The sediment-water interface of spiked-sediment toxicity tests is a complex exposure system, where multiple uptake pathways exist for benthic organisms. The freely dissolved concentration (C free ) in sediment pore water has been proposed as a relevant exposure metric to hydrophobic organic contaminants (HOCs) in this system. C free , however, has rarely been measured in spiked-sediment toxicity tests. In this study, we first developed a direct immersion SPME method for measuring C free in overlying and pore water in a sediment test using polydimethylsiloxane (PDMS)-coated glass fibers, resulting in sensitive and repeatable in situ measurements of HOCs. Then, we measured This article is protected by copyright. All rights reserved.
Accepted ArticleC free and total dissolved concentrations (C diss ) in the sediment test systems with the freshwater amphipod Hyalella azteca, thoroughly evaluated the temporal and spatial profiles of four HOCs (phenanthrene, pyrene, benzo[a]pyrene, and chlorpyrifos). Furthermore, we examined the relationship between the measured concentrations and the lethality of H. azteca. We found that the test system was far from an equilibrium state for all four chemicals tested, where C diss in overlying water changed over the test duration and a vertical C free gradient existed at the sediment-water interface. C diss was larger than C free by a factor of 170-220 in pore water for benzo[a]pyrene due to the strong binding to dissolved organic carbon. The comparison of the median lethal concentrations (LC50) of chlorpyrifos in the sediment test and those in water-only tests indicates that C free in pore water was the most representative indicator for toxicity of this chemical. The method and findings presented in this work warrant further research on the chemical transport mechanisms and the actual exposure in sediment tests using different chemicals, sediments, and test species.