Based on distinct land-use categories, a sampling campaign was carried out at eight locations across Toronto and the Greater Toronto Area in 2016-2017. Source sectors' dependent patterns of atmospheric concentrations of 9 organophosphate esters (OPEs), 9 polybrominated diphenyl ethers (PBDEs) and 5 novel flame retardants (NFRs) showed dominance of OPEs and PBDEs at highly commercialised urban and traffic sites, while NFRs, were dominant at residential sites. Overall, average concentrations of ΣOPEs (1790 pg/m) were two orders of magnitude higher than ΣPBDEs (9.17 pg/m) and ΣNFRs (8.14 pg/m). The atmospheric concentrations of given chemical classes also showed a general trend of lower levels in winter as compared to summer months. Statistically significant negative correlations between the natural logarithm of concentrations and inverse of temperature for some OPEs and PBDEs highlighted the role of volatilization from local sources at given sites as primarily influencing their atmospheric concentrations. Overall, this study adds to the current knowledge of urban settings as a major emitter of the chemicals of emerging concern and their replacements, as well as the ongoing problem of phased out PBDEs due to their presence in existing inventories of commercial/recycled products. It is recommended that long-term monitoring programs targeting flame retardants (FRs) include urban sites, which provide an early indicator of effectiveness of control measures of targeted FRs, while at the same time providing information on emission sources and trends of replacement FR chemicals.
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