Determination of metal ions by ion chromatography with precolumn electrochemical preconcentration

The determination of heavy metals in concentrations less than 10^-6 mol/L by ion chromatography with conductivity detection requires a preconcentration step. Therefore, a special electrochemical equipment and method was developed for the on-line preconcentration of the divalent metals Ni, Co, Zn and Cd and their subsequent ion chromatographic determination. The loop of the injection valve of an ion chromatograph was replaced by an electrochemical flow-through-cell with a gold working electrode, a platinum auxiliary electrode and a silver/silver sulphate reference electrode. The preconcentration step consists of the deposition of the reduced metals on the electrode surface during a continuous pumping of the sample solution through the cell. After switching of the mobile phase through the cell, the analytes are injected after their reoxidation directly into the mobile phase. A new preconcentration step is simultaneously possible during the actual chromatographic run. An effective separation of the analytes from the matrix is also possible with the proposed system. A maximum of metal ion accumulation was obtained after 120 min in the galvanostatic mode on a gold tube electrode. The detection limits for Co(II), Ni(II), Zn(II) and Cd(II) were improved by a factor of 7.7, 10.4, 11.2, 14.0, respectively, and were in the 0.1 mol/L concentration range with a RSD of 2–6%. The accumulation of metal ions was disturbed in the presence of Cr(III).