Analyses of Agricultural Chemicals in Golf Courses Using LC/MS/MS

Importance of the Topic

Golf courses often use a variety of agricultural chemicals to maintain turf quality, but runoff from these areas can introduce pesticides into surrounding water bodies. Monitoring these compounds at ultra-low levels is essential to protect aquatic ecosystems and comply with regulatory guidelines. The development of sensitive, reliable methods for detecting multiple pesticides in drainage water supports environmental risk assessment and informs management practices.

Objectives and Overview of the Study

This application note describes two analytical approaches using LC/MS/MS for measuring trace levels of agricultural chemicals in golf course drainage water:

• Individual quantitative methods for seven key pesticides including bensultap (nereistoxin oxalate), thiophanate-methyl, validamycin, hydroxyisoxazole (hymexazol), benomyl (carbendazim), MCPA salts, and trinexapac-ethyl.
• A simultaneous multi-component method for 44 pesticides in a single run.

The aim is to achieve detection limits at or below the Japanese Ministry of the Environment guideline values, with robust calibration, high reproducibility, and clear chromatographic separation.

Methodology and Used Instrumentation

Both approaches employ a Shimadzu UHPLC Nexera X2 system coupled to the LCMS-8050 triple-quadrupole mass spectrometer. Key elements include:

• Columns: Shim-pack Scepter C18-120 (100 × 2.0 mm, 1.9 µm) or Shim-pack XR-ODS (100 × 2.0 mm, 2.2 µm) for individual assays; L-column 2 ODS METAL FREE (100 × 2.0 mm, 3 µm) for multi-component screening.
• Mobile phases: ammonium acetate buffers with methanol or acetonitrile, gradient elution tailored to each analyte group.
• Electrospray ionization in positive or dual polarity for multi-component runs, with MRM transitions optimized per compound.
• Injection volumes ranged from 2 to 5 µL and flow rates of 0.2 mL/min. Column ovens were maintained at 40 °C.

Main Results and Discussion

Individual methods:

• Sensitivity met or exceeded guideline requirements (e.g., 0.01 ng for nereistoxin oxalate, 0.001 ng for carbendazim).
• Calibration curves showed linearity over relevant ranges (e.g., 0.0025–0.5 mg/L) with R2>0.997.
• Area reproducibility (%RSD) was typically below 5% at the lowest calibration levels.

Simultaneous multi-component analysis:

• Achieved one-hundredth of guideline concentration for all 44 pesticides, with calibration ranges from 0.0002 to 0.04 mg/L (higher for Iprodione, Boscalid, Dithiopyr).
• Typical %RSD values for area response were under 10% for most compounds.
• Total run time of about 22 minutes allowed comprehensive screening in a single injection.

Benefits and Practical Applications

The validated methods provide laboratories with:

• High sensitivity to detect ultra-trace pesticide residues in environmental water.
• Robust quantitation with excellent reproducibility, suitable for regulatory compliance.
• Flexibility to run targeted individual assays or broad multi-analyte screens depending on monitoring needs.

These protocols support water quality surveys around golf courses, remediation monitoring, and compliance with the Japanese MOE guidelines.

Future Trends and Applications

Advances in mass spectrometry instrumentation promise further enhancements in sensitivity and throughput. Potential developments include:

• Ultra-high-resolution accurate mass analysis for non-target screening of emerging contaminants.
• Automated sample preparation and online extraction to increase laboratory efficiency.
• Integration with data-processing algorithms and artificial intelligence for rapid result interpretation and trend analysis.

Such innovations will extend monitoring capabilities to broader classes of agrochemicals and support real-time environmental risk assessment.

Conclusion

The described LC/MS/MS methods demonstrate the ability to quantify a range of agricultural chemicals at levels well below regulatory limits in golf course drainage water. Both targeted individual analyses and comprehensive multi-compound assays exhibit strong linearity, low detection limits, and high reproducibility. These tools enable reliable water quality surveillance and contribute to environmental protection efforts.

Reference

Guideline for the Prevention of Water Pollution and Damage to Aquatic Animals and Plants by Agricultural Chemicals Used in Golf Courses (Ministry of the Environment, Japan; final amendment Nov. 30, 2018).