Insights into the Formation and Profile of Chlorinated Polycyclic Aromatic Hydrocarbons during Chlorobenzene and Chloroethylene Manufacturing Processes

Chlorinated polycyclic aromatic hydrocarbons including chlorinated naphthalenes and congeners with three to five rings are ubiquitous atmospheric pollutants. Congener profiles and formation mechanisms from typical chemical manufacturing have not been researched extensively. We measured the concentrations of 75 chlorinated naphthalenes and 18 chlorinated polycyclic aromatic hydrocarbons in raw materials, intermediates, products, and bottom residues from chemical plants producing monochlorobenzene and chloroethylene by different techniques. The findings confirmed that these chemical manufacturing processes are newly identified sources of atmospheric emissions of these compounds. More-chlorinated naphthalenes were formed from chloroethylene production than from monochlorobenzene production, which could be explained by the higher temperatures in the former process. Successive chlorination appeared to be an important formation pathway of polychlorinated naphthalenes according to their congener profiles and was supported by quantum chemical calculations of electrophilic chlorination on various positions of naphthalene. Chlorinated polycyclic aromatic hydrocarbons were more likely to be formed during the production of monochlorobenzene than chloroethylene. Moreover, we suggested that ring rearrangement and ring coupling are important transformation reactions between polychlorinated naphthalenes and chlorinated polycyclic aromatic hydrocarbons.