The purpose of this review paper is to present the technical basis for establishing sediment quality criteria using equilibrium partitioning (EqP). Equilibrium partitioning is chosen because it addresses the two principal technical issues that must be resolved: the varying bioavailability of chemicals in sediments and the choice of the appropriate biological effects concentration.

The data that are used to examine the question of varying bioavailability across sediments are from toxicity and bioaccumulation experiments utilizing the same chemical and test organism but different sediments. It has been found that if the different sediments in each experiment are compared, there is essentially no relationship between sediment chemical concentrations on a dry weight basis and biological effects. However, if the chemical concentrations in the pore water of the sediment are used (for chemicals that are not highly hydrophobic) or if the sediment chemical concentrations on an organic carbon basis are used, then the biological effects occur at similar concentrations (within a factor of two) for the different sediments. In addition, the effects concentrations are the same as, or they can be predicted from, the effects concentration determined in water- only exposures.

The EqP methodology rationalizes these results by assuming that the partitioning of the chemical between sediment organic carbon and pore water is at equilibrium. In each of these phases, the fugacity or activity of the chemical is the same at equilibrium. As a consequence, it is assumed that the organism receives an equivalent exposure from a water-only exposure or from any equilibrated phase, either from pore water via respiration, from sediment carbon via ingestion; or from a mixture of the routes. Thus, the pathway of exposure is not significant. The biological effect is produced by the chemical activity of the single phase or the equilibrated system.

Sediment quality criteria for nonionic organic chemicals are based on the chemical concentration in sediment organic carbon. For highly hydrophobic chemicals this is necessary because the pore water concentration is, for those chemicals, no longer a good estimate of the chemical activity. The pore water concentration is the sum of the free chemical concentration, which is bioavailable and represents the chemical activity, and the concentration of chemical complexed to dissolved organic carbon, which, as the data presented below illustrate, is not bioavailable. Using the chemical concentration in sediment organic carbon eliminates this ambiguity.

Sediment quality criteria also require that a chemical concentration be chosen that is sufficiently protective of benthic organisms. The final chronic value (FCV) from the U.S. Environmental Protection Agency (EPA) water quality criteria is proposed. An analysis of the data compiled in the water quality criteria documents demonstrates that benthic species, defined as either epibenthic or infaunal species, have a similar sensitivity to water column species. This is the case if the most sensitive species are compared and if all species are compared. The results of benthic colonization experiments also support the use of the FCV.

Equilibrium partitioning cannot remove all the variation in the experimentally observed sediment- effects concentration and the concentration predicted from water-only exposures. A variation of approximately a factor of two to three remains. Hence, it is recognized that a quantification of this uncertainty should accompany the sediment quality criteria.

The derivation of sediment quality criteria requires the octanol/water partition coefficient of the chemical. It should be measured with modern experimental techniques, which appear to remove the large variation in reported values. The derivation of the final chronic value should also be updated to include the most recent toxicological information.

https://setac.onlinelibrary.wiley.com/doi/pdf/10.1002/etc.5620101203

Technical basis for establishing sediment quality criteria for nonionic organic chemicals using equilibrium partitioning

The toxicity of chemicals in sediments is influenced by the extent that chemicals bind to the sediment. It is shown that acid volatile sulfide (AVS) is the sediment phase that determines the LC50 for cadmium in the marine sediments tested. Although it is well known that metals can form insoluble sulfides, it apparently has not been recognized that AVS is a reactive pool of solid phase sulfide that is available to bind with metals. Amphipod sediment toxicity tests were conducted in the laboratory and the observed amphipod LC50s on a normalized cadmium concentration basis, [Cd]/[AVS], is the same for sediments with over an order of magnitude difference in dry weight normalized cadmium LC50s.

Because other toxic metals also form insoluble sulfides, it is likely that AVS is important in determining their toxicity in sediments as well. Most freshwater and marine sediments contain sufficient acid volatile sulfide for this phase to be the predominant determinant of toxicity. The other sorption phases are expected to be important only for low AVS sediments, for example, fully oxidized sediments. From the point of view of sediment quality criteria the other sorption phases would be important for metals with large partition coefficients and large chronic water quality criteria.

Toxicity of cadmium in sediments: the role of acid volatile sulfide

The science of sediment toxicology essentially began in the late 1970s. It was largely a product of dredging concerns and recognition of widespread contamination of sediments. During the past few years, sediment toxicity research activity has increased dramatically. Currently, most tests are of an acute nature with fewer available for determining sublethal endpoints of chronic toxicity. Test systems of single and multiple species have included most levels of biological organization in aquatic ecosystems and have been conducted in the laboratory on whole sediments, interstitial waters, elutriates, or other extractable fractions under a wide variety of conditions. Evaluations of methodological effects and comparisons with in situ toxicity using surrogate test species and indigenous communities have, on occasion, shown significant differences in test responses. These differences may be attributed to laboratory-controlled parameters (e.g., light, species, life stage, exposure conditions, test phase, spiking method); sampling and laboratory-induced disruption of sediment integrity; alteration of toxicant partitioning due to manipulations and temporal effects; and failure to recognize other influencing ecosystem variables (e.g., organism niche and life cycle, sediment partitioning and gradient dynamics, physicochemical and biological process integration, biotic and abiotic disturbances, micro- and macrobiota patches, food-web interactions). Optimizing and standardizing test methods will require further studies of these variables to improve inter-laboratory comparisons and ecosystem validity. Despite the many unknowns that exist, a variety of sediment toxicity tests have been effectively used in assessing toxicant contamination by measuring the bioavailable fraction of the in-place pollutants. The optimal assays vary with the study and its objectives. Intergrative studies using several chemical, community, and toxicity measures are currently the most effective at defining ecosystem perturbations.

https://setac.onlinelibrary.wiley.com/doi/pdf/10.1002/etc.5620101204

Assessing the toxicity of freshwater sediments

Most of the thousands of substances and species that risk assessment has to deal with are not investigated empirically because of financial, practical, and ethical constraints. To facilitate extrapolation, we have developed a model for accumulation kinetics of organic substances as a function of the octanol-water partition ratio (Kow) of the chemical and the weight, lipid content, and trophic level of the species. The ecological parameters were obtained from a previous review on allometric regressions. The chemical parameters, that is, resistances that substances encounter in water and lipid layers of organisms, were calibrated on 1,939 rate constants for absorption from water for assimilation from food and for elimination. Their ratio was validated on 37 laboratory bioconcentration and biomagnification regressions and on 2,700 field bioaccumulation data. The rate constant for absorption increased with the hydrophobicity of the substances with a Kow up to about 1,000 and then leveled off, decreasing with the weight of the species. About 39% of the variation was explained by the model, while deviations of more than a factor of 5 were noted for labile, large, and less hydrophobic molecules as well as for algae, mollusks, and arthropods. The efficiency for assimilation of contaminants from food was determined mainly by the food digestibility and thus by the trophic level of the species. A distinction was made between substances that are stable, that is, with a minimum elimination only, and those that are labile, that is, with an excess elimination probably largely due to biotransformation. The rate constant for minimum elimination decreased with the hydrophobicity of the substance and the weight of the species. About 70% of the variation was explained by the model, while deviations of more than a factor of 5 were noted for algae, terrestrial plants, and benthic animals. Labile substances were eliminated faster than isolipophilic stable compounds, but differences in laboratory elimination and accumulation were small compared with those in field accumulation. Excess elimination by vertebrates was faster than by invertebrates. Differences between terrestrial and aquatic species were attributed to water turnover rates, whereas differences between trophic levels were due to the food digestibility. Food web accumulation, expressed as organism-organic solids and organism-food concentrations ratios could be largely explained by ecological variables only. The model is believed to facilitate various types of scientific interpretation as well as environmental risk assessment.

The power of size. 1. Rate constants and equilibrium ratios for accumulation of organic substances related to octanol-water partition ratio and species weight

From the viewpoint of protecting the natural environment, aquatic ecotoxicological assessment of new pesticides and many existing ones has increasingly become more important. To assess the impact of pesticides on aquatic organisms, international authorities (utilizing OECD and USEPA testing guidelines) require completion of many acute and chronic ecotoxicological studies. Among such studies is testing to measure the potential for bioconcentration. In addition, the authorities in these agencies insist that physico-chemical properties and environmental fate be determined for each registered pesticide. The rationale for such testing is based on the concept that, even if used in conformance with good agricultural practices, pesticides may enter surface waters by several routes such as spray drift, surface runoff, and field drainage, and they may be partitioned to bottom sediments (Katagi 2006). The endpoints of such ecotoxicological testing include mortality and effects on hatching, development, and reproduction. Such endpoints are usually expressed as median-lethal or median-effect concentrations (LC50 and EC50) and no-observed-effect-concentrations (NOEC); such values can be compared with predicted environmental concentrations in exposure media for purposes of risk assessment (Miyamoto et al. 2008). Because aquatic organisms interact with each other in the food web, knowledge of their tendency to bioconcentrate residues in water and from dietary exposure is important when evaluating real environmental pesticide effects. In general, bioconcentration is the most popular term for describing the process by which pesticides enter organisms directly from water through the gills or through epithelial tissues. In contrast, bioaccumulation includes the effect of dietary uptake through food consumption or intake of bottom sediments (Miyamoto et al. 1990). When the levels of a pesticide, accumulated by organisms, are concentrated through two or more trophic levels in a food web, the process is referred to as biomagnification (Connell 1988).

Bioconcentration, bioaccumulation, and metabolism of pesticides in aquatic organisms.

Comparaison de la bioconcentration des pesticides chez des insectes exposes directement au sediment contamine ou se trouvant dans l'eau situee au-dessus du sediment pour pouvoir suivre la vitesse de decontamination apres transfert en eau propre

G. P. Rawn

Papers

Bioconcentration of cypermethrin, deltamethrin, fenvalerate and permethrin by Chironomus tentans larvae in sediment and water