PBDEs in the marine environment: Sources, pathways and the role of microplastics

Brominated flame retardants (BFRs) are an important group of additives in plastics that increase resistance to ignition and slow down the rate of burning. Because of concerns about their environmental and human health impacts, however, some of the most widely employed BFRs, including hexabromocyclododecane (HBCD) and commercial mixtures of penta-, octa- and deca- (poly)bromodiphenyl ethers (PBDEs), have been restricted or phased out. In this review, the oceanic sources and pathways of PBDEs, the most widely used BFRs, are evaluated and quantified, with particular focus on emissions due to migration from plastics into the atmosphere versus emissions associated with the input of retarded or contaminated plastics themselves. Calculations based on available measurements of PBDEs in the environment suggest that 3.5 and 135 tonnes of PBDEs are annually deposited in the ocean when scavenged by aerosols and through air-water gas exchange, respectively, with rivers contributing a further ∼40 tonnes. Calculations based on PBDE migration from plastic products in use or awaiting or undergoing disposal yield similar net inputs to the ocean but indicate a relatively rapid decline over the next two decades in association with the reduction in the production and recycling of these chemicals. Estimates associated with the input of PBDEs to the ocean when "bound" to marine plastics and microplastics range from about 360 to 950 tonnes per year based on the annual production of plastics and PBDEs over the past decade, and from about 20 to 50 tonnes per annum based on the abundance and distribution of PBDEs in marine plastic litter. Because of the persistence and pervasiveness of plastics in the ocean and diffusion coefficients for PBDEs on the order of 10^-20 to 10^-27 m² s^-1, microplastics are likely to act as a long-term source of these chemicals though gradual migration. Locally, however, and more important from an ecotoxicological perspective, PBDE migration may be significantly enhanced when physically and chemically weathered microplastics are exposed to the oily digestive fluids conditions of fish and seabirds.