Copper Sediment Toxicity and Partitioning during Oxidation in a Flow-Through Flume.

The bioavailability of transition metals in sediments often depends on redox conditions in the sediment. We explored how the physicochemistry and toxicity of anoxic Cu-amended sediments changed as they aged (i.e., naturally oxidized) in a flow-through flume. We amended two sediments (Dow and Ocoee) with Cu, incubated the sediments in a flow-through flume, and measured sediment physicochemistry and toxicity over 213 days. As sediments aged, oxygen penetrated sediment to a greater depth, the relative abundance of Fe oxides increased in surface and deep sediments, and the concentration of acid volatile sulfide declined in Ocoee surface sediments. The total pool of Cu in sediments did not change during aging, but porewater Cu, and Cu bound to amorphous Fe oxides decreased while Cu associated with crystalline Fe oxides increased. The dose-response of the epibenthic amphipod Hyalella azteca to sediment total Cu changed over time, with older sediments being less toxic than freshly spiked sediments. We observed a strong dose-response relationship between porewater Cu and H. azteca growth across all sampling periods, and measurable declines in relative growth rates were observed at concentrations below interstitial water criteria established by the U.S. EPA. Further, solid-phase bioavailability models based on AVS and organic carbon were overprotective and poorly predicted toxicity in aged sediments. We suggest that sediment quality criteria for Cu is best established from measurement of Cu in pore water rather than estimating bioavailable Cu from the various solid-phase ligands, which vary temporally and spatially.