Technical basis for establishing sediment quality criteria for nonionic organic chemicals using equilibrium partitioning
01 Dec 1991-Environmental Toxicology and Chemistry (John Wiley & Sons, Ltd)-Vol. 10, Iss: 12, pp 1541-1583
TL;DR: In this article, the authors present the technical basis for establishing sediment quality criteria using equilibrium partitioning (EqP), which 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.
Abstract: 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.
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TL;DR: In this article, matching biological and chemical data were compiled from numerous modeling, laboratory, and field studies performed in marine and estuarine sediments, and two guideline values (an effects range low and an effects range median) were determined for nine trace metals, total PCBs, two pesticides, 13 polynuclear aromatic hydrocarbons (PAHs), and three classes of PAHs.
Abstract: Matching biological and chemical data were compiled from numerous modeling, laboratory, and field studies performed in marine and estuarine sediments. Using these data, two guideline values (an effects range-low and an effects range-median) were determined for nine trace metals, total PCBs, two pesticides, 13 polynuclear aromatic hydrocarbons (PAHs), and three classes of PAHs. The two values defined concentration ranges that were: (1) rarely, (2) occasionally, or (3) frequently associated with adverse effects. The values generally agreed within a factor of 3 or less with those developed with the same methods applied to other data and to those developed with other effects-based methods. The incidence of adverse effects was quantified within each of the three concentration ranges as the number of cases in which effects were observed divided by the total number of observations. The incidence of effects increased markedly with increasing concentrations of all of the individual PAHs, the three classes of PAHs, and most of the trace metals. Relatively poor relationships were observed between the incidence of effects and the concentrations of mercury, nickel, total PCB, total DDT and p,p′-DDE. Based upon this evaluation, the approach provided reliable guidelines for use in sediment quality assessments. This method is being used as a basis for developing National sediment quality guidelines for Canada and informal, sediment quality guidelines for Florida.
3,869 citations
TL;DR: It was concluded that the consensus-based SQGs provide a reliable basis for assessing sediment quality conditions in freshwater ecosystems.
Abstract: Numerical sediment quality guidelines (SQGs) for freshwater ecosystems have previously been developed using a variety of approaches. Each approach has certain advantages and limitations which influence their application in the sediment quality assessment process. In an effort to focus on the agreement among these various published SQGs, consensus-based SQGs were developed for 28 chemicals of concern in freshwater sediments (i.e., metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and pesticides). For each contaminant of concern, two SQGs were developed from the published SQGs, including a threshold effect concentration (TEC) and a probable effect concentration (PEC). The resultant SQGs for each chemical were evaluated for reliability using matching sediment chemistry and toxicity data from field studies conducted throughout the United States. The results of this evaluation indicated that most of the TECs (i.e., 21 of 28) provide an accurate basis for predicting the absence of sediment toxicity. Similarly, most of the PECs (i.e., 16 of 28) provide an accurate basis for predicting sediment toxicity. Mean PEC quotients were calculated to evaluate the combined effects of multiple contaminants in sediment. Results of the evaluation indicate that the incidence of toxicity is highly correlated to the mean PEC quotient (R(2) = 0.98 for 347 samples). It was concluded that the consensus-based SQGs provide a reliable basis for assessing sediment quality conditions in freshwater ecosystems.
2,732 citations
Cites background or methods from "Technical basis for establishing se..."
...Guidelines for assessing sediment quality relative to the potential for adverse effects on sediment-dwelling organisms in freshwater systems have been derived using a combination of theoretical and empirical approaches, primarily including the equilibrium partitioning approach (EqPA; Di Toro et al. 1991; NYSDEC 1994; US EPA 1997a), screening level concentration approach (SLCA; Persaud et al. 1993), effects range approach (ERA; Long and ......
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...The equilibrium partitioning (EqP) approach provides a theoretical basis for deriving sediment quality guidelines for the protection of freshwater organisms ( Di Toro et al. 1991; Zarba 1992)....
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Abstract: The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.
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...Further, it has been assumed that the predominant bioavailable portion of the total contaminant was the soluble form [40]....
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TL;DR: Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride, and PCBs could transfer from contaminated plastics to streaked shearwater chicks.
Abstract: Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2′-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g–1 to µg g–1. Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l–1 to mg l–1 and were correlated with the level of economic development.
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TL;DR: A comprehensive and critical review of the environmental fate of eighteen commercial phthalate esters with alkyl chains ranging from 1 to 13 carbons was performed by as discussed by the authors, which revealed that most published values exceed true water solubilities due to experimental difficulties associated with solubility determinations for these hydrophobic organic liquids.
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References
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Book•
01 Jan 1985
TL;DR: The first part of the book as mentioned in this paper is a general overview of the amount and general nature of dissolved organic carbon in natural waters, and the second part is a summary of the data that has accumulated from many disciplines over the last decade.
Abstract: This book is written as a reference on organic substances in natural waters and as a supplementary text for graduate students in water chemistry. The chapters address five topics: amount, origin, nature, geochemistry, and characterization of organic carbon. Of these topics, the main themes are the amount and nature of dissolved organic carbon in natural waters (mainly fresh water, although seawater is briefly discussed). It is hoped that the reader is familiar with organic chemistry, but it is not necessary. The first part of the book is a general overview of the amount and general nature of dissolved organic carbon. Over the past 10 years there has been an exponential increase in knowledge on organic substances in water, which is the result of money directed toward the research of organic compounds, of new methods of analysis (such as gas chromatography and mass spectrometry), and most importantly, the result of more people working in this field. Because of this exponential increase in knowledge, there is a need to pull together and summarize the data that has accumulated from many disciplines over the last decade.
2,803 citations
2,626 citations
TL;DR: In this paper, it was shown that acid volatile sulfide (AVS) is the sediment phase that determines the LC50 for cadmium in the marine sediments tested.
Abstract: 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.
800 citations
TL;DR: Sorption partition coefficients, indexed to organic carbon (Koc), are relatively invariant for natural sorbents as mentioned in this paper, and they can be estimated from other physical properties of pollutants (aqueous solubility or octanol/water partition coefficients).
Abstract: An understanding of sorption processes is an important key to describing pollutant fate in an aquatic system because sorption may alter significantly physical transport and chemical reactivity of pollutants. The sorption of uncharged organic chemicals to natural aquatic sorbents is dominated by “hydrophobic interactions.” For composite particulates (i.e., sediments/soils), organic matter is the primary sorbing constituent. Sorption partition coefficients, indexed to organic carbon (Koc), are relatively invariant for natural sorbents. Koc's can be estimated from other physical properties of pollutants (aqueous solubility or octanol/water partition coefficients). Hydrophilic contributions to sorption tend to occur with one or both of the following conditions: (1) High sorbate polarity; and (2) low organic carbon content of the sorbent, especially with coincident high clay content. Although a priori estimation techniques comparable to hydrophobic sorption are not presently available, hydrophilic contribution...
774 citations
TL;DR: In this article, the molar concentration of acid volatile sulfide (AVS) in the sediment is defined as the threshold below which these metals cease to exhibit an acute toxicity in freshwater and marine sediments.
Abstract: Laboratory toxicity tests using amphipods, oligochaetes, and snails with spiked freshwater and marine sediments and with contaminated sediments collected from an EPA Superfund site demonstrate that no significant mortality occurs relative to controls if the molar concentration of acid volatile sulfide (AVS) in the sediment is greater than the molar concentration of simultaneously extracted cadmium and/or nickel. Although it is well-known that these metals can form insoluble sulfides, it apparently has not been realized that AVS is a reactive pool of solid-phase sulfide that is available to bind metals and render that portion unavailable and nontoxic to biota. Thus, the AVS concentration of a sediment establishes the boundary below which these metals cease to exhibit an acute toxicity in freshwater and marine sediments.
642 citations