Sediment toxicity data and excess simultaneously extracted metals from field-collected samples: Comparison to United States Environmental Protection Agency benchmarks.

US Environmental Protection Agency (USEPA) Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms: Metal Mixtures are based on the principle that metals toxicity to benthic organisms is determined by bioavailable metals concentrations in porewater. One ESB is based on the difference between simultaneously extracted metal (SEM) and acid volatile sulfide (AVS) concentrations in sediment (excess SEM). The excess SEM ESBs include a lower uncertainty bound, below which most samples (95%) are expected to be "nontoxic" (defined as a bioassay mortality rate ≤24%), and an upper uncertainty bound, above which most samples (95%) are expected to be "toxic" (defined as a mortality rate >24%). Samples that fall between the upper and lower bounds are classified as "uncertain." Excess SEM ESBs can, in principle, be improved by normalizing for organic carbon (OC). OC is a binding phase that reduces metals bioavailability. OC normalization should improve the accuracy of bioavailable metal concentration estimates, thus tightening uncertainty bounds. We evaluated field-collected sediments from 13 studies with excess SEM, OC, and bioassay data (n = 740). Use of the OC-normalized excess SEM benchmarks did not improve prediction accuracy. The ESB model predicts OC-normalized excess SEM exceeding the upper benchmark even when toxicity is not observed, because error in the OC normalization model increases at low OC concentrations. To minimize the likelihood of incorrectly identifying nontoxic samples as toxic, we recommend that OC normalization of excess SEM should not be considered for sediments with an OC concentration <1% and is questionable for sediments with an OC concentration of 1%-4%. Additional focused studies are needed to confirm or refine the minimum sediment OC concentrations that are applicable for reducing uncertainty in toxicity predictions due to excess SEM. Integr Environ Assess Manag 2022;18:174-186. © 2021 SETAC.

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.

Refining our understanding of metal bioavailability in sediments using information from porewater: Application of a multimetal biotic ligand model as an extension of the equilibrium partitioning sediment benchmarks.

The equilibrium partitioning sediment benchmarks (ESBs) derived by the US Environmental Protection Agency (USEPA) in 2005 provide a mechanistic framework for understanding metal bioavailability in sediments by considering equilibrium partitioning (EqP) theory, which predicts that metal bioavailability in sediments is determined largely by partitioning to sediment particles. Factors that favor the partitioning of metals to sediment particles, such as the presence of acid volatile sulfide (AVS) and sediment organic matter, reduce metal bioavailability to benthic organisms. Because ESBs link metal bioavailability to partitioning to particles, they also predict that measuring metals in porewater can lead to a more accurate assessment of bioavailability and toxicity to benthic organisms. At the time of their development, sediment ESBs based on the analysis of porewater metal concentrations were limited to comparison with hardness-dependent metals criteria for the calculation of interstitial water benchmark units (IWBUs). However, the multimetal biotic ligand model (mBLM) provides a more comprehensive assessment of porewater metal concentrations, because it considers factors in addition to hardness, such as pH and dissolved organic carbon, and allows for interactions between metals. To evaluate the utility of the various sediment and porewater ESBs, four Hyalella azteca bioassay studies were identified that included sediment and porewater measurements of metals and porewater bioavailability parameters. Evaluations of excess simultaneously extracted metals, IWBUs, and mBLM toxic units (TUs) were compared among the bioassay studies. For porewater, IWBUs and mBLM TUs were calculated using porewater metal concentrations from samples collected using centrifugation and peepers. The percentage of correct predictions of toxicity was calculated for each benchmark comparison. The mBLM-based assessment using peeper data provided the most accurate predictions for the greatest number of samples among the evaluation methods considered. This evaluation demonstrates the value of porewater-based evaluations in conjunction with sediment chemistry in understanding toxicity observed in bioassay studies. Integr Environ Assess Manag 2022;18:1335-1347. © 2021 SETAC.