Gas chromatography-Orbitrap mass spectrometry screening of organic chemicals in fly ash samples from industrial sources and implications for understanding the formation mechanisms of unintentional persistent organic pollutants.

Clarifying the occurrences of organic chemicals in fly ash produced during industrial thermal processes is important for improving our understanding of the formation mechanisms of toxic pollutants such as polycyclic aromatic hydrocarbons (PAHs), halogenated PAHs, dioxins, and other unintentional persistent organic pollutants. We developed a highly sensitive gas chromatography-Orbitrap mass spectrometry (GC-Orbitrap/MS) method and applied it to screening of organic pollutants in fly ash samples from multiple industrial thermal processes. The GC-Orbitrap/MS method could detect and quantify organic pollutants at part per billion (ppb) levels. In total, 96 organic chemicals, including alkanes, benzene derivatives, phenols, polycyclic aromatic hydrocarbons, and biphenyl derivatives were identified in the fly ash samples. Several organic chemicals with chlorine or bromine substituents were abundant in secondary copper smelter fly ash, and these might act as precursors for formation of dioxins, brominated dioxins, and other dioxin-like compounds. Several chlorinated and brominated PAH compounds were also found in the secondary copper smelter fly ash. PAHs were dominant chemicals in the secondary aluminum smelter fly ash samples, and were present in much higher concentrations than in the samples from other industries. This indicates that there are different chemical formation pathways in different industries. Possible formation pathways of PAHs and dioxins were investigated and deduced in this study. These results improve our understanding of the formation mechanisms of toxic unintentional persistent organic pollutants and could be useful for reducing their source emissions.