Investigation of Daphnia magna Sub-Lethal Exposure to Organophosphate Esters in the Presence of Dissolved Organic Matter Using ¹H NMR-Based Metabolomics.

Organophosphate esters (OPEs) are frequently detected in aquatic environments. Hydrophobic OPEs with high octanol-water partition coefficients (Log KOW ) will likely sorb to dissolved organic matter (DOM) and consequently alter OPE bioavailability and sub-lethal toxicity. ¹H nuclear magnetic resonance (NMR)-based metabolomics was used to evaluate how DOM (5 mg organic carbon/L) alters the metabolic response of Daphnia magna exposed to sub-lethal concentrations of three individual OPEs with varying hydrophobicity. D. magna exposed to the hydrophilic contaminant (Log KOW = 1.43) tris(2-chloroethyl) phosphate (TCEP) did not have substantial metabolic changes and DOM did not alter the metabolic response. There were significant increases in amino acids and a decrease in glucose from exposure to the hydrophobic contaminant (Log KOW = 3.65) tris(2-butoxyethyl) phosphate (TBOEP) which DOM did not mitigate, likely due to the high sub-lethal toxicity of TBOEP. Exposure to DOM and the hydrophobic contaminant (Log KOW = 4.76) triphenyl phosphate (TPhP) resulted in a unique metabolic response which was unlike TPhP only exposure, perhaps because DOM may be an additional stressor with TPhP exposure. Therefore, Log KOW values may not always predict how sub-lethal contaminant toxicity will change with DOM and there should be more consideration to incorporate DOM in sub-lethal ecotoxicology testing.