Mechanistic Implications of the Varying Susceptibility of PAHs to Pyro-Catalytic Treatment as a Function of Their Ionization Potential and Hydrophobicity

• Published in: Environmental science & technology 2024-07, Vol.58 (30), p.13521-13528
• Main Authors: Denison, Sara B., Jin, Peixuan, Zygourakis, Kyriacos, Senftle, Thomas P., Alvarez, Pedro J. J.
• Format: Article
• Language: English
• Subjects: Active sites; Anthracene; Aromatic compounds; Bentonite; Carbon footprint; Cascade chemical reactions; Catalysts; Catalytic converters; Density functional theory; Electron transfer; Electrons; Energy requirements; Fertility; Hydrophobicity; Initiation (polymerization); Ion exchange; Ionization; Ionization potentials; Iron; Metallurgical constituents; Naphthalene; Occurrence, Fate, and Transport of Aquatic and Terrestrial Contaminants; Polycyclic aromatic hydrocarbons; Pyrolysis; Reaction centers; Remediation; Soil contamination; Soil pollution; Soil remediation; Soil temperature; Sustainable remediation; Temperature requirements; Transition metals
• ISSN: 0013-936X; 1520-5851; 1520-5851
• DOI: 10.1021/acs.est.4c04811

Transition metal catalysts in soil constituents (e.g., clays) can significantly decrease the pyrolytic treatment temperature and energy requirements for efficient removal of polycyclic aromatic hydrocarbons (PAHs) and, thus, lead to more sustainable remediation of contaminated soils. However, the catalytic mechanism and its rate-limiting steps are not fully understood. Here, we show that PAHs with lower ionization potential (IP) are more easily removed by pyro-catalytic treatment when deposited onto Fe-enriched bentonite (1.8% wt. ion-exchanged content). We used four PAHs with decreasing IP: naphthalene > pyrene > benz­(a)­anthracene > benzo­(g,h,i)­perylene. Density functional theory (DFT) calculations showed that lower IP results in stronger PAH adsorption to Fe­(III) sites and easier transfer of π-bond electrons from the aromatic ring to Fe­(III) at the onset of pyrolysis. We postulate that the formation of aromatic radicals via this direct electron transfer (DET) mechanism is the initiation step of a cascade of aromatic polymerization reactions that eventually convert PAHs to a non-toxic and fertility-preserving char, as we demonstrated earlier. However, IP is inversely correlated with PAH hydrophobicity (log K ow), which may limit access to the Fe­(III) catalytic sites (and thus DET) if it increases PAH sorption to soil OM. Thus, ensuring adequate contact between sorbed PAHs and the catalytic reaction centers represents an engineering challenge to achieve faster remediation with a lower carbon footprint via pyro-catalytic treatment.