Green and roasted arabica coffees differentiated by ripeness, process and cup quality via electrospray ionization mass spectrometry fingerprinting

direct infusion electrospray ionization mass spectrometry in both the negative esi(-)-ms and positive esi(+)-ms ion modes are investigated to differentiate green and roasted arabica coffees with different stages of ripeness (green, ripe and overripe), post-harvesting process (dry, wet and semi-wet) and coffees with different cup qualities. in the esi(-)-ms of green coffees, ions from deprotonated fatty acids and chlorogenic acids are the most important for ripeness discrimination. in the esi(+)-ms, maturity is differentiated by ions from protonated caffeine, chlorogenic acids and k+ adducts of fatty acids. to differentiate between post-harvesting process in both ionization modes, ions from fatty acids, chlorogenic acids, sugars and carboxylic acids generated in the fermentation process are the most representative. roasted arabica coffees are also well discriminated: in the esi(-)-ms, ions from chlorogenic acids and short-chain organic acids derived from sugars are important. in the esi(+)-ms, discrimination are mainly performed by low m/z ions such as protonated pyridine and alkylpiridines formed via trigonelline degradation. both esi(+)-ms and esi(-)-ms are able to differentiate cup quality for arabica roasted coffees and the ions used to perform discrimination are the same ones described in ripeness and post-harvesting processes.