Manganese chemistry in rivers and streams

Abstract

The speciation of Mn has been determined in 15 rivers and streams representing a wide variety of physico-chemical conditions. Using the technique of anodic stripping voltammetry ( asv), specific for reduced Mn(II) species, it is found that a major part of the <0.015 μm Mn size fraction is present in a reduced Mn(II), asv-labile, form. In some waters there is also a significant asv inactive Mn fraction considered to be present as a ‘small colloidal’ species. The soluble (<0.015 μm) Mn fraction represents 15–95% of total Mn and does not appear to be dependent upon pH, alkalinity, specific conductance or humic substance concentration in the water. It is argued that under the dynamic, short residence time, conditions that apply in most rivers the paniculate and soluble Mn fractions are decoupled, their respective presence being dependent principally upon the catchment hydrogeological conditions. This contrasts with a previously held view that the paniculate phase is coupled to the dissolved phase by the pH dependent oxidation of dissolved Mn(II) to highly insoluble Mn(IV) species (Graham et al., 1976). Consideration of manganese speciation in waters which were incubated for five months showed that pH becomes the controlling factor when equilibrium is approached.