Analyses of known and new types of polyhalogenated aromatic substances in oven ash from recycled aluminium production

Abstract

Persistent aromatic bromine, chlorine and mixed chlorine-bromine compounds were analysed from recycled aluminium smelter (ALS) ashes to explore the impact of brominated flame retardants (BFR) on their formation. Polybrominated diphenyl ethers (PBDE) were the most abundant original BFRs found. Induction furnace ash contained tetra- to octa-BDEs about 2000 ng g −1 in similar congener ratios as the original scrap, but contents of nona- and deca-BDEs were only 25 and 5 ng g −1 indicating their significant degradation in ALS process. In the most non-polar fraction, PCB levels and profiles were similar as earlier ALS ash samples in 1990s. The highest PCB level measured was that of deca-CB (450 ng g −1) in the induction furnace ash. In this fraction, bromo compounds were non-detectable (<5 ng g −1). Fraction of the most polar compounds (from reversed toluene elution of carbon column (“dioxin fraction”) contained PCDDs, PCDFs and polychlorinated dibenzothiophenes (PCDTs) in similar amounts and congener profiles as earlier investigated ALS ash samples. Bromine-containing dioxin and furan congeners were not detected. From individual PCDDs and PCDFs, octaCDF was the most abundant (205 ng g −1) in induction furnace ash. In this fraction, the original BFR, tetrabromo-bisphenol-A, was identified. Its level in the induction furnace ash was approximated to be 388 ng g −1. In addition, 12 novel brominated and chlorinated compounds were found as abundant (8–441 ng g −1 in the induction furnace ash) contaminants from the fraction. Four of them were bisphenol derivatives, five biphenylols, then octachlorofluorenone (OCFL) and octachlorobiphenylene (OCBP). Their structures or structure types were deduced from total low-resolution EI mass spectra by theoretical isotope cluster simulation (ICLU) and through known fragmentation rules.