Molecular insight into the binding properties of marine algogenic dissolved organic matter for polybrominated diphenyl ethers and their combined effect on marine zooplankton.

Polybrominated diphenyl ethers (PBDEs) are widespread in marine ecosystems, despite the limits placed on several congeners, and pose a threat to marine organisms. Many coexisting factors, especially dissolved organic matter (DOM), affect the environmental behavior and ecological risk of PBDEs. Since blooms frequently occur in coastal waters, we used algogenic DOM (A-DOM) from the diatom Skeletonem costatum and examined the interaction of A-DOM with 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Moreover, their combined effect on the rotifer Brachionus plicatilis was analyzed. During the stationary period, A-DOM had more proteins than polysaccharides, and 7 extracellular proteins were identified. A-DOM fluorescence was statically quenched by BDE-47, and amide, carbonyl, and hydroxyl groups in A-DOM were involved. Molecular docking analysis showed that all 5 selected proteins of A-DOM could spontaneously bind with BDE-47 and that hydrophobic interactions, van der Waals forces and pi-bond interactions existed. The reproductive damage, oxidative stress and inhibition of mitochondrial activity induced by BDE-47 in rotifers were relieved by A-DOM addition. Transcriptomic analysis further showed that A-DOM could activate energy metabolic pathways in rotifers and upregulate genes encoding metabolic detoxification proteins and DNA repair. Moreover, A-DOM alleviated the interference effect of BDE-47 on lysosomes, the extracellular matrix pathway and the calcium signaling system. Alcian blue staining and scanning electron microscopy showed that A-DOM aggregates were mainly stuck to the corona and cuticular surface of the rotifers; this mechanism, rather than a real increase in uptake, was the reason for enhanced bioconcentration. This study reveals the complex role of marine A-DOM in PBDEs bioavailability and enhances the knowledge related to risk assessments of PBDE-like contaminants in marine environments.

Investigation on the interaction differences of algogenic dissolved organic matter released by Prorocentrum donghaiense with phenanthrene and 3-methylphenanthrene using spectroscopy.

Despite the high algogenic dissolved organic matter (A-DOM) content in the marine environment, the impact of A-DOM on the environmental behavior of alkylated polycyclic aromatic hydrocarbons (A-PAHs) has rarely been reported. Thus, this study sought to investigate the changes in A-DOM and its interaction with phenanthrene (Phe) and 3-methylphenanthrene (3-MPhe). The results showed that the spectroscopic characteristics of A-DOM changed dynamically during the entire growth period of Prorocentrum donghaiense. The total proportions of humic-like components in A-DOM, including marine humic-like and longer wavelength humic-like components, increased from 26.30% at the initial phase to 40.42% at the decline phase, but those of protein-like components decreased. Humic-like components showed stronger interaction capabilities with Phe/3-MPhe than that of protein-like components. The interaction characteristics and increased the humic-like components content indicated their prominent role in the interaction of A-DOM and Phe/3-MPhe. 3-MPhe had stronger hydrophobic interactions with the humic-like components and the methyl group increased π-π interactions with A-DOM on day 28. Methyl group also increased the molecular weight and steric hindrance of 3-MPhe, resulting in a lower interaction capability with A-DOM than that of Phe on day 16. The diverse interaction behaviors of A-DOM fluorescent components with Phe and 3-MPhe were largely attributed to dynamic changes in the A-DOM characteristics. Methyl substitution varied the hydrophobicity and molecular weight of Phe and 3-MPhe, and further influenced the interactions with A-DOM fluorescent components. These results highlight the vital impact of dynamic A-DOM on the environmental behavior of PAHs, and the differences in the environmental behavior between parent and alkylated PAHs should also receive additional attention.