The atmospheric fate of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH): spatial patterns, seasonal variability, and deposition to Canadian coastal regions

Abstract

Brominated flame retardants (BFRs) that are gradually being phased out are being replaced by emerging BFRs. Here, we report the concentration of the α- and β-isomers of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH; also known as DBE-DBCH) in over 300 air, water, and precipitation samples collected between 2019 and 2022 using active air and deposition sampling as well as networks of passive air and water samplers. The sampling region includes Canada's most populated cities and areas along the St. Lawrence River and Estuary, Quebec, as well as around the Salish Sea, British Columbia. TBECH was detected in over 60 % of air samples at levels comparable to those of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47). Concentrations of TBECH and BDE-47 were typically higher in urban areas, with stronger correlations with population density during warmer deployments. Uniform α- / β-TBECH ratios across space, time, and environmental media indicate the highly similar atmospheric fate of the two isomers. Although TBECH air concentrations were strongly related to temperature in urban Toronto and a remote site on the east coast, the lack of such dependence at a remote site on the west coast can be explained by the small seasonal temperature range and summertime air mass transport from the Pacific Ocean. Despite there being no evidence that TBECH has been produced, or imported for use, in Canada, it is now one of the most abundant gaseous BFRs in the Canadian atmosphere. The recorded spatial and temporal variability of TBECH suggest that its emissions are not constrained to specific locations but are generally tied to the presence of humans. The most likely explanation for its environmental occurrence in Canada is the release from imported consumer products containing TBECH. Chiral analysis suggests that despite its urban origin, at least some fraction of TBECH has experienced enantioselective processing, i.e., has volatilized from reservoirs where it has undergone microbial transformations. Microbial processes in urban soils and in marine waters may have divergent enantioselectivity.