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The δ13CVPDB and δ18OVSMOW values of caffeine isolated from commercial caffeine-containing foods were determined by isotope ratio mass spectrometry (IRMS) using elemental analysis (EA) in the 'combustion' (C) and 'pyrolysis' (P) modes (EA-C/P-IRMS), respectively. In total, 69 samples (32 guarana products, 20 teas, 12 coffee products, and 5 maté teas) were analyzed together with three references of synthetic caffeine. Validation was done by excluding isotope discrimination in the course of sample preparation and determining linear dynamic ranges for EA-P-IRMS measurements. In total, five samples (one caffeine-containing soft drink and four guarana products) under study contained synthetic caffeine. [ABSTRACT FROM AUTHOR]