Jennifer Poulin

THE IDENTIFICATION OF HAFTING ADHESIVE ON A SLOTTED ANTLER POINT FROM A SOUTHWEST YUKON ICE PATCH

This article describes the identification of a hafting adhesive on an antler point, slotted for microblade insertion. The adhesive, found in the slots of the point, would have held the microblades in place. Radiocarbon dated to 7310 ± 40 B.P. (uncalibrated), the point is one of the oldest and best-preserved artifacts recovered from the melting alpine ice patches in southwestern Yukon, Canada. Because the artifact was frozen, the organic components have not degraded and a detailed chemical analysis was possible. Analyses of residue in the slots of the point by Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry showed that a conifer resin adhesive was used. The high concentration of diterpene resin acids with an abietane or pimerane skeleton confirmed a Pinaceae source for the resin. There were no chemical markers to indicate that the resin had been strongly heated to produce tar or pitch. Based on a comparison with five Pinaceae resins from trees common to southern Yukon, the resin from the slotted point most closely resembles the chemical profile of spruce (Picea sp.). The identification of this hafting adhesive on a slotted point adds significantly to our understanding of early hunting technology in Yukon.

Inside Amber: The Structural Role of Succinic Acid in Class Ia and Class Id Resinite

For the first time, molecular evidence of the structural role played by succinic acid within the macromolecular structure of Class Ia and Class Id resinite is presented. Using a novel gas chromatographic methodology, communol (Class Ia) and ozol (Class Id) moieties within the polylabdane matrix are shown to be cross-linked with succinic acid. Samples were analyzed using pyrolysis-gas chromatography-mass spectrometry with in situ hexamethyldisilazane derivatization, using a thermal separation probe to perform the pyrolysis and sample introduction. The relatively slow rate of heating and prolonged pyrolysis of resinites using this new methodology, combined with the use of a mild derivatization reagent, allowed communol pyrolysates from Class Ia resinite and ozol pyrolysates from Class Id resinite to elute with unbroken succinyl ester cross-linkages. These results provide direct molecular evidence that the key role of succinic acid within Class Ia and Class Id resinite is to cross-link the macromolecular structure. In the Class Id resinite, the methodology also allowed the detection of succinyl ester linkages between ozol pyrolysates and dehydroabietol, thus demonstrating that nonpolymerized diterpenes contribute structurally to the macromolecular structure of Class Id resinite.

Conservation Issues in Several Twentieth-Century Canadian Oil Paintings: The Role of Zinc Carboxylate Reaction Products

In an on-going study of the materials and techniques of twentieth-century Canadian painters, similar conservation issues in oil paintings by various artists have been noted. These include delamination and lifting paint, zinc soap protrusions and surface efflorescence or accretions. Examples of these phenomena are presented. Delamination in an oil painting from 1956 was found to be related to an underlayer with a high concentration of zinc fatty acid salts (zinc soaps). In two paintings that date from 1936 and 1937, zinc soaps have aggregated and formed protrusions that have broken through the paint surface. The protrusions were analysed using a combination of SEM-EDX, GCMS and FTIR. The FTIR spectra were compared to those of synthetic zinc palmitate, stearate, azelate and oleate. The combined GCMS and FTIR results indicate that the protrusions contain primarily zinc palmitate and stearate. Peak splitting in the FTIR spectrum, which is not observed in synthetic zinc palmitate, stearate or binary palmitate-stearate salts, is likely due to structural distortion. The final example describes a disfiguring surface accretion on a 1952–1954 painting caused by the reaction of zinc with a low molecular weight carboxylic acid (2-hydroxypropanoic or lactic acid).

Jack Chambers’ mixed media paintings from the 1960s and 1970s: Painting technique and condition

Abstract This study describes the examination and analysis of four mixed media paintings from the 1960s and 1970s by Canadian artist Jack Chambers (1931–1978). The documentary evidence about his materials and methods is summarized and compared with the results of analysis of multilayer paint samples. The combination of Fourier transform infrared spectroscopy (FTIR) and gas chromatography-mass spectrometry (GC-MS) allowed the components of the paint media to be characterized: ortho-phthalate alkyd resins, iso-phthalate alkyd resins, drying oils, dammar, Pinaceae resin, and turpentine were identified in varying proportions. Many pigments and fillers were identified by FTIR and Raman and are enumerated. The effect that Chambers’ complex technique has had on the aging and degradation of the paintings is discussed. The severe cracking of the paint layers in one of the four paintings may be the result of a high proportion of dammar and turpentine diluent mixed with the alkyd paint and may also be related to the type of alkyd resin medium. Different history and environmental conditions may also be factors.

A New Methodology for the Characterisation of Natural Dyes on Museum Objects Using Gas Chromatography–Mass Spectrometry

ABSTRACT The derivatising agent m-(trifluoromethyl)phenyltrimethylammonium hydroxide (TMTFTH) has been employed for more than a decade at the Canadian Conservation Institute (CCI) to extract natural dyes from historical textiles and other dyed substrates. The alkaline reagent breaks the bonds between the colourants and the mordant ions or functional groups of the substrate, releasing the dye compounds into the extraction solution, and derivatises polar functionalities to produce compounds that are amenable to subsequent analysis by gas chromatography–mass spectrometry (GC–MS). This approach allows for the identification of the colourants, and is also useful in determining the presence of degradation products from the dyes and substrates, non-dye marker compounds, auxiliary compounds added to the dye bath, and substances present on the object through anthropogenic use, conservation treatments, or possible pesticide contamination. This paper discusses compounds formed through the reactions of TMTFTH with flavonoid dyes (dyer’s buckthorn, old fustic, weld, red sandalwood, and brazilwood), quinone dyes (madder, Relbunium, Galium, cochineal, lac, and walnut), indigoid dyes (indigo, Tyrian purple, and indigo carmine), turmeric, marigold, lupin and several lichen species. Results from a selection of historical dyed textiles and other decorative objects analysed at the CCI are provided to illustrate applications of the methodology.

Historical mystery solved: a multi-analytical approach to the identification of a key marker for the historical use of brazilwood (Caesalpinia spp.) in paintings and textiles

Dyes derived from brazilwood (Caesalpinia spp.) are known to have been used in a diverse range of objects, from Medieval European textiles to North American First Nations objects, while pigments made from brazilwood feature in the palette of a number of painters, including Rembrandt and Van Gogh. For almost two decades, an unknown marker has been used to detect brazilwood colourants in historical objects. Limited sampling opportunities mean that the identification of the chemical structure of this marker has eluded scientists to date. Using a combination of synthesis, UPLC-ESI-MS/MS, HPLC, NMR and GC-MS, the identity of this unknown marker was confirmed as the benzochromenone, urolithin C. Structural identification provides a reliable reference compound for use across a range of analytical techniques employed in the cultural heritage sector and will enable the future development of non-destructive techniques for its identification on high-status objects.