Determination of ultra-trace amounts of silver in water by differential pulse anodic stripping voltammetry using a new modified carbon paste electrode

A highly sensitive and selective new procedure for the determination of silver in aqueous media was developed using a modified carbon paste electrode (MCPE) by differential pulse anodic stripping voltammetry (DPASV). The modified electrode was based on the incorporation of 2-hydroxybenzaldehyde benzoylhydrazone (2-HBBH) in the carbon paste electrode. Silver ions were preconcentrated on the modified electrode at open-circuit by complexation with the ligand and reduced to zero valent at a potential of 0 V, and followed by the reoxidation of adsorbed ions onto the electrode by scanning the potential in a positive direction. The oxidation peak of Ag(I) was observed at 0.2 V (versus Ag/AgCl). The analysis of Ag(I) was carried out in a cell containing the sample solution (20 mL) buffered by 0.1 mol L-1 K2HPO4/NaOH at pH 5.5 in aqueous solution and nitric acid (pH 1) in real water samples. The optimum conditions for the analysis of silver include a reduction potential of 0 V and a pulse amplitude of 100 mV, among others. The optimum carbon paste composition was found to be 14.1% (w/w) 2-HBBH, 56.2% (w/w) graphite powder and 29.7% (w/w) paraffin oil. Differential pulse anodic stripping voltammetric response was used as the analytical signal. Under the selected conditions, the voltammetric signal was proportional to the Ag(I) concentration in the range of 0.001-100 mu g L-1 with favorable limits of detection and quantification of 1.1 ng L-1 and 3.7 ng L-1 after 3 min of accumulation time, respectively. By increasing the accumulation time to 10 min, detection and quantification limits can be further improved up to 0.1 ng L-1 and 0.34 ng L-1, respectively. In addition, the results showed a highly reproducible procedure showing a relative standard deviation of 1.5% for 12 replicate measurements. Many coexisting metal ions were investigated and very few interferences were found on the determination of Ag(I). The proposed method was validated using certified reference estuarine waters (SLEW-3) with a relative error of - 1.3% and applied to the determination of silver ions in three river water samples collected from Guadalquivir river (relative errors of +3.4%, +1.5% and -0.7%). Moreover, the method was successfully applied to the speciation analysis of total silver, free silver ions and silver nanoparticles in aqueous solutions. The results were in good agreement with those obtained by inductively coupled plasma mass spectrometry (ICP-MS). (C) 2016 Elsevier B.V. All rights reserved.