Characterisation of archaeological waterlogged wood by pyrolytic and mass spectrometric techniques

1) Department of Chemistry and Industrial Chemistry, University of Pisa, via Risorgimento 35. 56126 Pisa, Italy ; 2) IRNAS-CSIC, Seville, Spain; E-mail address: [email protected] combination of two techniques based on analytical pyrolysis and mass spectrometry, including direct exposure-MS (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), was used to study the chemical composition of waterlogged archaeological wood. In particular, the two techniques were used to chemically characterise samples of archaeological wood from the excavation of the Site of the Ancient Ships of Pisa San Rossore in Pisa (Italy). The data were compared to those of native sound wood of the same species. The results highlight that DE-MS is a valuable technique for the characterisation of archaeological wood. DE-MS allows us to use a minimal sample size and to perform the analysis in a few minutes, thus avoiding the long wet-chemical procedures that are commonly used to characterise wood. The results also confirm the importance of Py-GC/MS as a tool for shedding light on the chemical modifications of wood in archaeological objects. The analyses demonstrated that waterlogged wood from the site of Pisa San Rossore have undergone an extensive loss of polysaccharides together with partial demethylation of lignin units, both guaiacyl and syringyl monomers. In fact, catechols and methoxy catechols were identified among the pyrolysis products of the waterlogged wood samples.The authors wish to thank Dott.ssa G. Giachi (Restoration Laboratories of the Archaeological Superintendence of Tuscany, Florence, Italy) for providing archaeological wood samples and for her valuable support and collaboration. Funding was provided by the Archaeological Superintendence of Tuscany and by the Italian MIUR (PRIN Cofin05).Peer reviewe

Effects of low sulfur dioxide concentrations on bioactive compounds and antioxidant properties of Aglianico red wine

This study analyzed the effect of low sulfur dioxide concentrations on the chromatic properties, phytochemical composition and antioxidant activity of Aglianico red wines with respect to wines produced from conventional winemaking. We determined the phytochemical composition by spectrophotometric methods and HPLC-DAD analysis and the in vitro antioxidant activity of different wine samples by the ORAC assay. The main important classes of fluorophore molecules in red wine were identified by Front-Face fluorescence spectroscopy, and the emission intensity trend was investigated at various sulfur dioxide concentrations. Lastly, we tested the effects of both conventional and low sulfite wines on ex vivo human erythrocytes under oxidative stimulus by the cellular antioxidant activity (CAA) assay and the hemolysis test. The addition of sulfur dioxide, which has well-known side effects, increased the content of certain bioactive components but did not raise the erythrocyte antioxidant capacity

The Still Bay and Howiesons Poort at Sibudu and Blombos: Understanding Middle Stone Age Technologies

The classification of archaeological assemblages in the Middle Stone Age of South Africa in terms of diversity and temporal continuity has significant implications with respect to recent cultural evolutionary models which propose either gradual accumulation or discontinuous, episodic processes for the emergence and diffusion of cultural traits. We present the results of a systematic technological and typological analysis of the Still Bay assemblages from Sibudu and Blombos. A similar approach is used in the analysis of the Howiesons Poort (HP) assemblages from Sibudu seen in comparison with broadly contemporaneous assemblages from Rose Cottage and Klasies River Cave 1A. Using our own and published data from other sites we report on the diversity between stone artifact assemblages and discuss to what extent they can be grouped into homogeneous lithic sets. The gradual evolution of debitage techniques within the Howiesons Poort sequence with a progressive abandonment of the HP technological style argues against the saltational model for its disappearance while the technological differences between the Sibudu and Blombos Still Bay artifacts considerably weaken an interpretation of similarities between the assemblages and their grouping into the same cultural unit. Limited sampling of a fragmented record may explain why simple models of cultural evolution do not seem to apply to a complex reality

Climatically Induced Degradation Processes in Conserved Archaeological Wood Studied by Timelapse Photography

Samples of conserved archaeological wood of different ages, origins, and conservation histories were aged in a climate chamber for seven months, while the humidity alternated between 30% RH for 12 hours and 80% RH for 12 hours at a constant temperature of 30°C. Photographs were taken once every hour, which enabled the creation of a time-lapse movie. Some samples degraded visibly, whereas others were unaffected. Most of the samples were robust and would be able to survive well even in a very poor museum climate. Among the sensitive samples, three types of degradation were identified, namely disintegration, pyrite oxidation, and efflorescence of white crystals. Disintegration was ascribed to dimensional changes caused by the RH alternations in very fragile wood. The white efflorescence was interpreted as the recrystallization of an alum-associated substance, possibly mercallite (KHSO4). The pyrite oxidation was observed as the efflorescence of a thick yellow, grey, and green powder. Characterization of selected samples was performed using X-ray fluorescence spectrometry, X-ray diffraction spectrometry, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma – optical emission spectroscopy, Fourier transform infrared spectroscopy, ionic conductivity – liquid chromatography, and pyrolysis-gas chromatography-mass spectrometry with in situ silylation using hexamethyldisilazane

Hafting of Middle Paleolithic tools in Latium (central Italy): New data from Fossellone and Sant'Agostino caves

Hafting of stone tools was an important advance in the technology of the Paleolithic. Evidence of hafting in the Middle Paleolithic is growing and is not limited to points hafted on spears for thrusting or throwing. This article describes the identification of adhesive used for hafting on a variety of stone tools from two Middle Paleolithic caves in Latium, Fossellone Cave and Sant'Agostino Cave. Analysis of the organic residue by gas chromatography/mass spectrometry shows that a conifer resin adhesive was used, in one case mixed with beeswax. Contrary to previous suggestions that the small Middle Paleolithic tools of Latium could be used by hand and that hafting was not needed since it did not improve their functionality, our evidence shows that hafting was used by Neandertals in central Italy. Ethnographic evidence indicates that resin, which dries when exposed to air, is generally warmed by exposure to a small fire thus softened to be molded and pushed in position in the haft. The use of resin at both sites suggests regular fire use, as confirmed by moderate frequencies of burnt lithics in both assemblages. Lithic analysis shows that hafting was applied to a variety of artifacts, irrespective of type, size and technology. Prior to our study evidence of hafting in the Middle Paleolithic of Italy was limited to one case only

Reply to Evans : Use of poison remains the most parsimonious explanation for Border Cave caster bean extract

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Blombos Still Bay, circular scrapers.

<p>All of silcrete. (1, 3, 4, 5) CC nos. 1, 32, 47, 49. (2) CAR no. 6. (6) CD no. 39. (7) CFA-CDB no. 8. (8) CE no. 17; (9a, b) CAB no. 53; (10) CB no. 18. (11) CD-CE no. 56. Scale bars = 1 cm.</p

Frequencies of classes of backed tools in GR, GS and PGS.

<p>Frequencies of classes of backed tools in GR, GS and PGS.</p

Sibudu Still Bay.

<p>Frequencies of shaping flake types in dolerite and hornfels.</p