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Speciation of Metals , Effects on Aquatic Biota

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The interaction of dissolved metal with biological surfaces of organisms is dependent on a full understanding of speciation in aquatic media. The understanding has been recently developed as a method for predicting the toxicity of metals in aquatic systems on a site-specific (i.e., water chemistry) basis. The approach has also been extended, with appropriate modifications, to predict metal toxicity soils and sediments. The biotic ligand modeling approach is mechanistically based and relies on the fact that waterborne metals bind to and/or are taken up at specific sites, that this uptake/binding can be reliably characterized, and that there is a direct correlation between bioaccumulation and toxicity. The conceptual foundation of the...

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Abbreviations

Biotic ligand model (BLM):

Is a conceptual model where toxicity is assumed to be proportional to metal binding at a site of toxic action (the Biotic Ligand often assumed to be the gill). Bound metal is influenced by metal complexation reactions in solution and competition with other cations for the biotic ligand. The amount of metal bound to the biotic ligand can be calculated using geochemical modeling techniques and tabulated equilibrium constants. In practice, BLM often refers to the computer code and/or set of constants predicting toxicity for a given dataset (organism and metal).

Free ion activity model (FIAM):

Is conceptually similar to the BLM. Here toxicity is assumed to be proportional to the free metal concentration. The free metal ion is assumed to be the most bioavailable. FIAM can take into account solution complexation protective effects but not cation competition protective effects on metal toxicity.

Geochemical modeling:

Refers to calculated equilibrium distribution of elements based on defined reaction stoichiometries and equilibrium constants. Numerically, simultaneous equilibria must be satisfied within the constraint of system mass balance and electroneutrality.

Natural organic matter (NOM):

Is a ubiquitous and important ligand for metal complexation in solution. NOM comes from breakdown of terrestrial organic matter (terrigenous carbon) or is generated in situ in the water column (autochthonous carbon) by the activity of microorganisms (i.e., bacteria, algae). For BLM predictions, NOM is approximated by the measurable quantity dissolved organic carbon (DOC). In many aquatic systems the most important components of NOM are humic and fulvic acids, which are macromolecular polyelectrolytes with metal binding functional groups such as phenolic and carboxylic.

Speciation:

Distribution of an element among its possible chemical and physical forms. For metallic elements, the terminology would be metal speciation. Speciation can refer to an analytical measurement or a chemical equilibrium calculation. Speciation can be coarsely resolved such as filtered (dissolved) versus unfilterable (particulate) metal, for example, or very specific such as measured or calculated molecular species (i.e., M, MOH, MCl, M-NOM, etc.). The sum of all chemical species corresponds to the total element (metal).

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Correspondence to James C. McGeer .

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McGeer, J.C., Smith, D.S., Brix, K.V., Adams, W.J. (2012). Speciation of Metals , Effects on Aquatic Biota. In: Meyers, R.A. (eds) Encyclopedia of Sustainability Science and Technology. Springer, New York, NY. https://doi.org/10.1007/978-1-4419-0851-3_291

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