Legacy and emerging organophosphate flame retardants (OPFRs) in water and sediment from the Pearl River Delta to the adjacent coastal waters of the South China Sea: Spatioseasonal variations, flux estimation and ecological risk

The industrialization and urbanization along the Pearl River Delta (PRD) have exacerbated the issue of pollution in aquatic environments by organophosphate flame retardants (OPFRs). Historical cumulative pollution from legacy OPFRs, combined with newly emerging OPFRs, has increased the severity and complexity of OPFR pollution in this region. We explored the contamination profile, input flux and risk of legacy and emerging OPFRs in surface waters and in sediment samples of the PRD. The results indicated that all OPFRs we targeted were detectable in the water samples; The sum concentration of OPFRs in the water ranged from 17.35 ng/L to 673.30 ng/L, with an average level of 215.11 ng/L; In sediments it ranged from 5.68 ng/g to 802.46 ng/g dry weight (dw). Tris(2-chloroisopropyl) phosphate (TCPP, 99.58 ng/L) and Bisphenol A diphenyl phosphate (BDP, 51.09 ng/g dw) were the most abundant OPFRs in the surface water and sediment, respectively. Notably, although Tetrekis (2-chlorethyl) dichloroisopentyl-diphosphate (V6) has only been used in recent years, its relatively high concentrations and proportions, both in water and sediment samples, demonstrate its now widespread occurrence in the PRD. The estimated annual flux of ΣOPFRs from the eight estuaries to the South China Sea was 45.04 t/y. The four estuaries (Humen, Modaomen, Hengmen and Honqimen) contribute 80% of the mass loading. Triphenyl phosphate (TPHP) and Tris (2-chloroethyl) phosphate (TCEP) in water posed relatively higher ecological risks to algae, daphnia, and fish than other OPFRs. Our results provide scientific support for continuing monitoring and control of OPFR pollution in the PRD.