Characterization of hafting adhesives using comprehensive two‐dimensional gas chromatography coupled to time‐of‐flight mass spectrometry

Abstract

The determination of the presence and the composition of residues from organic materials on archeological objects allows the behavior of our prehistoric ancestors to be better understood. The functional analysis of tools used for daily life activities, such as hunting or hide working, represents an important source of information. However, the chemical characterization of residues from archeological artifacts represents an analytical challenge. On one hand, the residues are made of different natural materials containing hundreds of chemicals. This complexity requires advanced analytical procedures to separate and identify the constituents. On the other hand, the low quantity and the advanced degradation require sensitive and non‐destructive methods. In this study, an approach employing headspace sampling (solid‐phase microextraction) with comprehensive two‐dimensional gas chromatography coupled to high‐resolution‐time‐of‐flight mass spectrometry was developed for the characterization of adhesive residues on simulated archeological artifacts. First, the performance of the analytical system was evaluated on a standard mixture and a pine resin sample. Next, adhesives and adhesives mixtures were analyzed that represented typical compositions that have been witnessed in archaeological applications. This analytical approach is a gateway into new potential for headspace organic residue characterization as a first step of analysis prior to altering residues for additional characterization.

Recent Advances in GC×GC and Chemometrics to Address Emerging Challenges in Nontargeted Analysis

“…42,56 Perrault et al also utilized peak tablebased FRA on data collected with GC×GC-HRMS to differentiate the volatile signature of adhesives commonly used for archeological artifacts. 57 Recently, both SepSolve and LECO released commercial versions of the tile-based FRA 21,29 called ChromCompare+ and ChromaTOF Tile, respectively, with several applications recently described. 58−64 It should be noted that ChromaTOF Tile uses the standard F-ratio calculation, whereas Chrom-Compare+ uses a "proprietary multivariate metric" calculated on each tile.…”

“…Similar to the exemplary work shown in Figure B, Purcaro et al utilized peak table-based FRA to discover 16 analytes that differentiated cells infected by respiratory syncytial virus . Furthermore, Dorman and co-workers have recently used FRA to discover dozens of compounds correlated to the declining health of smallmouth bass in polluted river basins. , Regarding food studies, peak table-based FRA was also employed to discover differences in wines based on grape maturity, vine management, and maceration times. , Perrault et al also utilized peak table-based FRA on data collected with GC×GC-HRMS to differentiate the volatile signature of adhesives commonly used for archeological artifacts …”

Comprehensive Two-Dimensional Gas Chromatography Advances in Technology and Applications: Biennial Update

“…Common materials in everyday products, plastics, and derivatives have become the target of many studies, mainly due to the presence of some components that can have a strong odor and potential contamination capacity, which can impact human health. Such studies focus mainly on packaging, ,, adhesives, , rubber, lacquers, , and paintings. , …”

“…Perrault et al 179 developed a first-step nondestructive SPME-GC×GC−TOFMS method to assess the composition of hafting adhesives, demonstrating its applicability to archeological studies. Seven laboratory-made adhesives composed of resins and beeswax as well as a 15-year-old reproduction of a stone tool were investigated.…”