Determination of histamine, agmatine, and putrescine in wine by ion chromatography- single quadrupole mass spectroscopy

Importance of the topic

Biogenic amines in wine such as histamine, agmatine, and putrescine can impact human health and product quality. Excess levels cause adverse reactions (headaches, hypotension, asthma) and serve as indicators of microbial activity and storage conditions. Reliable quantitation supports quality control in enology and food safety labs.

Objectives and study overview

This work evaluates ion chromatography (IC) with suppressed conductivity detection and single quadrupole mass spectrometry (IC-MS) to quantify histamine, agmatine, and putrescine in wine. Three wine types (sparkling, Chardonnay, Cabernet Sauvignon) were analyzed fresh and after three days of air exposure to assess amine formation during storage.

Methodology and instrumentation used

The method employs a Thermo Scientific Dionex ICS-6000 HPIC system coupled to an ISQ EC single quadrupole MS with HESI-II. Key features:

• Columns: Dionex IonPac CG19-4 µm guard (2 × 50 mm) and CS19-4 µm analytical (2 × 250 mm)
• Eluent: Methanesulfonic acid gradient (9 mM to 75 mM over 16 min), generated by EGC 500 cartridge and CR-CTC 600 trap
• Flow rate: 0.325 mL/min; separation at 20 °C; autosampler at 10 °C
• Detection 1: Suppressed conductivity (CDRS 600, 2 mm, 66 mA, external water mode)
• Detection 2: MS in positive ESI SIM mode (m/z 89.1, 112, 131); vaporizer 280 °C, transfer tube 355 °C, N₂ sheath 40 psi, aux 2 psi, sweep 0.5 psi

Main results and discussion

Calibration over 0.5–25 mg/L used quadratic fits (r²>0.9985). Method detection limits were 0.10–0.14 mg/L. Peak area RSDs were <2% for putrescine and agmatine, 7.3% for histamine. In fresh samples, Cabernet Sauvignon contained the highest amine levels (putrescine 6.08 mg/L, histamine 3.06 mg/L), while sparkling and Chardonnay were lower; agmatine was below MDL. After three days’ air exposure, putrescine increased by 20–73% and histamine doubled in white and red varieties, illustrating amine formation upon oxidation.

Benefits and practical applications

The combined IC-MS approach delivers sensitive, selective, and confirmatory analysis of biogenic amines without derivatization or extensive sample preparation. Dual detection ensures reliable quantitation and structural confirmation, making it ideal for routine quality control in wineries, fermentation monitoring, and food safety laboratories.

Future trends and applications

Emerging directions include high-resolution MS coupling for broader amine profiling, automated online sample preparation, integration with real-time fermentation monitoring, and application to other fermented foods and beverages.

Conclusion

Ion chromatography with suppressed conductivity and single quadrupole MS enables robust quantitation of histamine, agmatine, and putrescine at sub-mg/L levels in wine. The method differentiates amine content among wine types and tracks concentration increases due to air exposure, supporting quality assurance and consumer safety.

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