Fourier Transform Raman and Statistical Analysis of Thermally Altered Samples of Amber.

We report the experimental results that refer to a Fourier transform Raman (FT-Raman) survey of thermally altered Baltic and Romanian amber and the related statistical interpretation of data using principal component analysis (PCA). Although FT-Raman spectra show several small changes in the characteristic features of the investigated amber samples which may be used for discrimination, their visual recognition is relatively difficult, especially when interpreting data from archeological samples, and thus multivariate data analysis may be the solution to more accurately assign the geological origin based on overall characteristic spectral features. The two categories of amber have different behavior in terms of degradation during the experimental alteration, and Romanian amber is more susceptible to physico-chemical transformations by the aggressive environment when compared with Baltic amber. The obtained data were in accordance with the Fourier transform infrared (FT-IR) remarks published previously in a dedicated journal. The Raman technique is an alternative method that requires little to no sample preparation, water does not cause interference, and the spectra can be collected from a small volume (1-50 µm in diameter).

Thermal desorption/gas chromatography/mass spectrometry approach for characterization of the volatile fraction from amber specimens: a possibility of tracking geological origins.

Research on the chemical composition of fossil resins has evolved during the last decades as a multidisciplinary field and is strongly oriented toward the correlation with their geological and botanical origin. Various extraction procedures and chromatographic techniques have been used together for identifying the volatile compounds contained in the fossil resin matrix. Hyphenation between thermal desorption (TD), gas chromatography (GC) and mass spectrometry detection (MS) has been chosen to investigate the volatile compounds fraction from ambers with a focus on Romanite (Romanian amber) and Baltic amber species. A data analysis procedure was developed for the main purpose of fingerprinting ambers based on the MS identity of the peaks generated by the volatile fraction, together with their relative percentual area within the chromatogram. Chromatographic data analysis was based entirely on Automated Mass Spectral Deconvolution &Identification System (AMDIS) software to produce deconvoluted mass spectra which were used to build-up a mixed mass spectra and relative retention scale library. Multivariate data analysis was further applied on AMDIS results with successful discrimination between Romanite and Baltic ambers. A special trial was conducted to generate pyrolysis "like" macromolecular structure breakdown to volatile compounds by gamma irradiation with a high absorbed dose of 500 kGy. Contrary to our expectations the volatile fraction fingerprints were not modified after irradiation experiments. A complementary non-destructive new approach by ESR spectroscopy was also proposed for discriminating between Romanite and Baltic ambers.