Importance of equilibration time in the partitioning and toxicity of zinc in spiked sediment bioassays

The influences of spiked Zn concentrations (1-40 micromol/g) and equilibration time (approximately 95 d) on the partitioning of Zn between pore water (PW) and sediment were evaluated with estuarine sediments containing two levels (5 and 15 micromol/g) of acid volatile sulfides (AVS). Their influence on Zn bioavailability was also evaluated by a parallel, 10-d amphipod (Leptocheirus plumulosus) mortality test at 5, 20, and 85 d of equilibration. During the equilibration, AVS increased (up to twofold) with spiked Zn concentration ([Zn]), whereas Zn-simultaneously extracted metals ([SEM]; Zn with AVS) remained relatively constant. Concentrations of Zn in PW decreased most rapidly during the initial 30 d and by 11- to 23-fold during the whole 95-d equilibration period. The apparent partitioning coefficient (Kpw, ratio of [Zn] in SEM to PW) increased by 10- to 20-fold with time and decreased with spiked [Zn] in sediments. The decrease of PW [Zn] could be explained by a combination of changes in AVS and redistribution of Zn into more insoluble phases as the sediment aged. Amphipod mortality decreased significantly with the equilibration time, consistent with decrease in dissolved [Zn]. The median lethal concentration (LC50) value (33 microM) in the second bioassay, conducted after 20 d of equilibration, was twofold the LC50 in the initial bioassay at 5 d of equilibration, probably because of the change of dissolved Zn speciation. Sediment bioassay protocols employing a short equilibration time and high spiked metal concentrations could accentuate partitioning of metals to the dissolved phase and shift the pathway for metal exposure toward the dissolved phase.