Investigations were performed in order to clarify the origin of the broad baseline observed during Hg(II) trace electrochemical detection on gold electrode in the presence of Cl- anions. The influence of Cl- concentration on the shape of the voltammograms was studied in the presence and in the absence of Bovine Serum Albumin (BSA) in order to bring out adsorption/desorption processes. On the basis of these experiments, and contrary to what has been proposed by several authors in the literature, it was proved that the broad baseline does not result from calomel (Hg2Cl2) formation but is rather related to an interaction between Cl- and polycrystalline Au electrode surface. The evolution of the shape of the baseline was also studied in the presence of other halide anions, namely F-, Br-, and I-. The latter two were found to induce a broad baseline similar to that recorded in the presence of Cl-. Finally, it was shown that BSA addition is not suitable for Hg(II) detection since it prevents Hg(0) deposition onto the electrode surface. (C) 2013 Elsevier B.V. All rights reserved.