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Determination of picomolar levels of iron in seawater using catalytic cathodic stripping voltammetry.

A new procedure for the direct determination of picomolar levels of iron in seawater is presented. Cathodic stripping voltammetry (CSV) is preceded by adsorptive accumulation of the iron(III)-2,3-dihydroxynaphthalene (DHN) complex from seawater, containing 20 microM DHN at pH 8.0, onto a static mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is catalytically enhanced by the presence of 20 mM bromate. Optimized conditions include a 60-s adsorption period at -0.1 V and a voltammetric scan using sampled dc modulation at 10 Hz. In these conditions, a detection limit of 13 pM iron in seawater was achieved which can be lowered further by extending the adsorption time to 300 s. The new catalytic CSV method is approximately 5 times more sensitive than existing CSV methods and was tested on samples from the Atlantic Ocean.