Effect of humic acid on the underpotential deposition-stripping voltammetry of copper in acetic acid soil extract solutions at mercaptoacetic acid-modified gold electrodes

Electrochemical measurements were undertaken for the investigation of the underpotential deposition-stripping process of copper at bare and modified gold electrodes in 0.11 M acetic acid, the first fraction of the European Union’s Bureau Communautaire de Références (BCR) sequential extraction procedure for fractionating metals within soils and sediments. Gold electrodes modified with mercaptoacetic acid showed higher sensitivity for the detection of copper than bare gold electrodes, both in the absence and in the presence of humic acid in acetic acid solutions, using the underpotential deposition-stripping voltammetry (UPD-SV) method. In the presence of 50 mg l^-1 of humic acid, the mercaptoacetic acid modified electrode proved to be 1.5 times more sensitive than the bare gold electrode. The mercaptoacetic acid monolayer formed on the gold surface provided efficient protection against the adsorption of humic acid onto the gold electrode surface. Variation of the humic acid concentration in the solution showed little effect on the copper stripping signal at the modified electrode. UPD-SV at the modified electrode was applied to the analysis of soil extract samples. Linear correlation of the electrochemical results with atomic spectroscopic results yielded the straight-line equation y ((mu)g l^-1) = 1.10x - 44 (ppb) (R=0.992, n=6), indicating good agreement between the two methods.