Off-line pyrolysis coupled with GC-MS through SPME sampling, overcomes some of the limitation of online
Py-GC-MS configuration without laborious sample treatment. The introduction of on fiber silylation procedure
between SPME sampling and analysis allowed to obtain a complete silylation of polar pyrolysis products with
diagnostic relevance. The method was applied to the analysis of pure sugars and carbohydrates, providing a
picture of the type of anhydrosugars evolved by pyrolysis of natural gums, namely cellulose and polysaccharide
based gums (Arabic, Ghatti, Tragacanth, Guar, Karaya and Xanthan). Characteristic anhydrosugars produced by
pyrolysis of hexoses, pentoses and deoxyhexoses were tentatively identified. Despite an unambiguous marker
for uronic acids was not identified, the final method allowed to obtain, with minimalwork-up, a detailed picture
of polar pyrolysis products as those obtainable from carbohydrates, which can be easily used for identification
purposes.