Assessment of POPs in air from Spain using passive sampling from 2008 to 2015. Part I: Spatial and temporal observations of PBDEs

The Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) calls for the Parties’ effectiveness evaluation of those measures taken to meet the reduction and eventual elimination of POPs from the environment. With that goal, air concentrations of different POP families have been measured uninterruptedly since 2008 under the Spanish Monitoring Program (SMP) by means of passive air sampling. This work focuses on data for polybrominated diphenyl ethers (PBDEs) determined in a total of 321 samples collected seasonally each year in 5 urban and 7 background sites. Neither significant temporal trends nor significant seasonal variations for total PBDE air burdens were detected. In contrast, significant variations were found among PBDE congeners. Those related to the octa-PBDE formulation significantly decreased in the study period. However, PBDEs related to the penta-formulation showed steady concentrations while PBDE-209, the congener found at the greatest levels, showed increasing or steady levels in most sampling sites. Seasonal variations were also markedly different among congeners. Concentrations of the lightest PBDEs (tri- to penta-substituted) were highly influenced by ambient temperature (T), showing maximum values in summer probably due to higher volatilization rates compared to those of heavier PBDEs. Contrarily, no clear seasonal trends were found for hexa- to deca-PBDEs, which were negatively related to precipitation; thereby, indicating an efficient atmospheric wash out by wet deposition episodes. Regarding spatial patterns, overall significant greater PBDE levels were found in cities compared to background areas, pointing out the role of highly populated areas as sources for these pollutants in Spain. Yet and especially in the case of PBDE-209, our results suggested the presence of significant unknown sources of PBDEs in some background sites. Further monitoring efforts are needed to assess potential unknown sources in the sampling network as well a