Effects of fulvic acids on the electrochemical reactions and mass transfer properties of organic cation toluidine blue: Results of measurements by the method of rotating ring-disc electrode

This study examined effects of aquatic and soil natural organic matter (NOM) exemplified by standard Suwannee River fulvic acid (SRFA) and Pahokee Peat fulvic acid (PPFA), respectively, on the electrochemical (EC) reactivity and mass transfer properties of the cationic organic probe toluidine blue (TB) that forms complexes with NOM. EC measurements that were carried out using the method of rotating ring-disc electrode (RRDE) showed that for disc potentials below -0.4 V vs. the standard Ag/AgCl reference electrode, TB molecules undergo EC reduction accompanied by the formation of EC-active products that undergo oxidation at the ring electrode. EC reactions of TB in the range of potentials -0.2 to -0.4 V were determined to involve free TB⁺ cations and TB species adsorbed on the electrode surface. The EC reduction of TB species at the disc potentials < -0.4 V was controlled by the mass transfer of the free TB⁺ cations and TB/NOM complexes to the electrode surface. Formation of TB/NOM complexes caused the mass transfer-controlled TB currents to undergo a consistent decrease. The observed changes were correlated with the extent of TB/NOM complexation and decreases of the diffusion coefficients of TB/NOM complexes that have higher molecular weights (MW) than the free cations. Properties of the intermediates formed upon the reduction of TB⁺ cations were also affected by NOM. These results demonstrate that RRDE measurements of EC reactions of TB or possibly other EC active probes allow probing the complexation of EC-active organic species with NOM and mass transfer properties of NOM complexes and ultimately NOM itself.