Halogens and sulfur in solid samples according to EN 17813

Significance of the Topic

Accurate quantification of halogens and sulfur in solid materials is critical for environmental monitoring and compliance with waste disposal regulations such as EU 2000/76/EC and 99/31/EC. These analytes pose risks due to their persistence, toxicity, and formation of harmful by-products during incineration.

Objectives and Overview of the Study

This study validates a fully automated method based on oxidative pyrohydrolytic combustion coupled with ion chromatography (CIC) for simultaneous direct determination of fluoride, chloride, bromide, and sulfate in various solid matrices according to EN 17813:2023. Sample types include solid recovered fuel, wood, sludge, soil, and polymer.

Methodology and Instrumentation

Samples were pre-dried at 105 °C, ground to <250 µm, and weighed (25–50 mg) into ceramic cups. Pyrohydrolytic combustion was performed in a TEI oven with two temperature zones up to 1050 °C under an argon/oxygen stream and humidification. Evolved halogens and sulfur were captured in hydrogen peroxide absorber solution. Ion chromatographic separation used a Metrosep A Supp 19 - 150/4.0 column with carbonate/bicarbonate eluent produced by a 941 Eluent Production Module. Detection employed sequential suppression and conductivity. Calibration and injection were automated via intelligent Partial Loop Injection Technique (MiPT). Quality control included certified reference materials, blanks, and replicates.

Použitá instrumentace

• TEI Combustion Oven with ceramic combustion tube
• Solid Autosampler CIC (TEI)
• 920 Absorber Module
• 930 Compact IC Flex Oven/SeS/PP/Deg
• MagIC Net software
• 941 Eluent Production Module
• Metrosep A Supp 19 - 150/4.0 separation column with guard
• Metrosep A PCC 2 HC/4.0 preconcentration column

Main Results and Discussion

All four analytes were resolved and quantified within 20 minutes. Fluorine ranged from 14 to 559 mg/kg, chlorine from 351 to 7676 mg/kg, bromine from 9 to 1304 mg/kg, and sulfur from 189 to 8672 mg/kg across tested matrices. Relative standard deviations below 11 % indicate high method precision. Chromatogram overlays confirm baseline separation and absence of interferences.

Benefits and Practical Application of the Method

The CIC approach offers robust, reproducible analysis with minimal sample preparation and maintenance. The ceramic setup enhances consumable lifetime, while automated calibration and eluent production streamline workflow. Single-manufacturer integration ensures consistency and reliable compliance testing in environmental, industrial, and quality control laboratories.

Future Trends and Possibilities

Further developments may include expansion to additional solid matrices, coupling with mass spectrometric detectors for speciation analysis, integration into laboratory information management systems, and miniaturized or inline monitoring solutions to support real-time process control.

Conclusion

Combustion ion chromatography provides a validated, efficient, and automated solution for direct determination of halogens and sulfur in solids according to EN 17813:2023, ensuring compliance, environmental safety, and laboratory efficiency.

Reference

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