Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (FeR) in the absence and presence of 2 μM Dp, FeR being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H2O2 and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for FeR. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for FeR, iron(III) and iron(II), respectively, using a 60 s deposition time. The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of FeR ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.