Advanced oxidation of caffeine in water: on-line and real-time monitoring by electrospray ionization mass spectrometry.

High performance liquid chromatography (HPLC), ultraviolet spectroscopy (UV), and total organic carbon (TOC) analyses show that caffeine is quickly and completely degraded underthe oxidative conditions of the UV/H2O2,TiO2/ UV, and Fenton systems but that the organic carbon content of the solution decreases much more slowly. Continuous on-line and real-time monitoring by electrospray ionization mass (ESI-MS) and tandem mass spectrometric experiments (ESI-MS/MS) as well as high accuracy MS measurements and gas chromatography-mass spectrometry analysis show that caffeine is first oxidized to N-dimethylparabanic acid likely via initial OH insertion to the C4=C8 caffeine double bond. A second degradation intermediate, di(N-hidroxymethyl)parabanic acid, has been identified by ESI-MS and characterized by ESI-MS/MS and high accuracy mass measurements. This polar and likely relatively unstable compound, which is not detected by off-line GC-MS analysis, is likely formed via further oxidation of N-dimethylparabanic acid at both of its N-methyl groups and constitutes an unprecedented intermediate in the degradation of caffeine.