Determination of Biogenic Amines in Fermented and Non-Fermented Foods Using Ion Chromatography with Suppressed Conductivity and Integrated Pulsed Amperometric Detections

Significance of the Topic

The accurate determination of biogenic amines in food products is essential for food safety, as elevated levels of histamine, tyramine and other amines can provoke adverse physiological reactions. Fermented and non-fermented foods such as meat, fish, dairy, fruits and vegetables may accumulate these compounds during storage and processing, potentially leading to toxicity or spoilage indicators.

Objectives and Overview of the Study

This study evaluates an ion chromatography (IC) method using a weak cation-exchange IonPac CS18 column combined with suppressed conductivity and integrated pulsed amperometric detection (IPAD), with optional UV detection at 276 nm, for the direct analysis of ten underivatized biogenic amines in various food matrices. The goals included development of an electrolytically generated methanesulfonic acid gradient, optimization of IPAD waveform for minimal baseline disturbance, and application to real food samples under different storage conditions.

Instrumentation Used

The analytical platform comprised a Dionex ICS-3000 system with:

• DP Dual Pump with in-line degas option
• DC Detector/Chromatography module (suppressed conductivity and electrochemical cells)
• EG Eluent Generator module with EluGen EGC II MSA cartridge
• CSRS ULTRA II suppressor in external water mode
• Electrochemical cell with gold working electrode and pH/Ag/AgCl reference for IPAD
• AD25 UV-Vis absorbance detector set at 276 nm

Methodology and Experimental Procedure

Samples were extracted using trichloroacetic or methanesulfonic acid solutions to precipitate proteins and release biogenic amines. The eluent gradient (3–45 mM MSA over 45 min) was generated on-line. Postcolumn addition of 100 mM NaOH (0.24 mL/min) enabled IPAD with a multi-step waveform for continuous integration of oxidation currents. Suppressed conductivity detection followed the CSRS suppressor to quantify aliphatic amines, and UV detection confirmed aromatic amines like tyramine.

Main Results and Discussion

The method delivered linear calibration (r2 > 0.997), low limits of detection (3.5–81 μg/L for conductivity, 20–400 μg/L for IPAD), and robust precision (intraday peak area RSD < 5%). Application to canned tuna, cheeses and smoked sausage revealed varying amine profiles: tyramine and histamine in cheeses (up to 1 835 mg/kg tyramine in spoiled Swiss), spermidine and spermine in sausages, and putrescine and cadaverine during tuna spoilage. Storage studies at 4 °C and 25 °C showed significant amine increases (e.g., putrescine in tuna from

Benefits and Practical Application of the Method

• Direct analysis of underivatized amines eliminates complex derivatization.
• Electrolytic eluent generation ensures reproducibility and reduces manual preparation.
• Dual detection (conductivity/IPAD/UV) broadens applicability across amine classes.
• Suitable for routine QA/QC in food safety laboratories and research settings.

Future Trends and Possibilities for Use

Integration of on-line sample preparation, coupling with mass spectrometry for structural confirmation, miniaturized IC systems, advanced data processing and automation are poised to enhance sensitivity, throughput and automation. Development of more selective stationary phases and multi-detector workflows will further improve specificity for complex matrices.

Conclusion

The described IC method using IonPac CS18 with suppressed conductivity and IPAD offers a sensitive, reproducible and derivatization-free approach for comprehensive biogenic amine analysis in diverse food products. It supports food safety monitoring and shelf-life studies by reliably detecting changes during storage.

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