Evaluation of the Deterioration State of Archaeological Wooden Artifacts: A Nondestructive Protocol based on Direct Analysis in Real Time - Mass Spectrometry (DART-MS) Coupled to Chemometrics

Evaluating the deterioration state of archeological wood is obligatory before the preservation of archeological wooden artifacts. Herein, a nondestructive, accurate, and rapid methodology is first developed via direct analysis in real time-mass spectrometry (DART-MS) with chemometrics to classify archeological wood and recent wood into 3 groups according to their deterioration states. As water in wooden artifacts probably affected the ion fragmentation process during DART-MS, ions responsible for evaluating the deterioration state were separately screened toward waterlogged archeological wood and dried archeological wood by partial least-squares discriminant analysis (PLS-DA). The well-defined separation of severely decayed archeological wood, moderately decayed archeological wood and recent wood was revealed in PLS-DA models. Twenty and 27 wood fragment ions were further screened as key variables to evaluate the deterioration state of waterlogged archeological wood and dried archeological wood, respectively. They were tentatively identified as ions of lignin monomeric compositions, lignin dimers, lignin trimers, and oligosaccharides. Results strongly suggested that differences in the structure and relative abundances of wood cell wall components accounts for the evaluation of deterioration state by DART-MS coupled to chemometrics. PLS-DA models provided R²Y = 0.836, Q² = 0.817, and R²Y = 0.754, Q² = 0.682 were then established separately using mass spectral fingerprints of respective potential predictive wood fragment ions. Furthermore, archeological woods, consisting of Castanopsis, Quercus, Idesia, Populus, and Cunninghamia species and with an average MWC range of 103-465%, were used as an external validation set and evaluated with the methodology developed herein and the MWC criteria. Results showed that DART-MS coupled to chemometrics could accurately predict the inhomogeneous deterioration states of archeological wooden artifacts and avoid the interference of inorganic deposits, in comparison with the MWC criteria.