Collection and use of porewater data from sediment bioassay studies for understanding exposure to bioavailable metals

The US Environmental Protection Agency Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: Metal Mixtures (Cadmium, Copper, Lead, Nickel, Silver and Zinc) equilibrium partitioning approach causally link metal concentrations and toxicological effects; they apply to sediment and porewater (i.e., interstitial water). The evaluation of bioavailable metal concentrations in porewater, using tools such as the biotic ligand model, provides an advancement that complements sediment-based evaluations. However, porewater characterization is less commonly performed in sediment bioassays than sediment chemistry characterization due to the difficulty and expense of porewater collection as well as concerns about interpretation of porewater data. This study discusses the advantages and disadvantages of different porewater extraction methods for analysis of metals and bioavailability parameters during laboratory sediment bioassays, with a focus on peepers and centrifugation. The purpose is to provide recommendations to generate bioassay porewater data of sufficient quality for use in risk-based decision-making, such as for regulated cleanup actions. Comparisons of paired data from previous bioassay studies indicate that metal porewater concentrations collected via centrifugation tend to be higher than those collected via peepers. However, centrifugation disrupts the redox status of the sediment; also, metal concentrations can vary markedly based on centrifugation conditions. Data to compare the concentrations of peeper- and centrifugation-collected bioavailability parameters (e.g., major ions, pH) are much more limited, but indicate smaller differences than those observed for metal concentrations. While peepers can be sampled without altering the redox status of the porewater, the small volume of porewater peepers collected is enough for metal concentration analysis, but insufficient for analysis of all metal bioavailability parameters. Given the benefits of metal collection via peepers, it is optimal to use centrifugation and peepers in tandem for bioassay porewater collection to improve bioavailability predictions. Environ Assess Manag 2022;18:1321-1334. © 2021 SETAC.