Quartz crystal microbalance determination of trace metal ions in solution

This paper describes studies of a combined electrochemical/acoustic wave sensor for detection of metal ions in aqueous solutions. The sensor is based upon surface complexation of the metal ions at thiodisuccinic acid (TDS) functionalised self-assembled monolayer (SAM) modified electrodes on 10 MHz AT-cut quartz resonators, functioning as a quartz crystal microbalance (QCM). The SAM-modified electrodes were employed for the detection of Cd(II) ions in single and mixed metal ion solutions, with Pb(II) or Cu(II) as the interferants. Acoustic determination was based on the QCM frequency change associated with the binding to the surface-immobilised ligand of metal ions as a function of their concentration. Frequency response data were acquired under emersed and immersed conditions for ligand binding to the Au electrode and, subsequently, metal ion binding to the ligand. In the latter case, the data were interpreted according to a range of isotherms, of which the Temkin isotherm was found empirically best to describe the concentration dependence. The acoustic wave data yielded information on equilibrium binding stoichiometry and energetics. The extent of metal ion binding was also determined by coulometric assay (upon reduction to the zero-valent metal) after transfer to metal ion-free electrolyte solution. XPS studies of surface-bound metal-TDS ligand complexes confirmed the binding stoichiometry obtained from the electrochemical and acoustic wave responses, and provided information on the ligand–substrate binding and bound analyte oxidation state.