Using the Teledyne Tekmar HT3TM Headspace Analyzer to Meet the Requirements of the New Korean Standard Method for Water Pollution, ES04602.1, for Bromoform, Vinyl Chloride and Acrylonitrile

Significance of the Topic

The recent update of Korean wastewater regulations added bromoform, vinyl chloride and acrylonitrile to monitored pollutants. Reliable quantitation of these volatile compounds is essential for compliance and environmental protection. Headspace GC/MS offers a robust approach to detect trace levels in complex matrices such as industrial and municipal effluents.

Study Objectives and Overview

This application note evaluates the performance of the Teledyne Tekmar HT3 Headspace Analyzer combined with Agilent GC/MS in both static and dynamic headspace modes. Key goals: ensure linear response (r² > 0.98) over 5–50 ppb and achieve method detection limits (MDL) below 5 ppb for each target analyte, in accordance with Korean Standard Method ES04602.1.

Methodology and Instrumentation

The workflow includes: sample preparation with salt addition to enhance volatility, spiking with internal standards (fluorobenzene, chlorobenzene-d5, 1,4-dichlorobenzene-d4), and calibration at 5, 10 and 50 ppb. Results from static and dynamic headspace methods were compared.

• Headspace Analyzer: Teledyne Tekmar HT3 (static and dynamic modes).
• Gas Chromatograph/Mass Spectrometer: Agilent 7890 GC with 5975C XL MSD triple-axis detector.
• Column: Restek Rtx® VMS, 20 m × 0.18 mm ID, 1 µm film; constant flow 0.8 mL/min.
• Oven program: 35 °C (1 min) to 230 °C at 10 °C/min, hold 5 min.

Main Results and Discussion

Both headspace methods produced well-resolved chromatograms for a 5 ppb MDL standard. Calibration curves demonstrated exceptional linearity: r² ranged from 0.9966 to 1.0000. MDLs calculated from seven replicates were consistently below 5 ppb:

• Vinyl chloride: MDL 0.77–1.73 ppb
• Acrylonitrile: MDL 1.23–2.26 ppb
• Bromoform: MDL 1.50 ppb

Dynamic headspace slightly improved MDLs but both modes met regulatory requirements. The Teledyne HT3 trap (#9) ensured efficient analyte enrichment and reproducibility.

Benefits and Practical Applications

The combination of HT3 headspace analysis and GC/MS delivers:

• High sensitivity well below regulatory MDLs.
• Excellent linearity for accurate quantitation.
• Versatility to switch between static and dynamic modes without hardware changes.
• Streamlined sample throughput for routine wastewater monitoring.

Future Trends and Potential Applications

Advancements may include:

• Automated sample handling and expanded multiplexing for higher throughput.
• Integration of high-resolution mass spectrometry for non-target screening of emerging contaminants.
• Adaptation to real-time monitoring platforms and remote operation.
• Application to other environmental matrices such as soil pore-water and sediments.

Conclusion

The Teledyne Tekmar HT3 coupled with Agilent GC/MS consistently fulfills the Korean Standard Method ES04602.1 for bromoform, vinyl chloride and acrylonitrile in wastewater. Both static and dynamic headspace modes exceed the required linearity and detection limits, offering a reliable solution for environmental compliance.

Reference

1. Ministry of Environment, Republic of Korea, Korean Standard Method for Water Pollution ES04602.1, 2010.
2. Restek Drinking Water VOA MegaMix®, Catalog #30601.
3. Restek 502.2 Calibration Mix #1, Catalog #30042.