Gas Chromatography–Mass Spectrometry Assessment of Amines in Port Wine and Grape Juice after Fast Chloroformate Extraction/Derivatization

A simple, reliable, and sensitive gas chromatography-mass spectrometry method for the quantification of volatile and nonvolatile biogenic amines in Port wines and grape juices was developed and evaluated. The method was based on a previously reported two-phase derivatization procedure with isobutyl chloroformate in a toluene medium, which provides a quantitative reaction in 10 min. Following the derivatization step, the excess of reagent was eliminated by treatment with alkaline methanol. The derivatization procedure was performed directly on 1 mL of sample, avoiding any fastidious and time-consuming cleanup extraction steps. The method allows the simultaneous quantification of 22 amines, which can be found in wines: methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, isobutylamine, amylamine, isoamylamine, 2-methylbutylamine, hexylamine, pyrrolidine, piperidine, morpholine, 1,3-diaminopropane, putrescine, cadaverine, 1,6-diaminohexane, 2-phenylethylamine, histamine, and tyramine. Because of the fact that histamine and tyramine derivatives are degraded during the isobutyl chloroformate elimination step, the corresponding determination was made after removal of the excess of derivatizing reagent by evaporating an aliquot of the toluene layer obtained after the reaction. The presented method showed excellent analytical characteristics in what linearity, recovery, repeatability, and limit of detections were respected. It was used to assess the concentration of biogenic amines in juice grapes and Tawny and Vintage Port wines with different aging times. On the whole, the total content of amines in Port wines was low. Most of the amines found in wines have their origin in the raw material used for their elaboration, so the Port winemaking process is not prone to the production of this kind of compounds. Total biogenic amine contents have shown a decrease with the aging of both types of Port wines.