Studies into the formation of PBDEs and PBDD/Fs in the iron ore sintering process

Polybrominated diphenyl ethers (PBDEs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were detected in stack emissions from UK sinter plants. The sum of 36 PBDE congeners was measured at a mean concentration of 295ng/Nm³ with a standard deviation of 96ng/Nm³. The mean PBDD/F concentrations were 0.14ngWHO-TEQ/m³ (range=0.03-0.39). PBDD/F emission concentrations were approximately ten times lower than their PCDD/F homologues. To understand the possible formation mechanisms of brominated organic species in iron ore sintering, both full-scale and laboratory experiments using an experimental sintering process were carried out. A complete PBDE mass balance was undertaken for a full scale sinter plant showing that PBDEs were already present in the raw materials such as iron ores and coke breeze and that a significant proportion of the PBDE inputs were actually destroyed during the process. A number of controlled experiments were conducted using a laboratory-scale sintering apparatus (sinter pot). These were designed to investigate: (a) mass balance of PBDEs during sintering, (b) the relationship between the availability of bromide (as KBr) and PBDE emissions, and (c) the influence of the availability of both bromide and PBDEs on PBDD/F formation. As observed in the full scale plant, the PBDEs already present in the raw materials were mostly destroyed during the process (79-96%) for all sinter pot experiments. Increasing amounts of KBr in the raw sinter mix did not result in a significant increase in PBDE formation suggesting that there was no PBDE formation in sintering via de novo synthesis. No relationship was observed between PBDE inputs and PBDD/F emissions indicating that PBDEs did not act as precursors for PBDD/Fs formation. Finally, PBDD/F formation was enhanced substantially with increasing amounts of KBr suggesting that their formation mechanism was similar to that of PCDD/Fs via de novo synthesis.