The Speciation of Metals in Natural Waters

Abstract

The equilibria and rates of reactions of trace metals in natural waters are affected by their speciation or the form of the metal in the solution phase. Many workers have shown, for example, that biological uptake (Anderson and Morel in Limnol Oceanogr 27:789–813, 1982), the toxicity (Sunda and Ferguson in Trace metals in seawater, Plenum Press, New York, 1983) as well as the solubility (Millero et al. in Mar Chem 50:21–39, 1995; Liu and Millero in Geochim Cosmochim Acta 63:3487–3497, 1999) are affected by the speciation. For example, Fe(II) and Mn(II) are biologically available for marine organisms, while Fe(III) and Mn(IV) are normally not available. The speciation of metals also affects the rates of oxidation (Millero in Geochim Cosmochim Acta 49:547–553, 1985, Res Trends Curr Top Sol Chem 1:141–169, 1994; Sharma and Millero in Geochim Cosmochim Acta 53:2269–2276, 1989; Vazquez et al. in Geophys Res Lett 16:1363–1366, 1989) and reduction (Res Trends Curr Top Sol Chem 1:141–169, 1994; Millero et al. in Mar Chem 36:71–83, 1991) of metals in natural waters. The ionic interactions of metals are controlled by interactions with inorganic (Cl−, OH−, CO3 2−, etc.) and organic ligands (e.g., Fulvic and Humic acids). The speciation of metals is also affected by the oxidation potential (Eh) and the pH in the solution. In this paper we have developed a Pitzer Model (Pitzer in J Phys Chem 77:268–277, 1973, Activity coefficients in electrolyte solutions, 2nd edn, CRC Press, Boca Raton, 1991) that can be used to determine the speciation of trace metals in seawater and other natural waters. It is based upon the Miami Pitzer Model (Millero and Pierrot in Aquatic Geochem 4:153–199, 1998) that has been shown to predict reliable activity coefficients for the major components of seawater. The computer code (Pierrot in Ph.D. Thesis, University of Miami, Miami, Florida, 2002) for these calculations is described in detail, in this paper. It has been used in an earlier paper (Millero and Pierrot in Chemistry of marine water and sediments, Springer, Berlin, 2002) and more recently used to examine the effect of pH on the speciation of metals in seawater (Millero et al. in Oceanography 22(4):72–85, 2009).