the larger specimens of M. lusoria were collected selectively.     

The contents of unusual cone-shaped vessels (cornets) from the Chalcolithic of the southern Levant

Cornets are cone-shaped ceramic vessels, characteristic of the Chalcolithic period (ca. 4700–3700 BC) in Israel and Jordan. Their contents and use are unknown. Gas chromatography with flame ionization and mass-selective detection, showed that extracts of cornets from five different sites with different related activities (domestic, habitation cave and a cultic complex) all contain the same assemblage of mainly n-alkanes adsorbed within their walls. This assemblage differs from those found in other types of ceramic vessels from the same sites, as well as from the residues found within the associated sediments. The assemblage of odd and even-numbered n-alkanes found in the cornets is almost identical to that found in the residues of beeswax heated on modern ceramic fragments, as well as in a beehive from the Iron Age IIA strata at Tel Rehov, Israel. Thus the cornets are most likely to have contained beeswax. The presence of beeswax in the cornets contributes to our understanding of the Chalcolithic period; a time when secondary products such as milk, olive oil and wine are thought to have come into use.     

Roman blue-green bottle glass: chemical–optical analysis and high temperature viscosity modelling

Chemical analysis, optical absorption spectroscopy and mathematical modelling of high temperature viscosity have been carried out on five 1st–2nd century AD Roman blue-green bottle glass fragments from Coppergate, York. Modelled viscosities indicate remarkable consistency within the sample set studied and support the suggestion that temperatures of ∼1000–1150 °C were required to remelt these glasses and to provide suitable viscosities for forming articles. Iron redox ratios (Fe²⁺/ΣFe), analysed SO₃ contents and the absence of characteristic Fe³⁺–S²⁻ amber absorption bands suggest that melting conditions for all studied glasses were mildly, rather than strongly, reducing (estimated pO₂ ≈ 10⁻¹–10⁻⁶ bar). These furnace conditions are consistent with the effects of combustion gases and carbonaceous matter contained in the raw materials.     

Trace element concentrations in teeth – a modern Idaho baseline with implications for archeometry,forensics, and palaeontology

Concentrations of 69 minor and trace elements were measured in situ using laser ablation inductively-coupled plasma mass spectrometry in multiple teeth of modern herbivores (Cervus elaphus, Odocoileus hemionus, Odocoileus virginianus; n = 52), omnivores (Ursus americanus; n = 56), and carnivores (Felis concolor; n = 33; Canis lupus; n = 4) from Idaho, USA. On each tooth, two to five analyses were collected on enamel, primary dentine, and secondary dentine with spot diameters of 30–100 μm. Continuous 30-μm-wide line traverses were collected across deer, elk, and wolf teeth. Results confirm trace element concentrations below 1 ppm for many elements, including Li, Be, transition metals (excepting Mn, Fe and Zn), heavy metals (excepting Hg and Pb), the rare earths, and actinides. Strontium and Ba generally biopurify with increasing trophic level, but Ba shows decreasing discrimination with tissue type in the order secondary dentine – primary dentine – enamel. Most elements show strong zoning within tissues and variable trophic level behavior, so concentrations in omnivores rarely fall between herbivores and carnivores. Trace element mass balance suggests that soil and dust, not food, commonly deliver the largest trace element load in terrestrial carnivores and omnivores, even for elements that biopurify, like Ba. Use of trace elements for inferring past diets are likely compromised by unknown rates of dust and soil ingestion rather than indicating the degree of herbivory and carnivory. The low concentrations of many elements provide multiple sensitive markers of post-burial overprinting that can be used to discriminate altered vs. original biogenic compositions. REE and actinide trends do not directly follow bedrock compositions.     

Minateda rock shelters (Albacete) and post-palaeolithic art of the Mediterranean Basin in Spain: pigments,surfaces and patinas

The inorganic and organic fractions of two microsamples of prehistoric paint from the same site, the Minateda rock shelters, are analysed here for the first time. The two samples correspond to two rock shelters of different styles (Levantine and schematic) – Abrigo Grande de Minateda (The Great Rock Shelter of Minateda) and Abrigo del Barranco de la Mortaja (Del Barranco de la Mortaja Rock Shelter). Since its discovery, historiographical tradition has emphasised the Abrigo Grande de Minateda, with its magnificence and complexity, as emblematic of the origin and evolution of rock art in the Mediterranean Basin of the Iberian Peninsula (a UNESCO World Heritage Site). Four complementary techniques –Microphotography, Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDX), Raman Spectroscopy and Gas Chromatography–Mass Spectroscopy (GC–MS)– were combined to identify and characterise the physicochemical properties of the paint and of the surface. We present an interpretation of the results that leads us to define complex taphonomic alterations beyond the usual distinction of layers that include the surface, pigments and patinas.     

Palynological study of a Mi'kmaw shell midden,Northeast Nova Scotia,Canada

Before now, no palynological studies were made on shell midden deposits in Nova Scotia, despite a long history of archaeological research. A test study of samples taken from the shell midden at Maligomish (Indian Island) on the Northumberland Strait was conducted to determine if sufficient pollen, fern and moss spores, and other non-pollen palynomorphs (NPP's, including fungal remains, algal spores) could be recovered to allow interpretation of environmental conditions at the time of deposition. Several pollen processing methods were tested: sieving and swirling, chemical treatment with cold HCl, 5% KOH and brief exposure to 5% NH₄OH, and treatment with acetolysis solution. We recovered variable amounts of pollen, spores and NPP's from samples taken at 3–5 cm, 5–15 cm and 15–25 cm below surface. Abundant microcharcoal fragments prevented effective use of the swirling technique, but sufficient palynomorphs were recovered by chemical treatments to allow assessment of down-section changes in assemblages. Three radiocarbon ages from Mya arenaria and Crassostrea sp., and measurements of sediment grain size, moisture, organic and inorganic carbon, provide a framework for analysing palynological assemblage changes and context for interpreting differential palynomorph preservation. Despite some oxidation and microbial degradation of palynomorphs in the time interval (ca. 380–1600 cal yr BP), the midden assemblages correlate with pollen zones from marine and lake core sites within ca. 50 km of Maligomish. Shifts in abundances of algal spores, testate amoebae and aquatic plant pollen also indicate changes in depositional conditions during the time of midden use. The study provides the first reference for archaeologists attempting to use palynology for analysis of samples from Nova Scotian shell-bearing contexts.     

Stratigraphy and geochronology of La Playa archaeological site,Sonora, Mexico

La Playa archaeological site in northern Sonora, Mexico contains a long record of human activity that includes the Paleoindian period (terminal Pleistocene) and much of the Holocene. The size and complexity of La Playa has discouraged a systematic characterization of its stratigraphy and geochronology, a deficiency we redress in the study. We distinguished seven stratigraphic units ranging in age from >44,570 to 400 cal yr B.P. using ¹⁴C dates from charcoal and terrestrial gastropods found mostly in archaeological features. All of the buried (in situ) cultural remains are contained in Units B (4690–1580 cal yr B.P.) and C (1010–400 cal yr B.P.) and represent overbank deposition from the nearby Rio Boquillas. Occupation at the site peaks in Units B₄ and B₅, corresponding to the Cienega phase (2800–1800 cal yr B.P.) of the Early Agricultural period. This period coincides with the growth of early agricultural villages in the region and is marked at La Playa by thousands of archaeological features including roasting pits, human burials, and extensive canal irrigation systems. The presence of semi-aquatic and aquatic snails demonstrates that water was present year round in the canal systems constructed during this period. Stable and radiometric isotopic evidence suggests that early agriculturalists diverted ground water over several kilometers from the nearby Rio Boquillas. The extensive Cienega phase occupation ended after about 1700 cal yr B.P. with deep erosion of the site, an event also visible in alluvial records in southern Arizona that marked the end of the Early Agricultural period and significant changes in settlement organization in the region.     

Ancient-DNA reveals an Asian type of Mycobacterium leprae in medieval Scandinavia

Leprosy is a chronic infection of the skin and peripheral nerves caused by the pathogen Mycobacterium leprae. Its impact on human populations and societies of the past as well as its phylogeographic patterns around the world – at least in modern times – has been well documented. This slow growing bacterium has been shown to exist in distinct ‘SNP types’ that occur in relatively defined parts of the globe. The routes that the disease followed in the past are, however, still uncertain. This study of ancient-DNA typing of archaeological human remains from Sweden dated to early Medieval times provides genetic evidence that a transmission of M. leprae ‘SNP subtype’ 2G – found mainly in Asia – took or had already taken place at that time from the Middle East to Scandinavia. This finding is unique in the history of leprosy in Europe. All human specimens from this continent – both modern and ancient – that have been tested to date showed that the one responsible for the infection strains of M. leprae belong to ‘SNP type’ 3, whereas our results show that there were some European populations that were hosts to bacteria representing ‘SNP type’ 2 of the species as well.     

Estimating meagre (Argyrosomus regius) size from otoliths and vertebrae

This study presents a method for predicting meagre (Argyrosomus regius) body size (total length) from otoliths and vertebrae recovered from archaeological sites. The method involves regression equations calculated from a reference collection of 36 meagre skeletons and 113 meagre otoliths (sagitta) and allows the simultaneous estimation of original body size and minimum number of individuals (MNI) from archaeological bone structures. We selected the following measurements to predict meagre body size: greatest dorso-ventral height, greatest mediolateral breadth, and greatest anteroposterior length of the vertebrae centra; maximum anteroposterior length, medial anteroposterior length, and dorso-ventral height of the sagitta. Our results show that the original body size of meagre can be accurately predicted from many bone measurements (r² range: 0.921–0.992). We exemplify the use of the regressions in the assessment of size variation and MNI of meagre from four Portuguese Mesolithic sites. We show that regression results provide additional insight into the significant role that this fish played in the subsistence of coastal fisher-hunter-gatherers, who targeted medium-sized animals but were also capable of acquiring rather larger specimens.     

Macro- and micro-archaeobotanical study of a vessel content from a Late Neolithic structured deposition from southeastern Hungary

A well-preserved assemblage of pottery and a broken stone artefact were excavated within a long house in the southern part of Tiszasziget, near the town of Szeged, Hungary. The settlement had been inhabited by the Late Neolithic Tisza culture around 5000–4500 BC. Based on the position of the finds it is suggested that the objects represent an ideologically-charged structured deposition. A piece of organic residue found in a mug (No. 18) with three-fold articulation has been subjected to macro- and microfloral analysis. After precise sampling of the residue, the standard methods to recover organic and inorganic plant remains were utilised. Based on the macrofloral and amino acid content analysis, it is suggested that the organic remains were pieces of fermented pastry made of cereal flour. The recovered silicified tissues and articulated phytoliths were subjected to morphometric measurements, which revealed that the food remain placed in the structured deposition was prepared of Triticum and – probably wild – Avena species. Starch granules of cereals were also detected, whilst the palynological evidence supports morphologies most likely to be related to the accompanying weed flora. The fortunate survival of the organic matter and the complex macro- and micro-archaeobotanical approach provided an unique opportunity to gain a better insight to the food preparation of Late Neolithic communities of the Carpathian Basin.     

Birdmen, cemís and duhos: material studies and AMS C dating of Pre-Hispanic Caribbean wood sculptures in the British Museum

This paper presents 19 AMS radiocarbon dates from nine pre-Hispanic Caribbean (Taíno/Lucayan) wooden sculptures in the British Museum collections, provenanced to Jamaica, Hispaniola and the Bahamas. Together with strontium isotope results and wood and resin identifications, these data build a material and chronological context for some of the most recognised examples of Taíno art – from duhos (ceremonial seats) and cemís (free standing depictions of deities, ancestors and spirits) to canopied stands used to hold hallucinogenic drugs during the cohoba ceremony. Each sculpture widens our understanding of Caribbean carving traditions, stylistic variation, chronologies and material resource utilisation. A group of three sculptures recovered from Carpenters Mountains, Jamaica, carved by AD 1300 and brought together as a ceremonial ‘set’, each appear to have had their inlays renewed over a century later, suggesting long-term use. Three key examples of the main Caribbean duho categories (high-back, low-back and extended), provide insights into the diversity of styles present in the region post-AD 1100. The British Museum's corpus enables an exploration of regional styles, and potentially the work of individual artists.     

Identifying biomolecular origins of solid organic residues preserved in Iron Age Pottery using DTMS and MVA

The chemical characterisation of solid organic residues found in ceramic vessels, can provide archaeologists with valuable information about ancient diets. Although several selective analytical techniques have been applied to the analysis of specific classes of compounds, such as extractable lipids, waxes, terpenoids and protein fragments, a non-selective analytical technique is required to characterise and categorise complete solid organic residues. In this study, Direct Temperature-resolved Mass Spectrometry (DTMS) is used for the characterisation of 34 solid residues situated on vessels recovered from an indigenous settlement from the Roman period at Uitgeest – Groot Dorregeest (The Netherlands). Sample preparation is limited to grinding very small samples (5–10 μg) and suspending them in water. DTMS analysis of aliquots (1–2 μL) of this suspension gave information about a broad range of organic compounds, such as lipids, polynuclear aromatic hydrocarbons, markers for residual proteins and polysaccharides, and for newly formed complex condensed polymers. Multivariate analysis of the DTMS spectra identified five different chemotypes: groups of residues with comparable chemical characteristics. The biomolecular origin of each of these chemotypes is identified by comparison with experimentally charred reference materials. The chemotypes A₁ and A₂ consist of charred residues identified as starch-rich foods (mixed with animal or plant products), chemotype C consists of protein-rich charred animal products without starch, chemotype B contains smoke condensates from wood fires, and chemotype D consists of special protein-rich and lipid-free foods or non-food products.     

Chemical analysis of 17th century Millefiori glasses excavated in the Monastery of Sta. Clara-a-Velha,Portugal: comparison with Venetian and façon-de-Venise production

A set of ten Millefiori glass fragments dating from the 17th century, originated from archaeological excavations carried out at the Monastery of Sta. Clara-a-Velha (Coimbra, Portugal), were characterized by X-ray electron probe microanalysis (EPMA), Raman microscopy and UV–Visible absorption spectroscopy. All glasses are of soda-lime-silica type. The use of coastal plant ash is suggested by the relatively high content of MgO, K₂O and P₂O₅, as well as by the presence of chlorine. Tin oxide or calcium antimonate were the opacifiers used in the opaque glasses, cobalt in the blue glasses, copper in the turquoise glasses, iron in the yellow and greenish glasses, and iron and copper were found in the opaque red and aventurine glasses. Based on the concentrations of alumina and silica four different sources of silica were identified, allowing the classification of the glasses into the following compositional groups: low alumina (<2 wt%), which includes a sub-group of cristallo samples with SiO₂ > 70 wt%, medium alumina (2–3 wt%), high alumina (3–6 wt%) and very high alumina (>6 wt%). Comparison with genuine Venetian and façon-de-Venise compositions showed that two fragments are of Venetian production, one of Venetian or Spanish production and the remaining are of unknown provenance. In two fragments the glass of the decoration is probably Venetian or Spanish but the glass used in the body is also of unknown provenance.     

A high-resolution electron microscopic and energy-dispersive spectroscopic study on the molecular mechanism underpinning the natural preservation of 2300 Y.O. naturally-mummified human remains and the occurrence of small-sized [Zn][Al]Carbon spheres

In this paper we use Scanning and Transmission Electron Microscopy, and Energy Dispersive Spectroscopy to characterize the surface of the skin of a 2300 YO, naturally-preserved mummy, belonging to a two-year and eight month girl (“Pepita”), found inside a cave located in Altamira, Querétaro, México (21°40′–20°01′; 99°03′–100°36′). The cave was found in Sierra Gorda, an orographic region with a relief of sedimentary origin from the Gulf of Mexico, composed by high mountains with altitude values surpassing 3000 m above sea level, with ample and steep canyons, and a prominent role on the exploitation and distribution of cinnabar (HgS). The skin showed the presence of small-sized spherules, containing Al (≤43%) in the most exposed region (5–10 μm depth). Thin layers and structural microdomains covered small and large spheres. Structures conformed by stacked, nano-sized particles located far-from-the bunches contained C (≤45%), Zn and Si (≤10%), and minor amounts of Ca (≤2.6%). By contrast, regions between spheres contained high amounts of Ca (≤23%) and Al (≤15%), but lacked Zn and Si. Carbon spheres showed two distinctive composition, a signature that their formation might have occurred in a least two different stages via concentric growth mechanisms, with the incorporation of Zn and Al at a later stage. [Zn][Al]Carbon spheres showed morphology and growth patterns that compared to those resulting from the hydrothermal carbonization by Fe²⁺ ions under mild conditions, suggesting a common mechanism of formation. Textural changes of thin films found between [Zn][Al]Carbon spheres were attributed to differences in viscosity, which might have contributed to increases in functionality and specific surface area (by means of decreases in size) and, in turn, facilitating the sequestration of biomolecules. We propose that the presence of [Zn][Al]Carbon spheres provides protection against bacterial and UV attack. The physical properties of these spheres helped entrap biomolecules. Taken together, these factors contributed to the preservation of Pepita.     

Assessing the applicability of portable X-ray fluorescence spectrometry for obsidian provenance research in the Maya lowlands

Recent innovations in portable energy-dispersive X-ray fluorescence (PXRF) spectrometry have increased its utility for the geochemical characterization of obsidian artifacts for archaeological provenance research. However, concerns over the utility of PXRF instrumental analyses have been raised, focused on the validity and reliability of the geochemical data produced. Here we adopt the framework of Richard Hughes (On Reliability, Validity, and Scale in Obsidian Sourcing Research, 1998), whereby reliability addresses instrument stability and issues of measurement while validity pertains to an instrument’s ability to discern geochemical source provenance. This is done in order to test the utility of PXRF instruments for archaeological provenance research. k-Means cluster analysis was used to test the accuracy of PXRF through statistical comparison of data acquired via laboratory and portable energy-dispersive XRF instruments. Multivariate analysis was employed to demonstrate obsidian source representation at two Classic Maya archaeological sites in southern Belize – Uxbenká and Ek Xux – and to test the validity of data obtained from a PXRF instrument in answering archaeological research questions pertaining to regional interactions between lowland Maya polities. Results suggest that portable XRF instruments produce internally consistent results. However, data acquired from a PXRF instrument are not statistically equivalent to other XRF instruments. This is to say that while PXRF is not a reliable technique, it is valid for questions pertaining to geochemical source representation.     

Short-chain n-alkanes (C16–20) in ancient soil are useful molecular markers for prehistoric biomass burning

The incorporation of plant biomass into soil usually leads to long-chain n-alkanes with a relative predominance of odd carbon numbered homologues. Contrastingly, an increase in short-chain even carbon numbered n-alkanes was found in charred biomass with progressing temperatures. We applied lipid analysis to buried ancient topsoils that contained charred organic matter and to corresponding control soils, which were characterized by a lighter color and lower contents of charred materials. Commonly, the proportion of lipid extracts was found to be lower in the ancient soil than in the control samples, which indicated an enhanced degradation of organic matter, e.g., by thermal degradation. All samples displayed a particular pattern of short-chain and even carbon numbered n-alkanes (maximum at n-C₁₆ or n-C₁₈). The ratios CPI (carbon preference index) and ACL (average chain length) for the investigated soil samples matched the ratios found for maize and rye straw charred at 400 °C or 500 °C, respectively. These molecular ratios indicate the presence of charred biomass. The predominance of short-chain and even carbon numbered n-alkanes was a result of thermal degradation of biomass. The degradation products were preserved in ancient soils and could be applied as molecular markers in archaeological or palaeoenvironmental research.     

Paleoparasitological results from coprolites dated at the Pleistocene–Holocene transition as source of paleoecological evidence in Patagonia

Coprolites attributable to humans, dated from the Pleistocene–Holocene transition, obtained from the archaeological site Cerro Casa de Piedra, Santa Cruz Province, were examined for parasites. The feces were processed by rehydration and spontaneous sedimentation using conventional parasitic procedures. Helminthic eggs recovered were identified as Trichuris sp., Calodium sp., other capilariids, and ancylostomid (Nematoda), probably Hymenolepis sp. and anoplocephalid (Cestoda); one oocyst attributable to Eimeria macusaniensis (Apicomplexa) was also found. According to the life-cycles and specificity of the parasites found, it is possible to suggest that some species (i.e., E. macusaniensis and Calodium sp.) represent parasites in transit or pseudoparasitism. Paleoparasitological results revealed the existence of an intensive relationship between parasites and humans in the Pleistocene–Holocene transition in Patagonia. Evidence suggests an early association among parasites, rock shelters and hunter–gatherers in the region. It is also postulated that the ancient lifestyles associated with caves and rock shelters were conductive to illness.