Environmental Context. Metal bioavailability and toxicity are often related to free metal concentration rather than total metal concentration. Humic substances are chemically and physically heterogeneous complexants for metals in natural waters, and play an important role in trace metal transport, fate, and bioavailability. Metal bioavailability, which depends on chemical speciation of metals, is greatly influenced by the presence of other trace metals and major cations in natural waters. In this work, the effects of heterogeneity of humic substances, and of competition of trace metals on lead speciation in model solutions have been studied to gain a better understanding of these effects on complexation of trace metal lead and its bioavailability.

Abstract. Physicochemical heterogeneity of a well characterized humic acid (HA) in its complexation with a trace metal lead in model solutions was investigated using pseudo-polarography at a stationary mercury drop electrode, and the differential equilibrium function (DEF) of Pb(ii)–HA complexes was determined. The complexation of Pb(ii) by HA was determined by taking into account the dependence of the strength of the binding on the metal (Pb) loading. Also investigated were the effects of competition of the trace metals copper, nickel, and zinc on the DEF of Pb(ii)–HA complexes in model solutions. The results showed that these trace metals competed with trace metal lead for binding by HA even when present at the same concentrations as that of lead.