Mechanistic sediment quality guidelines based on contaminant bioavailability: equilibrium partitioning sediment benchmarks.

Globally, estimated costs to manage (i.e., remediate and monitor) contaminated sediments are in the billions of U.S. dollars. Biologically based approaches for assessing the contaminated sediments which pose the greatest ecological risk range from toxicity testing to benthic community analysis. In addition, chemically based sediment quality guidelines (SQGs) provide a relatively inexpensive line of evidence for supporting these assessments. The present study summarizes a mechanistic SQG based on equilibrium partitioning (EqP), which uses the dissolved concentrations of contaminants in sediment interstitial waters as a surrogate for bioavailable contaminant concentrations. The EqP-based mechanistic SQGs are called equilibrium partitioning sediment benchmarks (ESBs). Sediment concentrations less than or equal to the ESB values are not expected to result in adverse effects and benthic organisms should be protected, while sediment concentrations above the ESB values may result in adverse effects to benthic organisms. In the present study, ESB values are reported for 34 polycyclic aromatic hydrocarbon, 32 other organic contaminants, and seven metals (cadmium, chromium, copper, nickel, lead, silver, zinc). Also included is an overview of EqP theory, ESB derivation, examples of applying ESB values, and considerations when using ESBs. The ESBs are intended as a complement to existing sediment-assessment tools, to assist in determining the extent of sediment contamination, to help identify chemicals causing toxicity, and to serve as targets for pollutant loading control measures.

Using field data and weight of evidence to develop water quality criteria.

In the United States, ambient aquatic life water quality criteria are derived using guidelines developed in 1985 that include a clear and consistent methodology using data from standard toxicity tests. The methodology from these guidelines has been successful, but a broader methodology is needed because some effects of pollutants do not lend themselves to conventional toxicity testing. Criterion assessment is proposed as that methodology. In criterion assessment, a specific environmental goal is translated into a measurable benchmark of effect that is used together with a modeled exposure-response relationship to estimate a range of exposures that will achieve the specific goal. The model of the exposure-response relationships and the benchmark effect are developed from field data and laboratory data using multiple analytical methods. Then the model is solved for the effect, thereby estimating the criterion, an upper threshold for acceptable exposures. The resulting candidate criteria are synthesized to select criteria and other benchmark values, such as remedial goals. The criterion assessment process is illustrated using the US Environmental Protection Agency Framework for Developing for Suspended and Bedded Sediments Water Quality Criteria, which recommends developing alternative candidate criterion values and then evaluating them to select a final criterion. Candidate criteria may be derived from models of field observations, field manipulations, laboratory tests, or empirical and theoretical models. Final selection of a criterion uses a weight-of-evidence comparison that engenders confidence because causal associations are confirmed on the basis of different assumptions, independent data sets, and varied statistical methods, thereby compensating for the concerns raised by individual studies and methods. Thus, it becomes possible to specify criteria for agents with biological or physical modes of action, as well as those with chemical modes of action, to best achieve environmental goals.

Predicting sediment metal toxicity using a sediment biotic ligand model: methodology and initial application.

An extension of the simultaneously extracted metals/acid-volatile sulfide (SEM/AVS) procedure is presented that predicts the acute and chronic sediment metals effects concentrations. A biotic ligand model (BLM) and a pore water-sediment partitioning model are used to predict the sediment concentration that is in equilibrium with the biotic ligand effects concentration. This initial application considers only partitioning to sediment particulate organic carbon. This procedure bypasses the need to compute the details of the pore-water chemistry. Remarkably, the median lethal concentration on a sediment organic carbon (OC)-normalized basis, SEM*(x,OC), is essentially unchanged over a wide range of concentrations of pore-water hardness, salinity, dissolved organic carbon, and any other complexing or competing ligands. Only the pore-water pH is important. Both acute and chronic exposures in fresh- and saltwater sediments are compared to predictions for cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) based on the Daphnia magna BLM. The SEM*(x,OC) concentrations are similar for all the metals except cadmium. For pH = 8, the approximate values (micromol/gOC) are Cd-SEM*(xOC) approximately equal to 100, Cu-SEM*(x,OC) approximately equal to 900, Ni-SEMoc approximately equal to 1,100, Zn-SEM*(x,OC) approximately equal to 1,400, and Pb-SEM*(x,OC) approximately equal to 2,700. This similarity is the explanation for an empirically observed dose-response relationship between SEM and acute and chronic effects concentrations that had been observed previously. This initial application clearly demonstrates that BLMs can be used to predict toxic sediment concentrations without modeling the pore-water chemistry.

Predicting the toxicity of chromium in sediments.

Chromium exists in sediments in two oxidation states: Cr(III), which is relatively insoluble and nontoxic, and Cr(VI), which is much more soluble and toxic. Chromium(VI) is thermodynamically unstable in anoxic sediments, and acid-volatile sulfide (AVS) is formed only in anoxic sediments; therefore sediments with measurable AVS concentrations should not contain toxic Cr(VI). If this hypothesis holds true, measuring AVS could form the basis for a theoretically based guideline for Cr in sediments. Ten-day water-only and spiked sediment toxicity tests with the amphipod Ampelisca abdita were performed with Cr(VI) and Cr(III), along with sediments collected from a site contaminated with high concentrations of Cr. In sediments where AVS exceeded analytical detection limits, Cr concentrations in interstitial water were very low (<100 microg/L) and no significant toxicity to A. abdita was observed. In sediments in which AVS was not significantly greater than zero, Cr concentrations in interstitial waters increased significantly, with greater than 90% of the Cr present as Cr(VI), and mortality of A. abdita was elevated. These results demonstrate that measurements of AVS and interstitial water chromium can be useful in predicting the absence of acute effects from Cr contamination in sediments.

Toxicity testing, risk assessment, and options for dredged material management.

Programs for evaluating proposed discharges of dredged material into waters of the United States specify a tiered testing and evaluation protocol that includes performance of acute and chronic bioassays to assess toxicity of the dredged sediments. Although these evaluations reflect the toxicological risks associated with disposal activities to some degree, analysis activities are limited to the sediments of each dredging project separately. Cumulative risks to water column and benthic organisms at and near the designated disposal site are therefore difficult to assess. An alternate approach is to focus attention on the disposal site, with the goal of understanding more directly the risks of multiple disposal events to receiving ecosystems. Here we review current US toxicity testing and evaluation protocols, and describe an application of ecological risk assessment that allows consideration of the temporal and spatial components of risk to receiving aquatic ecosystems. When expanded to include other disposal options, this approach can provide the basis for holistic management of dredged material disposal.