Application of amalgam electrodes in studies of heavy metals under natural water conditions

The application of amalgam electrodes for measuring the degree of complexation of metal ions is described with respect to natural water conditions. The amalgam electrodes are compared with the corresponding capabilities of ion-selective electrodes. A special cell is described for preparing the amalgam and for filling a hanging amalgam drop electrode. Factors affecting the reproducibility of the standard potentials and slopes, the response time and detection limits are discussed. Complexation measurements are described with lead and zinc amalgam electrodes. Triethylenetetramine, carbonate and nitrolotriacetic acid are used as ligands, to test the ability of these electrodes to measure correctly8 the degree of complexation even at low total-metal. concentrations (down to ca. 10 −7 M) and at very low concentrations of free metal ion (10 −15 M). Results obtained with well-characterized fulvinc compound and an algal culture medium (AAP) are also reported. The observed results are in compl;ete accordance with theoretical predictions (based on Nernstian behaviour), evven at the lowest concentrations of tltal and free metal ion used. An important limitation is that any oxidant in the solution can interfere by oxidizing the amalgma. Solutions must be carefully degassed to eliminate oxygen. It is shown that the interfering actin of oxidants can be corrected for by means of equations which are theoretically sound, even when the nature of the oxidant is unknown, provided that its content is not too high. Compared to ion-selective electrodes, amalgam electrodes are more reproducible, inexpensive and readily prepared for various metal ions which cannot be measured with ion-selective electrodes.