Contamination and bioaccumulation of industrial persistent organic pollutants and their alternatives in the coastal environments of Korea

Abstract

Marine environment is the final reservoir of various pollutants originating from the terrestrial environment, and it is distributed and accumulated according to physicochemical properties in seawater, suspended particles, bottom sediments and various organisms constituting the foodweb. In this objective of study, the contamination status and bioaccumulation potential of industrial persistent organic pollutants (POPs) and their alternatives are investigated in multimedia from the three industrialized coastal environments of Korea including Masan Bay, Ulsan Bay, and Lake Shihwa (Incheon coast). The target industrial POPs are including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), per- and polyfluoroalkyl substances (PFASs), and their alternatives. The optimal instrument analysis and pretreatment conditions for the detection of industrial POPs among the marine environment matrices were established, and reliable QA/QC results were shown. The industrial POPs were detected in wide range of concentrations in water, surface and dated sediments, and various marine biota species from Masan Bay, Ulsan Bay, and Lake Shihwa (Incheon Coast) of Korea. The highest concentrations of industrial POPs in water and sediments were found at the locations from streams, rivers, and creeks surrounding by industrial complexes, indicating that industrial activities are the major sources of industrial POPs in coastal environments. The relative contributions of PBDEs and their alternative flame retardants (FRs) in sediments were different by industrial complexes and existence of wastewater treatment plant (WWTP). High ratios of decabromodiphenyl ethane (DBDPE)/decabrominated diphenyl ether (BDE-209) in sediments indicated a clear evidence on shift of consumption patterns of brominated flame retardants (BFRs) in Korean FRs industry. Significant declining trends of PBDE concentrations and changed profiles were observed in water and sediments due to domestic and global regulations. The industrial POPs levels in water and sediments may pose adverse health risks to avian wildlife, benthic aquatic organisms and human. The historical trends of FRs and PFASs reflects the domestic and global regulations on chemicals and coastal development activities. The highest industrial POPs concentrations were observed from 1970s to 1990s, while DBDPE which is representative alternative of deca-BDE were continuously increase at the present since 1990s. Shifted consumption pattern of FRs by the Korean industry reflected in dated sediments. High levels of PFAS precursors were observed in sediments core and their historical trends were related with operation and development of WWTP. Inventories and fluxes of PBDEs and HBCDDs were similar to or much higher than those of polychlorinated biphenyls (PCBs). The industrial POPs were bioaccumulated and biomagnified through the foodchain with different ratio by Korean coasts. PBDEs and HBCDDs showed the highest concentrations in fish and bivalve, while PFASs showed the highest concentrations in cephalopods. The PBDEs and HBCDDs levels were different by species, but the main accumulation compounds were the same in all species. Species- and tissue-specific accumulation of PFASs showed in biota. The BAF of PFSAs and long-chain perfluorinated carboxylic acid (PFCAs) were significantly increased by increasing carbon number. The trophic magnification factor (TMF) values of lower brominated BDEs and long-chain PFCAs exceed 1. Potential health risks of industrial POPs were observed to wildlife and human though the seafood consumption.