Factors influencing the inorganic speciation of trace metal cations in fresh waters

The effects of pH and major ion composition on the chemical speciation of the divalent cations of Co, Ni, Cu, Zn, Pb and Cd have been examined after consideration of the available thermodynamic database for solution complexes of these ions. Calculations were made for two model river waters representing the 1% and 99% extremes in composition of global river waters. The results show that inorganic speciation behaviour is of two characteristic types: (a) Cu, Zn and Co are dominated by bis-hydroxy- complexes at high pH and show the greatest reduction in the fraction of free aquo ion with increasing pH; (b) Pb, Ni and Cd are dominated by carbonato- complexes at high pH and show a more gradual decrease in the fraction of free aquo ion with increasing pH. For Cu, Pb and Ni significant fractions of the labile forms of these metal ions are present as inorganic complexes in the pH range of most natural waters, whereas for Zn, Co and Cd this is true only at moderately high pH (pH >7.5). Complexing with the major ions SO42- and Cl- is important only at low pH in river waters of high ionic strength.