@article{01KT3JMD0CCXFJS0A4TP9GS1CE,
  abstract     = {{Chlorine contaminants in postconsumer plastic pyrolysis oils are a major bottleneck to their further valorization in the steam cracking process, where typical feed specifications require less than 3 ppm of chlorine. Current chromatographic approaches lack sufficient elemental selectivity and compound-independent quantification for complex pyrolysis matrices. Here, we present the first chlorine-selective, quantitative, comprehensive two-dimensional gas chromatography method with atomic emission detection (GC×GC-AED) for the analysis of complex pyrolysis oils. AED parameters were systematically optimized for maximum selectivity and sensitivity to chlorine. AED exhibited a largely compound-independent response with <5% variability relative to the internal standard, 3-chlorothiophene, across 28 representative model compounds. This comprehensive technique enabled the selective detection and quantification of chlorine-containing compounds in five distinct pyrolysis oils derived from real polyvinyl chloride (PVC) waste and two from mixed plastic waste rich in polyolefins. Using this approach, 85–99% of detected chlorine compounds could be tentatively identified, and GC×GC-AED provided chlorine concentrations for each compound. The total chlorine content determined by combustion microcoulometry, X-ray fluorescence (XRF), and GC×GC-AED showed close agreement (<5% relative variation), highlighting the comprehensiveness and analytical reliability of the optimized AED method. This capability establishes GC×GC-AED as a powerful tool for understanding chlorine transformation pathways and for improving dechlorination strategies in waste-plastic valorization by mapping chlorine’s fate throughout the process.}},
  author       = {{Auersvald, Miloš and Havaei, Mohammadhossein and John Varghese, Robin and Straka, Petr and Van Geem, Kevin}},
  issn         = {{0003-2700}},
  journal      = {{ANALYTICAL CHEMISTRY}},
  keywords     = {{Chlorine,Chromatography,Hydrocarbons,Plastics,Wastes,2-DIMENSIONAL GAS-CHROMATOGRAPHY,ELECTRON-CAPTURE DETECTOR,ATOMIC-EMISSION DETECTION,VACUUM PYROLYSIS,PVC,DECOMPOSITION,SPECTROMETRY,CALIBRATION,PRODUCTS}},
  language     = {{eng}},
  number       = {{22}},
  pages        = {{16342--16354}},
  title        = {{Decoding chlorine contaminants in plastic-derived pyrolysis oils with chlorine-selective GC×GC-AED}},
  url          = {{http://doi.org/10.1021/acs.analchem.6c01163}},
  volume       = {{98}},
  year         = {{2026}},
}

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