Determination of chromium in estuarine waters by catalytic cathodic stripping voltammetry using a vibrating silver amalgam microwire electrode

Chromium (Cr-VI) in water can be determined by adsorptive catalytic cathodic stripping voltammetry in the presence of diethylenetriaminepentaacetic acid (DTPA) and nitrate on the hanging mercury drop electrode (HMDE). Predominately Cr-VI is detected and the water is UV-digested to convert all Cr to Cr-VI prior to analysis. We develop here an alternative to the HMDE by using a silver amalgam electrode based on a vibrating microwire. The microwire electrodes were 12.5 mu m in diameter and electrochemically coated with mercury, and were stable for a week. Conditions were re-optimised, and we used a DTPA concentration of 5 mM, 30 mM acetate pH buffer (pH 5.5 in seawater and pH 5.8 in pure water), and 1.5 M nitrate solution. The microwire was reactivated prior to each scan by applying a negative potential (-3 V) for 2 s which removed all deposited Cr. The detection limit for chromium in pH buffer was found to be 0.2 nM Cr-VI and in seawater 0.3 nM Cr-VI at a deposition time of 30 s. The response increased linearly with the concentration of Cr-VI up to 60 nM Cr-VI in seawater. The limit of detection is less good than using the HMDE, but the linear range is good and the microwire electrode could form the basis of apparatus for flow-analysis. The method was successfully tested on water samples from the estuary of the river Mersey (Liverpool Bay) giving chromium concentrations between 1.48 nM and 2.29 nM. (C) 2012 Elsevier B.V. All rights reserved.