The role of arsenic in Chalcolithic copper artefacts – insights from Vila Nova de São Pedro (Portugal)

The Castro of Vila Nova de São Pedro (VNSP) is an emblematic settlement located at Azambuja, Portuguese Estremadura. It was occupied during the third and second millennia BC, predominantly during the Chalcolithic period. A diversified collection of 53 copper-based artefacts (most part in a fragmentary condition), belonging to an extensive metallic collection recovered during excavations carried out in VNSP, was studied using micro-EDXRF spectrometry, optical microscopy and SEM-EDS. Additionally, Vickers microhardness measurements were performed to establish the effectiveness of the thermomechanical treatment in the hardness of the artefacts. Results show that the Largo do Carmo, artefact collection is mainly composed of copper or arsenical copper, being 37% of the artefacts made of copper alloyed with arsenic (As > 2%). A statistically significant association was found between copper alloyed with arsenic and artefacts classified as tools/weapons (arrowheads, daggers and knives). In several cases, the presence of arsenic rich phases in the microstructure, resulting from an inverse segregation phenomenon, shows no evidence of chemical homogeneity control during the artefact manufacture. Microstructural analyses also show that the majority of this group (73%) was shaped with forging plus annealing operation cycles and 23% of the artefacts received a final cold hammering after the forging and annealing. An association between the presence of a final forging treatment and artefacts presenting higher arsenic contents was also identified. Nevertheless, no direct correlation was found between the arsenic content of the alloy and its hardness. Also no direct correlation was found between the hardness and a final forging operation. However, it was observed that a harder forging was applied to the cutting edge of the artefacts and consequently a high hardness in this area was obtained despite the arsenic content of the alloy. Concerning arsenical copper alloys, all evidences point out that the potential for obtaining a harder material was not recognized by the ancient metallurgists and the selection of the alloy was possibly made based on colour.     

Particle size distribution of lithic assemblages and taphonomy of Palaeolithic sites

Lithic debris derived from knapping and used tools can be assimilated to simple sedimentary particles that may undergo size sorting when exposed to geomorphic processes such as streamflow or overland flow. Sorting can be identified by comparing the size distribution of archaeological assemblages to that of experimental core reduction sequences. A new database including different types of raw material (mainly flint and quartzite) and Palaeolithic debitage (blade, Levallois, discoid, on anvil, and shaping) has been built for this purpose. Palaeoeskimo data have also been added to illustrate microlithic industries. For all the debitages and raw materials, the particle size of knapping products >2 mm in width fits with a power-law distribution and shows only minor fluctuations, the range of which is always <15% between experiments (all steps of the chaîne opératoire included up to the final tool). A lithic assemblage derived from block/core knapping or blank/preform production will display a particle size distribution close to the experimental distributions if not subsequently modified. Modifications may originate either from sedimentary processes or from anthropogenic factors. To help distinguishing amongst these, data on the impact of both water flows on sedimentary particles or experimental assemblages, and anthropogenic processes such as importation-exportation (of core, preforms or finished tools) or uneven spatial distribution of the different steps in core reduction and tool production within a site, are reviewed. By contrast to anthropogenic modifications, sedimentary processes are generally typified by strong impoverishment in or selective accumulation of fine-grained (<10 mm) artefacts together with a low intra-site variability (spatial homogenization) or a downslope size trend. Archaeological case studies taken from French Palaeolithic site are then detailed. Evidence for lithic redistribution implies that care should be taken in archaeological site analysis since sorting may impact significantly the initial techno-typological balance of the assemblage.     

SYNCHROTRON FTIR MICRO‐SPECTROSCOPY APPLIED TO THE STUDY OF POLISHED SERPENTINITE ARTEFACTS: A NON‐DESTRUCTIVE ANALYTICAL APPROACH

In prehistory, serpentinite was one of the most frequently used raw materials to produce polished stone artefacts. Several conventional analytical techniques can be applied to identify the serpentine minerals, but their application generally requires a powdered sample. This implies that the artefacts to be analysed must be damaged, and the possibility of analysing a mixture of different serpentine polytypes is high. The use of spatially resolved techniques is therefore a necessity to overcome this problem. Several thin sections of serpentinitic rocks and prehistoric axes have been analysed by synchrotron radiation Fourier transform infrared micro‐spectroscopy. The spectra were acquired directly on specific points of polished stone artefacts and this allowed the recognition of the different polytypes of serpentine minerals without causing any damage to the objects. The results show the infrared micro‐spectroscopy technique to be a useful tool for the characterization of archaeological lithic material.     

Bronze production in Southwestern Iberian Peninsula: the Late Bronze Age metallurgical workshop from Entre Águas 5 (Portugal)

Archaeological works at Entre Águas 5 (Portugal) uncovered a seasonal LBA settlement with significant metallurgical remains (crucibles, moulds, prills and a tuyere) related to bronze production. Radiocarbon dating ascribes an occupation period (10th–9th century BC) previous to Phoenician establishment in Southwestern Iberia. In spite of the proliferation of metal artefacts during LBA, the production of bronze alloys is still poorly understood. An integrated analytical approach (EDXRF, optical microscopy, SEM–EDS, micro-EDXRF and Vickers microhardness) was used to characterise this metallurgy. Crucibles show immature slags with copious copper nodules, displaying variable tin content (c. 0–26 wt.%), low iron amount (<0.05 wt.%) and different cooling rates. Certain evidences point to direct reduction of oxide copper ores with cassiterite. Scorched moulds with residues of copper and tin indicate local casting of artefacts. Finished artefacts also recovered at the site have an analogous composition (bronze with ∼10 wt.% Sn and low amounts of Pb, As and Fe) typical of coeval metallurgy in SW Iberia. Some artefacts reveal a relationship between typology and composition or manufacture: a higher tin content for a golden coloured ring or absence of the final hammering for a bracelet. An uncommon gilded nail (gold foil c. 140 μm thick; 11.6 wt.% Ag; ∼1 wt.% Cu) attests the existence of evolved prestige typologies. This LBA settlement discloses a domestic metallurgy whose main features are typical in Iberian Peninsula. Finally, it should be emphasized that a collection as comprehensive and representative of a single workshop has rarely been studied, enabling a deeper understanding of the various operations involving the bronze production and manufacture of artefacts.     

MICROSCOPIC IDENTIFICATION AND SOURCING OF ANCIENT EGYPTIAN PLANT FIBRES USING LONGITUDINAL THIN SECTIONING*

Plant fibres and the artefacts constructed from them often remain overlooked in the archaeological record because of their poor survival and the problems related to the precise identification of the species to which the fibres belong. The goal of this study was to design a simple and accurate method of identifying archaeological plant fibre sources. Twenty‐two fibre samples from two sets of ancient Egyptian botanical artefacts were examined under both a stereomicroscope and a compound microscope, and compared to a large reference collection and to previously published research. By examining longitudinal thin sections of the ancient plant specimens, we identified plant fibres from the following species: Hyphaene thebeica, Cyperus papyrus, Desmostachya bipinnata, Imperata cylindrica, Phragmites australis and Linum usitatissimum. Our identification of these plant fibres reveals essential information about the materials used for producing ropes, baskets, sandals, mats and fabric. The results of this study demonstrate the value of longitudinal thin sectioning and light microscopy as a major means of identifying the source material of botanical artefacts, and advance our knowledge of ancient Egyptian plant exploitation as well as the associated technologies involved in constructing these types of artefacts.     

The Temple of Venus (Pompeii): a study of the pigments and painting techniques

We report here on a study of 57 fragments of wall painting excavated from the Temple of Venus (Pompeii). These samples were characterised by a wide range of analytical methods. Data showed that the palette is varied, although not so broad as that found in other buildings in Pompeii, and is consistent with pigments used elsewhere in Pompeii and in the Roman Empire. It is composed of: natural earths, minerals and rare artificial pigments. Paintings are made up of thin paint layers (0.01–0.10 mm thick) strongly adhering to the underlying preparation layer. Nonetheless, in some cases thicker layers (up to 0.40 mm) were recognised, often spread on other previous painting layers. Samples were also compared with the microstratigraphic criteria developed in Piovesan (2009) to distinguish wall painting techniques. This comparison demonstrated that both fresco and lime painting techniques were adopted.     

Complex raw materials and the supply system: Mineralogical and geochemical study of the jade artefacts of the Longshan Culture (2400–2000 bce) from Sujiacun site in coastal Shandong,China

X‐ray fluorescence (XRF), X‐ray diffraction (XRD) and Raman spectroscopy were employed to analyse the chemical compositions and phase structures of nine pieces of jade artefacts unearthed from Sujiacun, a Longshan Culture (2400–2000 bce ) site in coastal Shandong, eastern China. The results of the analyses indicated these samples were primarily made from multiple raw mineral materials, including antigorite, actinolite, clinochlore, turquoise and muscovite. No nephrite was recovered from the Sujiacun site. This is strikingly different from other top‐ranking settlements of Longshan Culture, such as Dantu, Liangchengzhen and Xizhufeng, in which nephrite was the main material of jade artefacts. This may reflect the distinctions in the supply system of jade raw materials among different rankings of Longshan period sites. In addition, laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) was used to analyse the composition of the rare earth elements of serpentine jade. These preliminary results were compared with published data on the composition of serpentine jade and it was found that the Sujiacun serpentine jade artefacts were likely sourced from the Taishan jade deposit.     

THE PROVENANCE OF OBSIDIAN ARTEFACTS FROM THE WĀDĪ ATH‐THAYYILAH 3 NEOLITHIC SITE (EASTERN YEMEN PLATEAU) BY LA–ICP–MS

The geological sources of obsidian in the Red Sea region provide the raw material used for the production of obsidian artefacts found in prehistoric sites on both sides of the Red Sea, as far afield as Egypt, the Persian Gulf and Mesopotamia. This paper presents the chemical characterization of five obsidian geological samples and 20 prehistoric artefacts from a systematically excavated Neolithic settlement in highland Yemen. The major element concentrations were determined by SEM–EDS analysis and the trace element concentrations were analysed by the LA–ICP–MS method, an almost non‐destructive technique capable of chemically characterizing the volcanic glass. A comparison of archaeological and geological determinations allows the provenance of the obsidian used for the Neolithic artefacts to be traced to definite sources in the volcanic district of the central Yemen Plateau.     

Non-destructive pXRF of mafic stone tools

Archaeological use of non-destructive pXRF has been most systematically applied to the classification and provenancing of volcanic glass (obsidian) artefacts. Comparable work has yet to be developed for non-vitreous artefacts. We report results of pXRF analysis for a sample of grey to black (mafic) aboriginal hatchets from Sydney and adjacent coastal regions to the north and south. The study shows both broad and detailed classification is achievable depending on rock type and degree of elemental depletion or enrichment of the samples. PXRF analysis reveals not only distinct patterns of resource use between the three regions of this study but also enables a high degree of geographic resolution in the case of the basalt artefacts of our sample. We conclude that non-destructive pXRF is effective for reliable characterisation of non-vitreous stone artefacts that have a sufficiently complex and enriched compositional signature (i.e., unaltered basalts); with ∼50% of the basalt hatchets in our sample matched with spatially and geologically specific sources.     

REPRODUCIBILITY OF ELEMENTAL ANALYSES OF BASALTIC STONE ARTEFACTS BY QUADRUPLE ICP–MS USING DIFFERENT SAMPLE SIZES AND DIGESTION METHODS,WITH IMPLICATIONS FOR ARCHAEOLOGICAL RESEARCH

Using high‐precision inductively coupled plasma mass spectrometry (ICP–MS), we measured >40 elements in basalts sampled by diamond micro‐drills to evaluate the effectiveness of different digestion methods and the reproducibility of elemental analysis for different sample sizes from 5 mg to 100 mg. The results indicate that those elements that are most suitable for geochemical characterization, such as rare earth elements (REE), high‐field strength elements (HFSE) and certain mobile elements (Rb, Sr, Th, U), show excellent reproducibility with an average relative standard deviation (RSD) of 3% between open‐beaker and pressured ‘bomb’ digestion methods. This observation rules out the presence of refractory phases such as zircon, which can only dissolve in pressured ‘bombs’, and suggests that the results from open‐beaker digestion are reliable. The ICP–MS data for powders of different weights ranging from 10 to 100 mg collected from two fine‐grained basalt artefacts display excellent reproducibility, with a RSD of <5% for the most important elements. The reproducibility is reduced when including the 5 mg weight fraction (RSD of ～2–9%), which is still sufficient for archaeological applications. Our results demonstrate the usefulness of 10 mg samples for elemental measurement, which is valuable for geochemical characterization and sourcing of fine‐grained basalt artefacts from museum collections that require minimal destructive sampling.     

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

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

Microscopic examination of ground sections – a simple method for distinguishing between bone and antler?

Both bones and antlers have been used throughout history for manufacturing various products. Therefore, archaeologists often have to distinguish between these materials. The more the raw material (bone or antler) has been treated, the more complicated it is to distinguish. For this study, recent macerated and archaeological samples of bone and antler and their products have been compared. Antler is usually very easy to distinguish based on the characteristic surface structure; however, the original surface is not preserved in all artefacts. The inner surface of the diaphysis of long bones is mostly compact with prominent trabeculae and lamellae, whereas, after removal of the spongiosa, the inner surface of antler is characterised by numerous grooves. Sometimes, however, artefacts are found which are composed only of the compact bone substance, without inner and outer surfaces, and it is not possible to distinguish between bones and antlers macroscopically. Haversian systems can be found in histological and ground sections of both bones and antlers. In contrast to bones, antlers have few interstitial lamellae. The osteons of antler seem to be smaller and to consist of fewer layers than those of bone. Inner and outer circumferential lamellae cannot be distinguished in antlers. Although microscopic examination of sectioned samples does not allow distinction between bones and antlers in every case, it represents a valuable additional tool for distinguishing between these two materials in historic artefacts. Copyright © 2007 John Wiley & Sons, Ltd.     

Representative archaeological finds of <Emphasis Type="Italic">pietra ollare</Emphasis> from Comacchio (Italy): identifying provenance and high-T mineral breakdown reactions hindering lithotype classification

Three different lithotype groups have been recognized in representative fragments of pietra ollare artefacts found in the mediaeval archaeological excavations of Comacchio (Italy). Petrographic, mineralogical and chemical compositions clearly show that Valchiavenna and Valmalenco, in the Central Alps, represent the provenance areas of two of the pietra ollare groups, i.e. grey carbonate talc schist (also known as soapstone) and green chlorite schist, respectively. The third representative pietra ollare group consists of whitish-yellowish rocks inferred to be Alpine talc schists that have suffered some artificial pyrometamorphic transformation hindering their classification in the framework of pietra ollare lithotype categories and source localities reported in literature. A distinguishing feature of these high temperature-fired (HT-fired) talc schist samples is the occurrence of talc and chlorite dehydroxylation and subsolidus reaction products, mainly protoenstatite/enstatite + forsterite, together with relatively low loss on ignition values. These talc schists might have been exposed to temperatures >900 °C (with the resulting talc dehydroxylation producing a void-rich texture), but never reaching 1200 °C, which is the sintering temperature for soapstones. The whitish-yellowish artefacts were definitely not used as containers for cooking food at temperatures below or around 500–600 °C (as instead shown by the preservation of the original physical features of the grey pietra ollare lithotypes), but in some kind of higher-T pyrotechnological processes.     

SOURCING OBSIDIAN FROM NEOLITHIC ÇATALHÖYÜK (TURKEY) USING ENERGY DISPERSIVE X‐RAY FLUORESCENCE*

This paper details the chemical sourcing of 42 obsidian artefacts from a single Neolithic structure at Çatalhöyük (central Anatolia), using Energy Dispersive X‐Ray Fluorescence (EDXRF). The chemical signatures of the samples match those of two geological sources in southern Cappadocia: East Göllü Da? and Nenezi Da?. The data provide a counterpoint for previous analyses at the site, and suggest possible intra‐community distinctions with regard to shifts in raw material procurement and technical change.     

Recognising burnt vein quartz artefacts in archaeological assemblages

The primary aims of this study were to determine how vein quartz behaves in an open wood fire and to suggest how burnt quartz may reliably be distinguished from unburnt quartz. Experimental burning was conducted on 10–50 mm pieces of knapped quartz collected from outcrops and beach cobbles near a later Mesolithic and Neolithic quartz scatter at Belderrig, north County Mayo, Ireland. Burning resulted in considerable fragmentation, with the majority of post-burning fragments <10 mm in size. Compared to experiments with flint, few quartz pieces were expelled from the hearth during burning, probably due to lower water content. Burning reduced the lustre and transparency of quartz and oxidized any iron-bearing rock impurities to a red-brown or pink colour, but these changes could only be diagnostic of burning where unburnt quartz of the same type is available for comparison. Burning did not affect the texture of the quartz, though quartz grain boundaries became more visible in some samples. Under the microscope, all >5 μm fluid inclusions in quartz lost their fluid contents, often with the development of fluid escape structures, and this is likely to be a reliable discriminant between burnt and unburnt vein quartz generally, even in the absence of unburnt material for comparison. Burning also creates microfractures, but this feature does not provide a diagnostic test of burning as there is considerable overlap between burnt and unburnt samples in microfracture density.     

Infra-red Photoacoustic and Secondary Ion Mass Spectrometry Measurements of Obsidian Hydration Rims

A procedure has been developed for measuring obsidian hydration rim thicknesses on archaeological artefacts using infra-red photoacoustic spectroscopy (IR-PAS). Calibration of the IR-PAS values with depth was completed using secondary ion mass spectrometry (SIMS) and optical microscopy to relate the quantity of diffused water to the measured thickness of the hydration layer. By monitoring the absorbance intensity at 1630 cm⁻¹wavenumbers, hydration rims between approximately 1 μm and 12 μm may be accurately measured and used for chronometric age estimates. SIMS depth profiling has the ability to measure layers less than 1 μm thick, extending the age calibration to samples of less than 100 years in age.     

Application of magnetic susceptibility on polished stone tools from Western Hungary and the Eastern part of the Czech Republic (Central Europe)

A non-destructive method – magnetic susceptibility (MS, κ) measurement – was used to characterize about 360 Neolithic, Copper and Bronze age polished stone tools of the Miháldy collection (Laczkó Dezső Museum, Veszprém, Hungary), composed of artefacts from three Neolithic (Moravian Painted Ware) workshops around a source of greenschist at Želešice near Brno (Moravia, Czech Republic) and semifinished artefacts from workshops at Neolithic mines in the Jizerské hory Mts. (Bohemia, Czech Republic); in addition, rock reference samples collected from the possible provenance areas and rock outcrops in the Czech Republic, Slovakia and Hungary were analysed as comparative material with the same method. We elaborated a model experience to control the thickness correction factor (TCF) following Williams-Thorpe et al. (2000).Among various stone raw materials of polished artefacts we found basaltic rocks and greenschists-metabasites as the most common.     

Stress‐dependent transport properties of fractured arkosic sandstone

We measure the fluid transport properties of microfractures and macrofractures in low‐porosity polyphase sandstone and investigate the controls of in situ stress state on fluid flow conduits in fractured rock. For this study, the permeability and porosity of the Punchbowl Formation sandstone, a hydrothermally altered arkosic sandstone, were measured and mapped in stress space under intact, microfractured, and macrofractured deformation states. In contrast to crystalline and other sedimentary rocks, the distributed intragranular and grain‐boundary microfracturing that precedes macroscopic fracture formation has little effect on the fluid transport properties. The permeability and porosity of microfractured and intact sandstone depend strongly on mean stress and are relatively insensitive to differential stress and proximity to the frictional sliding envelope. Porosity variations occur by elastic pore closure with intergranular sliding and pore collapse caused by microfracturing along weakly cemented grain contacts. The macroscopic fractured samples are best described as a two‐component system consisting (i) a tabular fracture with a 0.5‐mm‐thick gouge zone bounded by 1 mm thick zones of concentrated transgranular and intragranular microfractures and (ii) damaged sandstone. Using bulk porosity and permeability measurements and finite element methods models, we show that the tabular fracture is at least two orders of magnitude more permeable than the host rock at mean stresses up to 90 MPa. Further, we show that the tabular fracture zone dilates as the stress state approaches the friction envelope resulting in up to a three order of magnitude increase in fracture permeability. These results indicate that the enhanced and stress‐sensitive permeability in fault damage zones and sedimentary basins composed of arkosic sandstones will be controlled by the distribution of macroscopic fractures rather than microfractures.     

The World's Oldest Stone Artefacts from Gona, Ethiopia: Their Implications for Understanding Stone Technology and Patterns of Human Evolution Between 2·6–1·5 Million Years Ago

The systematic archaeological and geological survey and excavations at Gona between 1992–1994 led to the discovery of well-flaked stone artefacts which are currently the oldest known from anywhere in the world. More than 3000 surface and excavated artefacts were recovered at 15 localities documented east and west of the Kada Gona river. Based on radioisotopic dating (⁴⁰Ar/³⁹Ar) and magnetostratigraphy, the artefacts are dated between 2·6–2·5 million years ago (Ma). EG10 and EG12 from East Gona are the most informative with the highest density, providing the best opportunity for characterizing the oldest assemblages and for understanding the stone working capability of the earliest tool makers. Slightly younger artefact occurrences dated to 2·4–2·3 Ma are known from Hadar and Omo in Ethiopia, and from Lokalalei in Kenya. Cut-marked bones dated to 2·5 Ma from Bouri in Ethiopia are now providing important clues on the function of these artefacts. In addition, Australopithecus garhi known from contemporary deposits at Bouri may be the best candidate responsible for the oldest artefacts. Surprisingly, the makers of the Gona artefacts had a sophisticated understanding of stone fracture mechanics and control similar to what is observed for Oldowan assemblages dated between 2·0–1·5 Ma. This observation was corroborated by the recent archaeological discoveries made at Lokalalei. Because of the similarities seen in the techniques of artefact manufacture during the Late Pliocene–Early Pleistocene, it is argued here that the stone assemblages dated between 2·6–1·5 Ma group into the Oldowan Industry. The similarity and simplicity of the artefacts from this time interval suggests a technological stasis in the Oldowan.     

Obsidian provenance studies in Colombia and Ecuador: obsidian sources revisited

The field occurrences, elemental compositions and formation ages of Colombian and Ecuadorian obsidians are revisited. It is shown that the regional sources of this raw material are linked to two major volcanic structures: the Chacana and the Paletara calderas, localised on the eastern cordillera of Ecuador and on the central Andean cordillera of south Colombia respectively. Seventy-two samples were analysed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS) and/or particle induced X-ray emission (PIXE). The same 10 types of elemental compositions were identified independently from ICP and PIXE. Four of these types were previously unknown. The formation ages of these obsidians previously determined by fission tracks dating are in the range 0.17–1.58 Ma at Chacana and 3.46–4.27 Ma at Paletara. Most Colombian and Ecuadorian pre-Hispanic artefacts present elemental compositions compatible with a Chacana- or Paletara-derived origin of the raw material. However, some of them present fission track ages discordant with the present-day known obsidian occurrences, which implies that the regional source inventory is not yet exhaustive.