Discrepancies in determination of biogenic amines in beer samples by reversed phase and hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry

Abstract

Biogenic amines (BAs) are nitrogenous organic bases occurring mainly in fermented food and beverages as a result of free amino acids bacterial decarboxylation. The reversed phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) based methods were compared in terms of usefulness for determination of BAs in beer samples. Analysis of BAs with the use of RPLC method were carried out after their derivatization with p-toluenesulfonyl chloride (tosyl chloride), while for HILIC one sample preparation consisted of only dilution. For RPLC method the limits of detection (LODs) and quantitation (LOQs) were in the range 0.54–4.3 ng/mL and 1.6–13 ng/mL, respectively. The obtained recoveries were from 75 to 125% with coefficient of variation (CV) less than 8%. The developed HILIC based method turned out to be less sensitive and not specific sufficiently for the determination of most BAs in native state in beer samples. In this case, the LODs and LOQs values were in the range 12–94 ng/mL and 35–290 ng/mL, respectively. The observed matrix effects during analysis of beer samples were significant enough to distort the BAs content. The obtained recoveries were often below 75% with CVs less than 11%. Finally, both developed methods were applied for analysis of BAs in samples of lager beers. Due to the low recoveries and strong influence of matrix the HILIC method could be only applied to qualitative analysis of some BAs in beer samples. Regardless of the relatively lengthy sample preparation for RPLC method (time of derivatization – 2 h), it was proven that a derivatization reaction is required for such matrix as beer.