Chlorate induced false reduction in chemical oxygen demand (COD) based on standard dichromate method: Countermeasure...

Deliberate addition of mildly oxidative chlorate (ClO₃^-), so-called "chemical oxygen demand (COD) remover", into wastewater in China or electrochemical production of ClO₃^- from Cl^- induces the false COD reduction, which would bring about false appearance of effluents meeting the COD discharge standards. In this study, an easy sulfite-based reduction method was developed for the first time to remove ClO₃^- from the water samples before COD determination to eliminate this interference of ClO₃^-. In this reaction system, keeping the reaction temperature of sulfite reducing ClO₃^- at 60 ^°C was crucial for fast ClO₃^- removal rate, fixed molar [sulfite]_ini/[chlorate]_ini ratio value and the synchronous exhaustion of sulfite and ClO₃^-, which were of great significance for the real application of this improved COD determination method. The ClO₃^- interference on COD determination could be successfully eliminated after 20 min reduction of ClO₃^- by sulfite at pH_ini 4.0∼6.0 with the molar [sulfite]_ini/[chlorate]_ini ratio value in the range of 5∼6 when concentration of ClO₃^- was below 5 mM. Despite of the involvement of SO₄^·- in the sulfite reducing ClO₃^- system, the degradation of organic matters by SO₄^·- could be greatly impeded due to the lessened dissolved oxygen for SO₄^·- production at high reaction temperature and the scavenging of SO₄^·- by sulfite. In this reaction system, ClO₂, ClO₂^- and ClO^- were also generated and could be further reduced by sulfite stoichiometrically via oxygen transfer process with Cl^- as the final product. In general, this study pioneered an effective, fast and convenient method for COD determination of the ClO₃^--laden wastewaters and evaluating the real electrochemical wastewater treatment performance in terms of COD removal.