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. T...
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 concen-
The sorption of seven divalent metals (Ba, Sr, Cd, Mn, Zn, Co, and Ni) was measured on calcite over a large initial metal (Me) concentration range (lo-' to 10e4 mol/L) in constant ionic strength (I = 0. l), equilibrium CaC03(s)-CaCOs(aq) suspensions that varied in pH. At higher initial Me concentrations (10m5 to 10m4 mol/L) geochemical calculations indicated that the equilibrium solutions were saturated with discrete solid phases of the sorbates: CdCOx(s), MnCO,(s), Zn5(OH),(C0,)2(s), Co(OH),(s), and Ni(OH),(s), implying that aqueous concentrations were governed by solubility. However, significant sorption of all the metals except for Ba and Sr was observed at aqueous concentrations below saturation with Me-solid phases. Divalent metal ion sorption was dependent on aqueous Ca concentration, and the following selectivity sequence was observed: Cd > Zn 2 Mn > Co > Ni 4 Ba = Sr. The metals varied in their sorption reversibility, which was correlated with the single-ion hydration energies of the metal sorbates. The strongly hydrated metals (Zn, Co, and Ni) were most desorbable. A sorption model that included aqueous speciation and Me*+-Ca*+ exchange on cation-specific surface sites was developed that described most of the data well. The chemical nature of the surface complex used in this model was unspecified and could represent either a hydrated or dehydrated surface complex, or a surface precipitate. A single exchange constant for Cd, Mn, Co, and Ni could describe the sorption of that metal over a wide range in pH, Ca concentration, and surface concentration. Zinc, however, exhibited nonlinear sorption behavior and required exchange constants that varied with surface coverage. Our data suggested that (i) Cd and Mn dehydrate soon after their adsorption to calcite and form a phase that behaves like a surface precipitate, and (ii) Zn. Co. and Ni form surface complexes that remain hydrated until the ions are incorporated into the structure by recrystallization.
Abstract-The multimedia equilibrium criterion model, which can be used to evaluate the environmental fate of a variety of chemicals, is described. The model treats chemicals that fall into three categories. In the first the chemicals may partition into all environmental media, in the second they are involatile, and in the third they are insoluble in water. The structure of the model, the process equations, and the required input data for each chemical type are described. By undertaking a sequence of level I, II, and III calculations, increasing information is obtained about the chemical's partitioning, its susceptibility to transformation and transport, and the environmental process and the chemical characteristics that most influence chemical fate. Output data, consisting of tables and charts, give a complete picture of the chemical's fate in an evaluative or generic environment. The model is illustrated by applying it to two chemicals, pyrene, which is a chemical of the first type, and lead, which is of a second type. The role of this model as a tool for assessing the fate of new and existing chemicals is discussed.
Chromate adsorption was measured with and without reactive cosolutes on four subsurface soil horizons differing in pH and mineralogy, and on clay fractions from two of the oxide‐containing subsoils. Chromate adsorption was greatest in lower pH materials enriched in kaolinite and crystalline iron oxides. Over a range in pH, chromate adsorption to subsoil was similar to that observed for pure‐phase oxides. Chromate binding was reversible to pH and was depressed in the presence of SO2‐4 and dissolved inorganic C, which compete for adsorption sites. A surface site density for crystalline Al‐substituted iron oxides in the subsoils was estimated from chromate adsorption on the clay fractions using the model FITEQL and outer sphere surface coordination constants from Al‐goethite. The estimated site density for soil crystalline iron oxides was well below that of clean oxides, suggesting surface saturation by indigenous soil ions. The calculated site density and surface binding constants for Al‐goethite were used in the Triple Layer Model to calculate the effect of ionic strength, cosolutes, solids concentration, and sorbate concentration on CrO2‐4 adsorption. Model calculations were in good qualitative agreement with experimental results.
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