A new approach to study cadmium complexes with oxalic acid in soil solution

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI–MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH2) were observed. In order to verify the possible formation of complexes with OAH2, aqueous solutions of OAH2 with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI–MS, which follow the general formula [Cdn(X,Y)(2n+1)]−, where n is the number of cadmium atoms, X = Cl−, and Y = OAH−. Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions.