Profiling the occurrence of biogenic amines in different types of tuna samples using an improved analytical approach

Food deterioration caused by microbial agents often involve the formation of biogenic amines (BAs), which can have harmful effects on human health. In this study a set of BAs - tryptamine, cadaverine, putrescine, spermine, histamine, tyramine, and spermidine, were simultaneously analysed to monitor their occurrence in different types of tuna samples. An improved extraction approach involving ultrasound-assisted microextraction (USA mu ET) followed by derivatization with dansyl chloride (DnsCl) and analysis by ultrahigh performance liquid chromatography (UHPLC) with fluorescence detection was validated for BAs quantification. The performance of the USA mu ET/UHPLC-FLD was assessed by studying the limits of detection (LOD) and quantification (LOQ), linear dynamic range (LDR), precision (intra and inter-day) and matrix effect (ME). Good linearity (r(2) > 0.98), LODs (from 0.98 to 8.57 mg kg(-1)) and LOQs (3.20-25.6 mg kg(-1)) were achieved for all BAs analysed. Recoveries ranged from 76% to 106%, with relative standard deviations (RSD) lower than 5.0%. ME was determined from 7.52 to 50% and the intra and inter-day precisions ranged from 4.7 to 11.6% and 5.5-14.2%, respectively. BAs levels varied significantly from 4.09 +/- 0.8 mg kg(-1) of putrescine in olive oil canned samples to 577.9 +/- 5.9 mg kg(-1) of cadaverine in natural canned samples. Tryptamine and tyramine were not detected in any of the samples analysed, while spermine and spermidine were found in 85.7% of the assayed tuna samples. Cadaverine was the most dominant BA with concentrations ranging from 54.3 +/- 2.5 mg kg(-1), in olive oil canned tuna, to 577.9 +/- 5.9 mg kg(-1), in natural canned samples, whereas putrescine had the lowest concentration (average 6.9 +/- 2.5 mg kg(-1)). The validated methodology revealed important improvements in terms of simplification of the experimental layout, expressed in the low sample and reagent amounts, in addition to less time-consuming and labour-intensive requirements that did not compromise the analytical performance.

Automated summary

The study successfully developed a validated method for quantitative analysis of various biogenic amines in tuna samples using ultrasound-assisted microextraction and UHPLC-FLD analysis techniques. The results showed significant variations in biogenic amine levels in the samples, and the validated method demonstrated high reliability and accuracy.