Mixture Risk Drivers in Freshwater Sediments and Their Bioavailability Determined Using Passive Equilibrium Sampling

The identification of mixture risk drivers is a great challenge for sediment assessment, especially when taking bioavailability into consideration. The bioavailable portion, which comprises the organic contaminants in pore water and the ones bound to organic carbon, was accessed by equilibrium partitioning to polydimethylsiloxane (PDMS). The exhaustive solvent and PDMS extracts were toxicologically characterized with a battery of in vitro reporter gene assays and chemically analyzed with liquid and gas chromatography coupled to high-resolution mass spectrometry. The bioavailable fractions of mixture effects and individual chemicals were mostly lower than 0.1, indicating that more than 90% of the substances are strongly bound and would not pose an immediate risk but could potentially be remobilized in the long term. Despite 655 organic chemicals analyzed, only 0.1-28% of the observed biological effects was explained by the detected compounds in whole sediments, while 0.009-3.3% was explained by bioavailable chemicals. The mixture effects were not only dominated by legacy pollutants (e.g., polycyclic aromatic hydrocarbons (PAHs) in the bioassay for activation of the aryl-hydrocarbon receptor (AhR) and oxidative stress response (AREc32)) but also by present-use chemicals (e.g., plastic additives for binding to the peroxisome proliferator-activated receptor γ (PPARγ)), with different fingerprints between whole sediments and bioavailable extracts. Our results highlight the necessity to involve different bioassays with diverse effect profiles and broader selection of contaminants along with bioavailability for the risk assessment of chemical mixtures in sediments.