A New Approach for the Characterization of Organic Residues from Stone Tools Using GC×GC-TOFMS

Abstract

Headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) have traditionally been used, in combination with other analyses, for the chemical characterization of organic residues recovered from archaeological specimens. Recently in many life science fields, comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GCˆGC-TOFMS) has provided numerous benefits over GC-MS. This study represents the first use of HS-SPME-GCˆGC-TOFMS to characterize specimens from an experimental modern reference collection. Solvent extractions and direct analyses were performed on materials such as ivory, bone, antlers, animal tissue, human tissue, sediment, and resin. Thicker film column sets were preferred due to reduced column overloading. The samples analyzed by HS-SPME directly on a specimen appeared to give unique signatures and generally produced a higher response than for the solvent-extracted residues. A non-destructive screening approach of specimens may, therefore, be possible. Resin and beeswax mixtures prepared by heating for different lengths of time appeared to provide distinctly different volatile signatures, suggesting that GCˆGC-TOFMS may be capable of differentiating alterations to resin in future studies. Further development of GCˆGC-TOFMS methods for archaeological applications will provide a valuable tool to uncover significant information on prehistoric technological changes and cultural behavior.

Fingerprinting Glues Using HS‐SPME GC×GC–HRTOFMS: a New Powerful Method Allows Tracking Glues Back in Time

“…A recent study by the authors demonstrated that the use of comprehensive two‐dimensional gas chromatography coupled to time‐of‐flight mass spectrometry (GC×GC‐TOFMS) afforded an increase in separation resolution and sensitivity when analysing these highly complex glues (Perrault et al . ). In addition, the headspace solid‐phase microextraction (SPME) enabled us to develop a sampling method that was as non‐destructive as possible (Hamm et al .…”

“…A recent study by the authors demonstrated that the use of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) afforded an increase in separation resolution and sensitivity when analysing these highly complex glues ). In addition, the headspace solid-phase microextraction (SPME) enabled us to develop a sampling method that was as nondestructive as possible (Hamm et al 2003;Regert et al 2006;Perrault et al 2016). However, HS-SPME coupled with traditional GC-MS (Hamm et al 2003;Regert et al 2006) is rather limited in both separation power and identification capabilities, which may hamper the identification of the numerous individual compounds of these complex organic mixtures.…”

“…A fibre blank was performed at the beginning of each sequence and between each set of 10 samples (Perrault et al . ).…”

“…More recently, the extraction of VOCs using HS‐SPME and analysis using comprehensive two‐dimensional gas chromatography – time‐of‐flight mass spectrometry (GC×GC–TOFMS) on various experimental residues resulted in an improved molecular separation of complex glue samples (i.e., resin and beeswax) (Perrault et al . ). However, the differentiation of the hundreds of molecular components of resin–beeswax proved to be limited by the TOFMS detection system.…”

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

“…Previous reports have determined that these archaeological adhesives and their associated components can contain various structural isomers across compound classes . This has been particularly emphasized for terpene and terpenoid compounds originating from plant origins .…”