Novel multi-residue method for rapid determination of pesticides in wines using GC-MS/MS

Significance of the topic

Viticulture relies on effective pest control to protect grape quality and ensure consumer safety. Monitoring pesticide residues in wine is critical to comply with stringent regulations, maintain product integrity, and minimize environmental impact. A rapid, sensitive, and cost-efficient analytical approach supports both quality assurance and regulatory adherence across global wine production.

Objectives and overview of the study

This work aimed to develop and validate a multi-residue method for quantifying 63 pesticides in diverse wine matrices using a miniaturized sample enrichment technique combined with triple quadrupole GC-MS/MS. The study assessed method performance across young red, aged red, white, sparkling Cava, and sweet Port wines, in line with EU regulatory guidelines.

Methodology and instrumentation

A scalable microextraction approach was employed to enrich pesticides from small wine aliquots, followed by targeted GC-MS/MS analysis. Key steps included:

• Sample preparation: 0.4 mL wine diluted to 35 mL with water, followed by addition of a proprietary extractant–dispersant mixture and centrifugation to form a single enriched droplet.
• Instrumental analysis: Automated injection into a Bruker 436 GC equipped with a PTV injector and a 30 m × 0.25 mm BR-5ms column, coupled to an EVOQ GC-Triple Quadrupole mass spectrometer operating in MRM mode.
• Data processing: Quantitation and confirmation managed by Bruker Compass TQ software, with criteria aligned to SANTE/12682/2019 guidelines for pesticide residue analysis.

Instrumentation

• Gas chromatograph: Bruker 436 GC with PTV injector (1079 inert).
• Column: BR-5ms, 30 m × 0.25 mm, 0.25 µm film.
• Carrier gas: Helium at 1 mL/min.
• Mass spectrometer: EVOQ GC-Triple Quadrupole; electron ionization source at 280 °C; transfer line at 280 °C; argon collision gas at 2 mTorr.
• Software: Bruker Compass TQ for MRM acquisition and quantitative screening.

Key results and discussion

• Linearity: Coefficients of determination (R²) ≥ 0.990 for all 63 pesticides across all wine types.
• Sensitivity: Method reporting limit (MRL) of 1 ppb and method detection limit (MDL) of 0.5 ppb with reliable quantitation and confirmation ions (S/N > 10).
• Matrix effects: Negligible after ~100-fold dilution, with slope variations below 6 %.
• Precision: Relative standard deviations below 25 % at the 10 ppb level in all matrices.

Benefits and practical applications

The miniaturized extraction workflow offers rapid turnaround (11 min per batch of 40 samples), minimal solvent consumption (120 mL for 40 samples), and low sample volume requirements (0.4 mL). It reduces hazardous waste and labor costs compared to liquid–liquid extraction, SPE, or QuEChERS, while achieving ultra-sensitive detection suitable for routine quality control of wines and related aqueous matrices.

Future trends and potential applications

Expansion of this microextraction strategy to other beverages, food products, and environmental waters can broaden multi-residue screening capabilities. Integration with high-throughput automation, method miniaturization, and coupling to alternative detection platforms may further enhance analytical efficiency and green chemistry compliance.

Conclusion

The combined µDROP enrichment and EVOQ GC-TQ analysis constitutes a robust, ultra-sensitive, and cost-effective multi-residue method for pesticide determination in wines. It meets regulatory validation standards, offers high throughput, and aligns with sustainability goals, making it an ideal solution for modern analytical laboratories.

References

1. Bruker Application Note LCMS-136: Determination of SVOCs in water samples using the Bruker µDROP method for the EVOQ GC-TQ system.
2. European Commission SANTE/12682/2019: Analytical quality control and method validation procedures for pesticide residues analysis in food and feed.
3. Directive 2009/128/EC: Establishing a framework for the sustainable use of pesticides.
4. Regulation (EC) No 1107/2009: Concerning the placing of plant protection products on the market.
5. Regulation (EU) No 652/2014: On statistics relating to plant protection products.
6. OIV 2018: Statistical Report on World Vitiviniculture.
7. EU Pesticides Database: Public access to EU-approved active substances and MRLs.
8. Commission Implementing Regulation (EU) 2019/533: Rules for the implementation of Regulation (EC) No 396/2005.