Contribution ratio of freely to total dissolved concentrations of polycyclic aromatic hydrocarbons in natural river waters

The bioavailability and ecological risk of hydrophobic organic compounds (HOCs) in aquatic environments largely depends on their freely dissolved concentrations. In this work, the freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) including phenanthrene, pyrene, and chrysene were determined for the Yellow River, Haihe River and Yongding River of China using polyethylene devices (PEDs). The results indicated that the order of ratios of freely to total dissolved concentrations of the three PAHs was phenanthrene (66.8 ± 20.1%) > pyrene (48.8 ± 26.4%) > chrysene (5.5 ± 3.3%) for the three rivers. The ratios were significantly negatively correlated with the log K_ow values of the PAHs. In addition, the ratios were negatively correlated with the suspended sediment (SPS) and dissolved organic carbon (DOC) concentrations in the river water, and the characteristics of the SPS and DOC were also important factors. Simulation experiments showed that the ratio of freely to total dissolved concentrations of pyrene in the aqueous phase decreased with increasing SPS concentration; when the sediment concentration increased from 2 g L^?1 to 10 g L^?1, the ratio decreased from 67.6% to 38.4% for Yellow River sediment and decreased from 50.4% to 33.6% for Haihe River sediment. This was because with increasing SPS concentration, more and more DOC, small particles and colloids (<0.45 μm) would enter the aqueous phase. Because high SPS and DOC concentrations exist in many rivers, their effect on the freely dissolved concentrations of HOCs should be considered when conducting an ecological risk assessment.