Phthalate monoesters as markers of phthalate contamination in wild marine organisms

The level of phthalate esters (PAEs) alone is not considered to be a sufficient indicator of PAE pollution due to the quick metabolism of PAEs in the biota. The primary metabolites of PAEs, monoalkyl phthalate esters (MPEs), may also be an important indicator. However, PAE metabolism has scarcely been documented in wild marine organisms. We analysed five PAEs [dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DNOP)] and their corresponding MPEs [mono-methyl phthalate (MMP), mono-ethyl phthalate (MEP), mono-n-butyl phthalate (MBP), mono-2-ethylhexyl phthalate (MEHP), and mono-n-octyl phthalate (MNOP)] in 95 wild aquatic marine samples (including fish, prawns and molluscs) collected from the Yangtze River Delta area of the East China Sea. The species-dependent distribution of these compounds was associated with the food habits, living patterns and trophic levels of the biota. Slightly higher levels of hydrophobic PAEs (DBP and DEHP, logK_OW 4.27 and 7.33, respectively) were observed in fish species consuming benthic organisms or in demersal fish species, suggesting the importance of benthic organisms and sediment. Trophic dilution of both PAEs and MPEs implies further metabolic transformation at higher trophic levels. MPE tissue distributions in fish demonstrate that the highest concentrations were always observed in bile. Metabolism via the kidney and gill is a probable main way for the relatively less hydrophobic MPEs (logK_OW = <4.73, from MMP to MEHP), whereas metabolism via the liver is likely the main way for the most hydrophobic MNOP (logK_OW 5.22). Generally, higher detection frequencies of MPEs were observed than those of parent PAEs. Significant liner correlations were observed between the levels of short-branched (carbon atom per chain = <4) MPEs and the sum of PAEs and MPEs (n = 95, p < 0.01), demonstrating that short-branched MPEs can be used as biomarkers of exposure to quantitatively reflect parent PAE contamination in wild marine organisms.