Towards a zero-blank, preconcentration-free voltammetric method for iron analysis at picomolar concentrations in unbuffered seawater

• Exploitation of pH rise after buffer removal in diffusion layer HMDE for Fe AdCSV.
• Oxygen reduction provides catalytic reagent and optimum pH for FeDHN method.
• Fe analysis preconcentration-free zero-blank in seawater at picomolar range.

A method with negligible blank values for the determination of total iron at the ultratrace level in seawater has been optimized and validated exploring for the first time the performance and limitations of Adsorptive Cathodic Stripping Voltammetry (AdCSV) in non-buffered solutions. The method is based on the CSV determination of the Fe-dihydroxynaphthalene (DHN) complex using atmospheric oxygen to catalytically enhance the signal via hydrogen peroxide formation at the electrode/solution interface. The accumulation of hydroxyl ions, the by-product of the hydrogen peroxide formation, increased the pH in the diffusion layer in the absence of buffer bringing it to 9, the optimum for the analytical performance of the method. Voltammograms in UV digested seawater showed no stability or reproducibility drawbacks. The negligible, lower than 5 pM, blank level, is due to the simplicity of the procedure requiring no sample manipulation and a maximum of three reagents only, necessarily the ligand DHN and a base only for those samples previously acidified to raise the pH to circumneutral values (here HCl and NH3 according to common trace metals protocols). These reagents do not require cleaning before use, further simplifying the overall procedure. Analysis of seawater previously acidified at pH ~1.5 with HCl and neutralized with ammonia showed interferences due to the buffering properties of the NH3/NH4Cl couple and the transient formation of a volatile electroactive interference that can be easily removed by simply allowing a set time before analysis. In general, the proposed method features several advantages, including high sample throughput, an excellent limit of detection at 12 pM, minimum sample handling (no preconcentration or change of matrix is required), cost effectiveness and mainly a negligible blank. The method was successfully validated using open ocean consensus samples (SAFe D2 and S).

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