Temperature-dependent profiles of dioxin-like toxicants from combustion of brominated flame retardants

Literature provides detailed mechanisms underpinning the formation of a wide array of bromine (Br)-containing molecules with a prime focus on dioxin-like compounds. However, from a more applied point of view, the practical deployment of attained thermo-kinetic parameters remains inadequate in the absence of a robust kinetic model that connects bromine transformation at the molecular level with pertinent experimental observations. Herein and to fill in this gap, this study constructs a chemical kinetic model to account for the "homogenous gas phase" emission of Br-aromatic pollutants from the oxidative thermal decomposition of a monobromobenzene molecule (MBZ). The latter serves as a model compound for brominated flame retardants (BFRs) present in e-waste. The model consists of sub-mechanisms (that include reaction rate constants and thermochemical T-dependent functions) for HBr oxidation, combustion mechanism of C₁-C₆ species, bromine transformation, and synthesis of Br dioxin-like compounds. Reaction rate parameters were obtained for a large array of reactions that constitute the core of the model. For instance, the obtained activation energies for the initial pathways in the formation of brominated biphenyls reside in the range of ~15-45 kJ/mol. Considering oxidation of 5000 ppm MBZ in a plug flow reactor, the model reasonably predicts the temperature-dependent profiles (between 500 and 1200 °C at atmospheric pressure) of a few PBDD/Fs (i.e., polybrominated dibenzo-p-dioxins) isomers in reference to limited corresponding experimental measurements. Most Br dioxin-like compounds appear in the narrow temperature window of 600-1000 °C and achieve their highest abundance at molar yields in the range of 1.0-15 mmol/mol MBZ. A high load (100-120 mmol/mol MBZ) of brominated environmentally persistent free radicals (Br-EPFR) emerges and shifts from bromophenoxy radicals to bromocyclopentadienyl radicals around 700 °C. Oxidation of a 2-bromophenol molecule results in the formation of higher yields of Br-toxicants when compared with that of MBZ. The assembled model provides an informed hazards assessment into the potential emission inventories of Br-compounds in the gas phase at conditions encountered in real scenarios, such as open burning and primitive treatment of e-waste. Via an atomic-base understanding of the complex bromine chemistry and speciation, the model allows the underlying operational conditions that reduce the emission of Br-notorious pollutants to be surveyed and fine-tuned.