Effect of electrolyte composition on electrochemical oxidation: Active sulfate formation, benzotriazole degradation, and chlorinated by-products distribution

Electrochemical oxidation is an effective technique for treating persistent organic pollutants, which are hardly removed in conventional wastewater treatment plants. Sulfate and chloride salts commonly used and present in natural wastewater influence the electrochemical degradation process. In this study, the effect of electrolyte composition on the active sulfate species (SO₄^●⁻ and S₂O₈²⁻) formation, benzotriazole degradation-a model organic compound, and chlorinated by-products distribution have been investigated while using a boron-doped diamond (BDD) anode. Different Na₂SO₄:NaNO₃ and Na₂SO₄:NaCl ratios with constant conductivity of 10 mS/cm were used in the experiments and applied anode potential was kept constant at 4.3 V vs. Ag/AgCl. The electrogenerated SO₄^●⁻ and S₂O₈²⁻ formation were faster in 10:1 and 2:1 Na₂SO₄:NaNO₃ ratios than in the 1:0 ratio. The ^●OH-mediated SO₄^●⁻ production has prevailed in 10:1 and 2:1 ratios. However, ^●OH-mediated SO₄^●⁻ production has hindered the 1:0 ratio due to excess chemisorption of SO₄²⁻ on the BDD anode. Similarly, the faster benzotriazole degradation, mineralization, and lowest energy consumption were achieved in the 10:1 Na₂SO₄:NaNO₃ and Na₂SO₄:NaCl ratio. Besides, chlorinated organic by-product concentration (AOX) was lower in the 10:1 Na₂SO₄:NaCl ratio but increased with the increasing chloride ratio in the electrolyte. LC-MS analysis shows that several chlorinated organic transformation products were produced in 0:1 to 2:1 ratio, which was not found in the 10:1 Na₂SO₄:NaCl ratio. A comparatively higher amount of ClO₄⁻ was formed in the 10:1 ratio than in 2:1 to 0:1 ratio. This ClO₄⁻ formation train evidence the effective ^●OH generation in a sulfate-enriched condition because the ClO₄⁻ formation is positively correlated to ^●OH concentration. Overall results show that sulfate-enriched electrolyte compositions are beneficial for electrochemical oxidation of biorecalcitrant organic pollutants.