Extracellular electron transfer modes and rate-limiting steps in denitrifying biocathodes

Denitrifying bioelectrochemical system provided an alternative technology for nitrogen removal, even power recovery from wastewater, and its nitrogen removal performance and intermediate accumulation were affected by the extracellular electron transfer modes and rate-limiting steps in denitrifying biocathodes. In the current study, the extracellular electron transfer modes and rate-limiting steps for nitrate reduction and nitrite reduction of denitrifying biocathode were investigated through cyclic voltammetry. When the cathode potential swept from 0.003 to − 0.897 V (vs. Ag/AgCl), denitrifiers were indispensable for electrochemical denitrification. Three peak potentials were found in the cyclic voltammogram of denitrifying biocathode, where E₁ (− 0.471 to − 0.465 V) and E₂ (− 0.412 to − 0.428 V) represented respectively nitrate reduction and nitrite oxidation while E₃ (− 0.822 to − 0.826 V) represented nitrite reduction. Nitrate reduction involved the direct electron transfer mode while nitrite reduction involved the mediated electron transfer mode. Intracellular catalytic reaction was the rate-limiting step for nitrate reduction, independent on the electrochemical activity of denitrifying biocathode and the nitrate supply. The nitrate supply posed an effect on the rate-limiting step for nitrite reduction. The mediator transfer was the rate-limiting step for nitrite reduction in the absence of nitrate. But both mediator transfer and intracellular catalytic reaction became the rate-limiting steps for nitrite reduction in the presence of sufficient nitrate.