Evaluation of a Tobacco Fractionation Procedure Using Pyrolysis Mass Spectrometry Combined with Multivariate Analysis

Abstract

SUMMARYThis paper presents an evaluation of a fractionation procedure for use with tobacco. Correlation coefficients calculated from the weights of the polymer fractions obtained and data obtained with classical wetchemical methods show that these parameters have a low resolving power, which precludes any detailed distinction between tobaccos and tobacco-derived fractions. Pyrolysis mass spectrometry combined with multivariate analysis is presented as a promising approach for investigating the variability in the chemical composition of tobacco. Multivariate analysis performed on the pyrolysis mass-spectrometric fingerprints of all tobacco fractions indicates that the differences between the individual tobaccos are smaller than the differences induced by the fractionation procedure. Multivariate analysis of subfdes of the pyrolysis mass-spectrometric fingerprints of separate polymer fractions is an excel- lent method for classifying tobaccos. Leaf and stem material can easily be distinguished. A further differentiation is made between the flue-cured and Burley-type tobaccos. The strong clustering of tobacco samples after treatment with potassium hydroxide points to a uniform cell-wall skdeton. The greater variability in the ethanolized tobacco samples, and samples subjected to hot-water extractia:n or amylase digestion, is related to the cytosol characteristics. These fractions appear to reflect both the dissimilarities between the distinct tobacco types and phenotypic variations due to differences in cultural management. Pyrolysis mass spectrometry of the K.lason lignin residues points to a large variety of chemical constituents unrelated to lignin. Pyrolysis gas-chromatography mass-spectrometric data on the K.lason lignin residues of a Burley tobacco showed that the correlation made between the organic-nitrogen content and the protein content of this fraction might be misleading. As a consequence the maximum value for the lignin content of this tobacco is estimated incorrectly. sieurs variables (multivariance) se rC:vele une approche prometteuse pour !'etude des differences de composition chimique des tabacs. L'analyse des spectres de masse (fingerprints) obtenus aprh pyrolyse de toutes les fractions de tabac montre que les differences existant entre les divers types de tabac soot plus faibles que celles qui soot induites par la mC:tbode de fractionnement. L'analyse (multivariance) realisee separement sur les spectres de masse des differentes fractions polymeres est une excellente methode pour la classification des tabacs. Les cOtes et les feuilles se distinguent facilement; le tabac Hurley et le tabac «flue-cured• soot aussi nettement differencies. La formation marquee de grappes (cluster) parmi les ecbantillons apres traitement par l'hydroxyde de potassium indique que la structure de la paroi cellulaire semble etre la meme chez tous les tabacs. Apres extraction par l'Ctbanol suivie d'une extraction par I' eau chaude ou d'un traitement par !'amylase, on obtient dans chaque cas des residus presentant une varia...

Application of time-of-flight mass spectrometry with laser-based photoionization methods for analytical pyrolysis of PVC and tobacco

“…In contrast, oxygen-containing compounds show the opposite behaviour and decrease (44,56,58,68,70,82,86, and 96 m/z) as well as vinylpyridine 105 and 84 m/z. The species 68 m/z is difficult to assign and furan and isoprene are two possible candidates [44,[47][48][49]. Since 68 m/z shows the same behaviour as oxygen-containing compounds it is suggested that the main part of this mass is attributable to furan rather than isoprene.…”

“…43,44,56,58,72,82,86,96,98, and 110 m/z) as well as proteins and amino acids (e.g. 67, 69, 79, 81, and 93 m/z) are present [44][45][46][47][48][49][50][51].…”

Molecular Products and Radicals from Pyrolysis of Lignin

“…Biomass pyrolysis remains a critical chemical process in the utilization of renewable energy and feed stocks, generation of aromatic feed stocks, and destruction of forests by fires. , The intricate nature and uncertain processes occurring in the pyrolysis of biomass have generated interest in the study of thermal degradation of lignin. Lignin is a highly cross-linked polyphenolic polymer without any ordered repeating units and is perhaps one of the most complex organic aromatic polymers in nature. − The lignin fraction of biomass is an important source of benzene, phenol, and dihydroxybenzenes during burning . Among the major components of biomass, lignin presents the greatest difficulty in understanding the relationship between structure and the devolatilization mechanisms occurring during typical thermochemical conversion processes .…”

Thermal desorption/pyrolysis coupled with photo ionisation time-of-flight mass spectrometry for the analysis and discrimination of pure tobacco samples

“…Furthermore, typical decomposition products from thermal degradation of carbohydrates such as cellulose, lignin and sugars (e.g. 43,44,56,58,72,82,86,96, and 98 m/z) are present [12,16,22,23,68,[70][71][72]. Moving to even higher masses, two signals at 228 and 256 m/z emerge at 250 8C, which can be assigned to fatty acids, namely myristic and palmitic acid, respectively.…”

“…In the past, a wide range of pyrolysis and TGA studies on tobacco, e.g. [11][12][13][14][15][16][17][18][19][20][21] have been carried out, mainly by application of conventional analytical methods such as gas chromatography/mass spectrometry and Fourier transformed infrared spectroscopy (FT-IR). However, in recent years, application of soft ionisation methods, e.g.…”