Chemical analyses of extremely degraded wood using analytical pyrolysis and inductively coupled plasma atomic emission spectroscopy

Alum-treated archaeological woods from the Oseberg collection, excavated and treated in the early 1900s demonstrate an extreme deterioration, only discovered in the past decade. This research was aimed at understanding the characteristics of the naturally aged material through chemical analyses of both organic and inorganic components, in order to provide information for the preservation/conservation of these precious objects. Analytical pyrolysis-gas chromatography/mass spectrometry with in situ silylation using hexamethyldisilazane (Py(HMDS)-GC/MS) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) were used to investigate a set of samples of alum-treated archaeological wood and untreated archaeological wood. Sound woods of the same species were also analysed in order to compare the results. Results from Py(HMDS)-GC/MS analyses of alum-treated woods from Oseberg showed an extreme depletion of carbohydrates and a highly deteriorated lignin network. The majority of the lignin had undergone oxidation reactions, illustrated by high relative amounts of acidic pyrolysis products. In particular, p-hydroxy-benzoic acid was detected for the first time as a degradation product of archaeological wood. Results from ICP-AES showed variable concentrations of aluminium and potassium from the alum treatment, as well as iron, copper, zinc and calcium. The extent of oxidation observed by Py(HMDS)-GC/MS appeared to correlate with relative amounts of iron and calcium in the samples, which may suggest that degradation promoted by iron compounds is inhibited in the presence of calcium compounds. The results obtained for a sample of archaeological wood treated with alum salts five years ago showed that chemical deterioration of lignin had already begun, mainly involving depolymerisation reactions, though only a slight increase in oxidation was evident. In addition to increased insight into potential deterioration reactions, occurring in a complex material such as alum-treated archaeological wood, it was possible to relate the degree of chemical degradation of the Oseberg woods to their visual condition (observed with the naked eye). © 2015 Elsevier B.V

Controlled depolymerisation, as assessed by analytical ultracentrifugation, of low molecular weight chitosan for potential use in archaeological conservation

The heterogeneity and molecular weight of a chitosan of low molecular weight (molar mass) and low degree of acetylation (0.1), for potential use as a consolidant for decayed archaeological wood, has been examined by sedimentation velocity and sedimentation equilibriumin the analytical ultracentrifuge before and after depolymerisation. Sedimentation velocity before polymerisation revealed a uniform distribution of sedimentation coefficient with little concentration dependence. SEDFIT-MSTAR analysis revealed a weight average molecular weight Mw of (14.2 + 1.2) kDa, and polydispersity index of ~ 1.2. Further analysis using MULTISIG revealed a distribution of material between 2-20 kDa and consistent with the weight average Mw. Controlled depolymerisation using hydrogen peroxide and UV in an acetic acid medium reduced this to (4.9 + 0.7) kDa, with a similar polydispersity. The depolymerised material appears to be within the range that has been predicted to fully penetrate into archaeological wood. The consequences for this and the use of the analytical ultracentrifuge in wood conservation strategies is considered

The Clacton Spear: the last one hundred years

In 1911 an eminent amateur prehistorian pulled the broken end of a pointed wooden shaft from Palaeolithic-age sediments at a seaside town in Essex. This artefact, still the earliest worked wood to be discovered in the world, became known as the Clacton Spear. Over the past 100 years it has variously been interpreted as a projectile weapon, a stave, a digging stick, a snow probe, a lance, a game stake and a prod to ward off rival scavengers. These perspectives have followed academic fashions, as the popular views of early hominins have altered. Since discovery the Clacton spear has also been replicated twice, has undergone physical transformations due to preservation treatments, and has featured in two public exhibitions. Within this article the changing context of the spear, its parallels, and all previous conservation treatments and their impacts are assessed.© 2015 Royal Archaeological Institute. This is an Accepted Manuscript of an article published by Taylor & Francis in The Archaeological Journal on 3rd March 2015, available online: http://www.tandfonline.com/doi.org/10.1080/00665983.2015.1008839.The attached document is the author(’s’) final accepted/submitted version of the journal article. You are advised to consult the publisher’s version if you wish to cite from it

Physical and chemical effects of red cells in the shear-induced aggregation of human platelets.

Both chemical and physical effects of red cells have been implicated in the spontaneous aggregation of platelets in sheared whole blood (WB). To determine whether the chemical effect is due to ADP leaking from the red cells, a previously described technique for measuring the concentration and size of single platelets and aggregates was used to study the shear-induced aggregation of platelets in WB flowing through 1.19-mm-diameter polyethylene tubing in the presence and absence of the ADP scavenger enzyme system phosphocreatine-creatine phosphokinase (CP-CPK). Significant spontaneous aggregation was observed at mean tube shear rates, (G) = 41.9 and 335 s-1 (42% and 13% decrease in single platelets after a mean transit time (t) = 43 s, compared to 89 and 95% decrease with 0.2 microM ADP). The addition of CP-CPK, either at the time of, or 30 min before each run, completely abolished aggregation. In the presence of 0.2 microM ADP, CP-CPK caused a reversal of aggregation at (t) = 17 s after 30% of single cells had aggregated. To determine whether red cells exert a physical effect by increasing the time of interaction of two colliding platelets (thereby increasing the proportion of collisions resulting in the formation of aggregates), an optically transparent suspension of 40% reconstituted red cell ghosts in serum containing 2.5-micron-diameter latex spheres (3 x 10(5)/microliters) flowing through 100-microns-diameter tubes was used as a model of platelets in blood, and the results were compared with those obtained in a control suspension of latex spheres in serum alone. Two-body collisions between microspheres in the interior of the flowing ghost cell or serum suspensions at shear rates from 5 to 90 s-1 were recorded on cine film. The films were subsequently analyzed, and the measured doublet lifetime, tau meas, was compared with that predicted by theory in the absence of interactions with other particles, tau theor. The mean (tau meas/tau theor) for doublets in ghost cell suspensions was 1.614 +/- 1.795 (SD; n = 320), compared to a value of 1.001 +/- 0.312 (n = 90) for doublets in serum. Whereas 11% of doublets in ghost cell suspensions had lifetimes from 2.5 to 5 times greater than predicted, in serum, no doublets had lifetimes greater than 1.91 times that predicted. There was no statistically significant correlation between tau meas/tau theor and shear rate, but the values of tau meas/tau theor for low-angle collisions in ghost cell suspensions were significantly greater than for high-angle collisions

New insights into the degradation processes and influence of the conservation treatment in alum treated wood from the Oseberg collection

The Oseberg collection includes the most complete ensemble of wooden remains from the Viking Age. However, since many of the wooden objects were treated with alum in the early 1900s, they now suffer from dramatic conservation issues. A multi-analytical approach was adopted to investigate both the organic and the inorganic components of some selected wood fragments, with the aim of fully characterising the materials and their decomposition products. A particular focus was taken on the differences between the surface and the core of the fragments analysed, and on the correlations between the results obtained by the different techniques, in order to disclose possible interactions between the materials during degradation. In addition to differences in alum concentration and wood alteration between the surface and the core, some decomposition/transformation products of alum, such as mercallite (KHSO4), were identified by FTIR and XRD. Contextual interpretation of the results obtained by ICP-OES elemental analysis of inorganic components and Py(HMDS)-GC/MS characterisation of degraded lignocellulosic materials supported some previous observations about potential relationships between specific metals (Al, Fe, Ca) and wood degradation and enabled new correlations to be highlighted. Although similar degradation patterns were revealed in the investigated objects–depletion of holocellulose, oxidation of lignin and some transformation of alum - a notable variability at the molecular level was highlighted. This is an important factor to be taken into account for the planning of re-treatment strategies of these extremely precious artefacts

Development of Storage and Assessment methods suited for organic Archaeological artefacts (StAr) - JPI-CH project

StAr project - Development of Storage and assessment methods suited for organic archaeological artefacts - started in 2020 within the framework of Joint Programming Initiative on Cultural Heritage and Global Change (JPI-CH) Conservation, Protection and Use. The project arises from the need for chemical-physical stabilization strategies of archaeological finds (mainly wood and leather), for long time (up to several months) in the waterlogged state, i.e., under pre-treatment conditions, without compromising the archaeological and scientific evidences they contain. Several methods of controlling storage conditions will be tested on archaeological wooden and leather objects. The experimentations will entail a systematic chemical analysis and monitoring of the organic materials before, during and after storage in different conditions, both in laboratory and on-field at the Biskupin archaeological excavation site in Poland